Hongzhang Chen - Lignocellulose Biorefinery Engineering - Principles and Applications-Woodhead Publishing (2015)

Lignocellulose Biorefinery Engineering
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Advances in biorefineries
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Woodhead Publishing Series in Energy:
Number 74
Lignocellulose Biorefinery
Engineering
Principles and Applications
Hongzhang Chen
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74 Lignocellulose biorefinery engineering: Principles and applications
Hongzhang Chen
Preface
The slow decline of fossil resources and increasing deterioration of the environment
have prompted people to rethink profoundly the impacts on the earth of the thought-
less use of nonrenewable resources and to look attentively for sustainable resources
and energy. Lignocellulose is a proper resource to displace fossil resources for energy
and useful chemical production owing to its renewable character and abundance in
nature. In practice, lignocellulose, however, shows heterogeneity in both structure
and composition, which makes it economically infeasible to produce a single product
using lignocellulose as feedstock. Therefore, the concept of biorefining is proposed to
replace petroleum refining for the full and integrated utilization of lignocellulosic
resources. Based on the heterogeneity of lignocellulosic feedstock and the multiprod-
ucts integration concept, this book systematically elaborates the basic principles and
applications of lignocellulose biorefinery engineering.
Starting with the porous structure of lignocellulosic feedstock, this book introduces
the basic principles of lignocellulose biorefinery engineering by the transfer theory of
porous media, which is critical for solving the key issues in lignocellulose biorefinery
engineering. The book elucidates effective methods for the fractionation and
conversion of the lignocellulose feedstock, which take into account its complicated
composition. The aim is the integrated utilization of lignocellulose following the
guiding principles of cleaner production and a circular economy. In addition, several
models of integrated industrial biorefinery chains are summarized in this book to
highlight the advantages of integrated utilization. Consequently, this book provides
a basic academic introduction to the lignocellulose biorefinery and some instructive
references for readers about the related area of lignocellulosic resources utilization
and industrial development.
This book is a monograph that systematically discusses the basic principles of
lignocellulose biorefining and its application. First, Chapter 1 introduces the signifi-
cance and development of lignocellulose biorefining. Chapter 2 elaborates the theo-
retical basis of lignocellulose biorefinery engineering, including the essence of the
lignocellulose porous medium and lignocellulose recalcitrance. Chapters 3, 4, 5, 6,
and 7, respectively, introduce raw materials engineering, conversion engineering,
products engineering, process engineering, and integrated industrial models of ligno-
cellulose biorefinery modes in detail. Finally, Chapter 8 reviews several future trends
of lignocellulose biorefinery engineering.
My research is financially supported by the National Basic Research Program of
China (973 Project, No. 2011CB707401), and the National High Technology
Research and Development Program (863 Program, 2012AA021302). In addition,
the participation of my PhD and Masters students were essential preconditions for
xii Preface
publishing this book. In particular, Dr Guanhua Wang, Master Lanzhi Qin, Master
Meixue Shao, Dr Ning Wang, Dr Junying Zhao, Dr Zhihua Liu, Dr Zhimin Zhao,
Dr Wenjie Sui, Dr Menglei Xia, Dr Litong Ma, and Dr Guanhua Li participated in
writing some chapters. This book cites many references from our predecessors and
colleagues. I wish to express my sincere thanks to all of them.
Some errors may exist in this book. Please point out the mistakes and give direc-
tions to me whenever you see any weaknesses or shortages. I sincerely hope to receive
correction and guidance letters from readers.
Chen Hongzhang
Institute of Process Engineering
Chinese Academy of Sciences
Beijing, China
Lignocellulose biorefinery
engineering: an overview 1
1.1 Resources, energy, and environment
1.1.1 Definition and classification of resources
Natural resources are the material elements needed for human survival and develop-
ment. They are natural and self-existing, and include mineral resources, water
resources, land resources, and biological resources. Resources can be categorized
according to their renewability into renewable resources and nonrenewable resources
(Figure 1.1). Renewable resources can be regenerated by human activity, such as agri-
culture. With the correct cultivations, soil fertility can be maintained, and this con-
stantly provides agricultural products for mankind. Nonrenewable resources, also
known as exhaustible resources, are those whose reserves and volume can be mea-
sured, such as mineral resources. Renewable resources can be further divided into
recyclable resources (such as solar, air, rain, wind, hydroenergy and tidal energy,
etc.) and biological resources (including a variety of plants, animals, microorganisms,
and their surroundings, consisting of ecosystems). Of course, the distinction between
renewable resources and nonrenewable resources is relative. For example, oil, coal,
and natural gas are nonrenewable resources, but they are the products of ancient ani-
mals and plants following the long-term effects of physical, chemical, and geological
changes in the strata of the earth. Therefore, renewable resources and nonrenewable
resources can be transformed into each other (Zhou, 2013).
According to the status of resources recycling and its contributions to the various
sectors of the national economy, the famous economist Tietenberg divided resources
into five categories, which had great practical value. The main types are as follows.
First, exhaustible but nonrecyclable resources mainly refer to oil, coal, natural gas,
uranium, and other energy resources. Second, recyclable resources mainly refer to
mining, paper, glass, and so on. Third are available but exhaustible resources, such
as water and air resources. Fourth, renewable resources mainly refer to agricultural
natural resources, including land and fishery resources. Fifth are stored and renewable
resources, such as forest resources and crop resources.
1.1.2 Resource issues and resource crises

1.1.2.1 Resource issues
Resource issues are mainly due to the overexploitation, irrational development, and
excessive utilization of resources combined with population growth and economic
development, which results in a range of issues affecting the resource quality. Just
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Copyright © 2015 Elsevier Ltd. All rights reserved.
2 Lignocellulose Biorefinery Engineering
Recyclable resources (such as metal deposits)

Nonrenewable
resources
Denatured or destroyed resources after use (such as fossil fuels)
Natural Geophysical processes (such as wind energy,

resources Direct solar
tidal energy, hydro-energy)
Long-term (such as wood)

Renewable Photosynthesis
Indirect solar
resources process
Short-term (such as crop)
Geothermal energy
Figure 1.1 Natural resources classification according to their renewability.
as population issues and environmental issues are related to development, so too are
resource issues. Population growth, a series of worldwide shortages of resources, envi-
ronmental degradation, and ecological crises have become a direct threat to human
survival. Specific resource issues include excessive exploitation, excessive waste,
and continuous consumption of resources.
1.1.2.2 Resource crises

A resource crisis occurs when the effects of resource depletion and damage accu-
mulate to such an extent that the functionality of the resource system has been dam-
aged and it has become difficult to maintain the needs of human economic activity
in part or as a whole; perhaps even directly threatening human survival and devel-
opment. It includes the energy crisis, the minerals crisis, the water crisis, the food
crisis, and the ecological crisis. Therefore, it can be said that the resource crisis is
the emerging scarcity of mineral resources, fresh water, arable land, forests, wild-
life, and other natural resources that coincides with population growth and eco-
nomic development.
The energy crisis is the most prominent resource crisis. Energy is the strategic
resource with the largest international market, and it is also the power source of eco-
nomic development. The energy crisis is the result of energy supply shortages or price
increases, usually involving a shortage of oil, coal, natural gas, or other natural
resources. Population growth, economic development, and energy waste have resulted
in a long-term tightening of the energy supply.
Global water resources are limited, and available freshwater resources are more
limited (equivalent to less than 1% of the world’s total water). Coupled with increas-
ingly serious water pollution and the reduced amount of available water resources, the
water shortage is getting worse. Internationally, it is predicted that the water crisis will
be the next big resource crisis, and will also be the most destructive resource crisis.
The food crisis has become one of the major resource crises on the planet. In most
decades, global grain consumption has been higher than its production. So far this
decade, the world’s grain reserves have been depleted, and food trade in the
An overview 3
international market is also declining. Worse still, the population is growing and the
extent and quality of arable land are declining.
The ecological crisis is due to excessive human activities that damage the structure
and function of the earth’s ecological system, which is not conducive to human sur-
vival and development. The crisis includes two aspects: the damage to the ecosystem’s
structure and function, which cannot be restored, and collapse of life-support systems,
referring to the species crisis, the habitat crisis, the forest crisis, and wildlife resources
crisis. Environmental pollution, ecological destruction, and declining biodiversity
lead to a shortage of wildlife resources, resulting in the species crisis. With the
massive loss of forest resources, soil erosion, and grassland degradation, desertifi-
cation also ensues. Once the ecological crisis formed, it was difficult to recover in
the longer term.
1.2 Resource recycling and waste reuse

1.2.1 Resource recycling
The circular economy is a new, advanced economic form that combines economics,
technology, and social integration systems engineering. Its essence is an ecological
economy, and it advocates a model of economic development and environmental har-
mony. It needs to meet the requirement of reducing the impact of economic activities
on the natural environment to the smallest extent possible. The development of a cir-
cular economy is not only an important way to achieve sustainable development, but
also the fundamental means of environmental protection and pollution abatement. The
operating mechanism of a circular economy can be categorized into five basic points,
four cycles, and three principles, as described below.
l
The five basic points are clean production, industrial ecology, sustainable agriculture, green
consumption, and waste disposal.
l
The four cycles are the internal cycle, the cycle between production, the whole society cycle,
and the energy and material cycles.
l
The three principles are the principles of reduction, reuse, and recycling.
Recycling of resources is the comprehensive development of natural resources, full utili-

zation of energy and raw material, and recycling and reuse of waste. All aspects of resource
functions should be exploited by repeated use of each unit process. Recycling of resources is
one of the most important means of achieving recycling and an ecological economy.
1.2.2 Waste reuse

Waste reuse involves the recycling of a lot of the valuable material and energy that
would otherwise be lost in the normal waste disposal and emissions that occur during
production processes. The discharge of waste is greatly reduced through recycling.
Meanwhile, limited resources can be fully utilized, which meets the requirements
of sustainable development.
1.2.3 Biomass recycling

Biomass recycling is recycling supported by renewable biomass resources. Figure 1.2
shows the patterns of energy in the farming cycle. The energy recycling model takes
the produced biogas as fuel, saving the use of traditional fuels. Residue and biogas
slurry can be used as chemical fertilizer, which reduces fertilizer use and improves
soil fertility.
Biomass has attracted worldwide attention because of its versatility in conversion
and recycling. First, solar, wind, hydroenergy, and other renewable energy sources can
provide energy, but they cannot create a material product, unlike coal and oil, which
form a huge coal and petroleum industry and produce thousands of chemical products.
Biomass is not only a renewable energy source, but can also be used to produce thou-
sands of chemical products. The main component of biomass is carbohydrate, which
does not affect the environment during production processes. Second, biomass
includes agricultural and forestry waste and environmental pollutants, such as crop
residues, animal manure, forestry waste, and organic waste. The energy preserved
in plant and material resources will be comprehensively developed and recycled.
Third, and perhaps more important, biomass is a part of agricultural production, which
is helpful in developing the rural economy and farmers’ income. Therefore, the ver-
satile biomass industry with its recycling of resources is close to the three themes of
resources, energy, and the environment, which play an overall and substantive role in
the economy. Biomass recycling is an efficient solution to solve energy supply prob-
lems and alleviate environmental pollution.
1.2.4 Eco-industrial systems and eco-industrial parks

The development of social, environmental, and ecological issues is increasingly
becoming the focus of attention, and an ecological perspective is gradually penetrating
all industries. In nature, material and energy are utilized by organisms, and its waste
should be the nutrients for other organisms, forming a continuous material flow, which
results in an ecological balance. According to this theory, people build and develop
eco-industry. In industrial production, humans simulate ecological principles and
design a production process where waste generated in the production process becomes
the raw material of the next process. In this way, multilevel classification and utiliza-
tion of raw materials and energy are achieved in the production process, forming a
Novel fuel
Biogas
Manure Biogas
Livestock production
Agricultural waste
Cultivation of
grain, vegetables,
Fermented liquid
fruit trees
and residue
Feed
Figure 1.2 Energy recycling model for the agricultural industry.

An overview 5
continuous material flow and energy flow. People seek to get the best use of resources,
fully exploit the potential production of resources, and hence promote a virtuous
cycle. Meanwhile, this can be useful for the society by producing more goods, and
it can achieve the simultaneous development of economic and ecological benefits.
This industrial production system is called eco-industry (Chen, 2008).
The eco-industry concept is based on clean industrial production, in which the pro-
duction process design is according to the ideas of a recycling economy. It promotes
the recycling of raw materials and energy and achieves the dual benefits of economic
growth and environmental protection. An eco-industrial park is an important way to
achieve eco-industry, whereby the natural ecosystem is simulated and a symbiotic
network is formed through proper industrial park design in terms of logistics and
energy. The eco-industrial park is a new industrial park design based on the concept
of a circular economy, industrial ecology principles, and clean production. It connects
different factories and businesses by logistics or energy transfer, forming enterprises
in a symbiotic combination to share resources and exchange by-products. As a result, a
“producer–consumer–decomposer” material circulation method should be estab-
lished, of which the waste or by-products of a factory become the raw materials or
energy of another factory (Chen, 2008).
The biomass industry conforms to the general definition of ecological engineer-
ing, building a stratified multistage material production process or even forming a
network from the determination of land cultivation, selection and production of plant
materials, screening and breeding of microorganisms, enzymes optimization, design
and optimization of the production process, to the production of the desired products,
by-products, waste recycling, as well as logistics and transport. It follows the prin-
ciples of species symbiosis, recycling, and coordination of structure and function,
which promotes healthy circulation and fully exploits production potential to prevent
environment pollution and achieve economies of simultaneous development.
1.3 Lignocellulosic resources

1.3.1 Lignocellulose definition and classification
Biomass includes organisms using air, water, and land through photosynthesis; in
other words, every piece of organic matter that can grow is biomass. In the photosyn-
thesis process, carbon dioxide in air and water is taken as a raw material, solar energy
is the energy source, and the resultant product is stored as biomass. Meanwhile, oxy-
gen is released as a by-product. Synthesis of biomass is from carbon dioxide, and
carbon dioxide will be generated after the biomass utilization. Therefore, compared
with other fossil resources, biomass resources have the advantage of zero carbon diox-
ide emissions. Because biomass resources have these advantages, the development
and utilization of biomass have attracted growing attention.
Broadly, biomass includes all plants, microorganisms, animals, and their waste
products. Representative biomass includes crops, crop waste, wood, wood waste,
and animal dung. From a narrower perspective, biomass mainly refers to stalks, trees,
and other wood cellulose, agro-industrial waste, forestry waste, and other substances
created during agricultural and forestry production processes, except for food and
fruit. Lignocellulosic biomass is mainly composed of cellulose, hemicellulose, lignin,
and a small amount of other substances. The wide variety of lignocellulosic resources
also have multiple ways of conversion, various end-products, and wide application
areas; however, at present the overall utilization rate is low, production costs are high,
and industrialization processes are slow.
Lignocellulosic resources are classified as either forestry resources or agricultural
resources. According to the 7th National Forest Inventory results completed in 2010,
China’s forest area is 1.95 million km2, and the total carbon reserves of forest vege-
tation are 7.811 billion tons. Forestry resources are produced mainly in reforestation,
forest protection, forest cutting, and other processes. Agricultural resources include
agricultural crops and agricultural wastes (such as crop straw and by-products and
waste from agricultural activities). Straw refers to inedible stalk residues, leaves,
and other by-products after the harvest of rice, wheat, corn, and other crops in the
process of agricultural production. Lignocellulosic resources include various species,
are widely distributed, and are thought to total a theoretical resource of about 820 mil-
lion tons (dry weight). Agricultural and forestry renewable lignocellulose has a short
cycle, and is easily biodegradable and environmentally friendly. Therefore, the use of
agricultural and forestry lignocellulosic resources to supplement and gradually
replace nonrenewable resources should be vigorously developed by using modern
science and technology; this is an effective way to deal with the crises of resources
and energy and is consistent with the requirements of environmental protection and
sustainable development. Based on the ideology of the biorefinery, conversion of agri-
cultural and forestry lignocellulose into fuels, chemicals, and materials has become
a hot topic.
1.3.2 Characteristics of lignocellulosic resources

Lignocellulose is formed directly from plant photosynthesis, and mainly contains cel-
lulose, hemicellulose, and lignin. These three components form the main composition
of the plant cell wall. Lignocellulosic material has the following characteristics:
(1) Renewability. As long as solar radiation is present, photosynthesis of green plants will not
stop; hence, lignocellulosic resources will never dry up. Therefore, lignocelluloses are
inexhaustible.
(2) Richness. It is estimated that the amount of lignocellulose produced by the photosynthesis
of plants on the earth is approximately 2 1011 tons per year.
(3) Alternative. Lignocellulose energy is a carbon resource that is an alternative to fossil fuels
via conversion into liquid and gaseous fuels and other chemicals and products. Therefore,
this reduces the dependence on fossil resources.
(4) Cleaning performance. Lignocellulosic resources can reduce emissions of SO2, CO2, and
other pollutants by replacing fossil fuels, and hence improve environmental quality. There
is almost no SO2 produced in the course of lignocellulose biorefining. The CO2 released is
approximately equivalent to the amount of CO2 absorbed by photosynthesis, and the CO2
emissions from the application of lignocellulose processing may be considered to be zero.
An overview 7
(5) Degradation. Lignocellulose derived from nature can be degraded by microbes and, there-
fore, it will not create solid waste and pollute the environment.
(6) Lignocellulose contains three kinds of elements – carbon, hydrogen, and oxygen – and is an
organic polymer material. It has the general characteristics of an organic polymer, such as
flammability, molecular weight, and molecular weight distribution inhomogeneity. Mean-
while, it can be associated with the functional group of polymer chemistry and has a dif-
ferent state of aggregation structure.
(7) Lignocellulosic biomass can react chemically with functional groups related to the poly-
mer, which is an important basis for modifying lignocellulose. According to the lignocel-
lulose functional group, the right chemical reactions can be designed to achieve modified
lignocellulose. For example, based on the esterification of cellulose hydroxyl groups,
various modified celluloses – including nitrocellulose, cellulose acetate, and cellulose
sulfonate ester – can be prepared.
(8) The impact of moisture on the lignocellulose performance is obvious. The effect of water on
lignocellulose is more significant than most of the synthetic polymer materials, because the
lignocelluloses have rich hydroxyl, amino, carboxyl, and hydrophilic groups. These hydro-
philic groups are connected by a hydrogen bond, which results in obvious moisture absorp-
tion effects in lignocellulose. From a macro aspect, it exhibits expansion after moisture
absorption and shrinkage after drying, accompanied by property changes.
1.3.3 Utilization history of lignocellulosic resources

In ancient times, lignocellulosic materials were a most important resource due to the
relative scarcity of other resources. Just as the ancients picked up a stick to drive the
beast, and accessed fire by rubbing sticks, lignocellulose was both a material and an
energy resource for them. With advances in production technology, the use of ligno-
cellulosic resources gradually expanded. In addition to being used in energy areas, it
also had mechanical uses, architectural uses, and applications in the paper and textile
fields. Nonfood lignocellulosic material resources, which were not abandoned by the
ancients, were well developed and were applied based on their characteristics. It also
reflects the “God without waste” concept of Zhu Xi in China in the twelfth century.
The utilization of lignocellulosic resources was introduced and developed in the fields
of energy and materials as discussed below.
1.3.3.1 History of lignocellulose utilization for energy

Energy is a driving force of social development and economic growth, and it is the
basis for human survival and development. In a real sense, the history of energy use
begins with the first use of fire by humans. The main source of energy in ancient
society includes biomass, as well as fossil energy, and so on. The use of a variety of
energy sources provided a fundamental guarantee for the continued development of
ancient society. Lignocellulose was the earliest and most widespread energy
resource used by our ancient ancestors due to its availability, renewability, and ease
of use. It also played an important role in the production of ancient society. The
ancient Chinese developed very rich and diverse biomass energy usage, which con-
stituted a complete biomass energy system, including woody plants, herbs, charcoal,
bio-oils, waxes, wine, and so on. A great wealth of knowledge and experience was
accumulated based on the characteristics of different lignocellulosic sources and
their use. People can reasonably choose different types of energy for different pur-
poses to achieve the desired results. The main means of energy utilization was the
original and simple form of direct combustion.
Since the emergence of the industrial society, traditional lignocellulosic fuels have
not been able to meet the needs of energy, and the main source of energy for life and
production of human society was coal in the nineteenth century and oil and gas in the
twentieth century, supporting a brilliant industrial civilization. But this will not last
long; these nonrenewable fossil energy resources are becoming exhausted after
200 years of mining and consumption, and the heavy pressures on the environment
have caused great concerns within the international community. Since the 1990s,
“Agenda 2l” and the “Kyoto Protocol” have been published, and “sustainable devel-
opment” has become a byword of the times. When people focus their attention on
renewable, clean energy, biomass energy receives attention as a renewable energy.
Of course, it is not simply burned, but will be used based on efficient, modern tech-
nology. In the 1930s, the United States began to develop a surplus of agricultural prod-
ucts, such as corn starch, soybean for printing inks, and other industrial products. The
oil crisis of the 1970s aroused the study of biofuels as a replacement for oil. The
United States and Brazil used corn and sugarcane to produce fuel ethanol and Europe
took rapeseed as a raw material to produce biodiesel and used forestry waste to pro-
duce methane, which opened a new alternative energy window for the ancient ligno-
cellulose industry with a vibrant outlook.
1.3.3.2 History of lignocellulose utilization for materials

Lignocellulose is plentiful, which is why it is a major resource in the materials field. It
is mainly used in two ways. One is its overall direct utilization as a raw material, such
as in machinery materials and building materials, and the other is the use of isolated
fibers, such as in paper and textiles. Lignocellulosic material utilization in these main
areas is introduced below.
Machinery includes the tools and devices that help people reduce the difficulty of
their work or increase their labor strength. It is also the basis of the human transfor-
mation of nature. Material is the basic element of machinery. The strength, hardness,
flexibility, and processing conditions of the material obviously affect machinery
manufacturing. In the long course of human history, the earliest era is the stone tools
era. That is to say that the earliest raw material was stone. However, in this period,
humans also used wood tools. For example, a stick could be used as a hunting and
self-defense weapon, but it could also be used to knock fruit off a tree. From the
Stone Age therefore, humans began to use wood as a tool material.
Wood was once widely used for building in China. Whether it is magnificent pal-
aces or ordinary houses, wooden architecture is in an overwhelmingly dominant posi-
tion in China, which is not the same in the West. Westerners used brick to build their
homes and expected the houses to last forever. However, this does not agree with
oriental philosophy. In Chinese philosophy, timber is an endless and eternal symbol
An overview 9
of reincarnation, so the wooden structure of the building system lasted seven thousand
years. The main advantages of wooden architecture include:
(1) Accessibility; easy processing.

(2) Adaptability; flexible interior space. A wooden building has load-bearing columns while
walls are not load bearing. Beams, purlins, and other components form the frame to support
the roof and the floor is easy to adapt to different climatic conditions.
(3) Good seismic performance. The composition of the wood frame uses a combination tenon.
The flexible wood itself combined with the tenon node has a degree of activity, and the
entire wooden frame has great potential in terms of reducing seismic force.
(4) Faster construction. Wood processing is faster than stone processing.
(5) Easy to repair; relocation. Tenon nodes can be removed and the replacement of certain com-
ponents or the demolition of the whole house is relatively easy.
The raw material of paper is plant fiber. In the handmade paper era, hemp, woody bast,
bamboo, rice, and wheat straw were the main raw materials for papermaking. Paper-
making raw materials can be divided into two categories. The first category is the bast
fibers, present in the phloem of plants. These can be further divided into herbaceous and
woody fibers. Herbaceous fiber includes hemp, while woody fiber comes from peren-
nials, such as mulberry and rattan. The second category is stalk fibers and includes
mostly monocots. These can be further divided into annual and perennial plants.
Annuals include rice and wheat, while perennials include a variety of bamboo. The fiber
aspect ratio is different in different materials, which accounts for the different quality of
papers. In general, long fibers are better than short fibers for paper, while the slender
fibers are better than the stubby fibers. In the beating process, the fibers are broken,
but there is still enough length of slender fiber. When paper is organized, it has high
tensile strength. Slender fibers have a large surface area and a good interlacing effect.
In addition to the use of cellulose obtained from lignocellulosic resources in the
paper industry, it also has major applications in textiles. In fact, the history of cellulose
as a textile raw material is longer than that of the paper. Furthermore, the initial paper-
making raw materials, such as rags and fishing nets, were from recycled textile
materials.
With the emergence of the steam engine, which used coal combustion as its power
source, the age of using lignocellulose combustion as a power source ended. Due to
large-scale mining and the application of oil resources, utilization of lignocellulosic
materials was gradually reducing, especially in the textile industry. Synthetic fibers
replaced the traditional cotton yarn. The traditional uses of lignocellulose were
replaced by other resources and lignocellulosic resources were called waste in a con-
siderable number of areas due to uncertainties in how to use it.
The ancients only used lignocellulose for combustion or building material. A later
application was to isolate the high purity fibers for textiles or paper. The application of
lignocellulose was not related to its essential chemical composition. Today, it is
already known that lignocellulose includes cellulose, hemicellulose, and lignin, and
cellulose and hemicellulose are polymerized from monosaccharides, which can be
transformed into more readily available sugars under certain conditions. Lignin is
an aromatic polymer that can be converted to phenolic compounds. Therefore, the
utilization model of lignocellulose is not just the so-called first processing; it may also
be converted to materials or chemicals that can be comparable to those from petroleum
resources. The “initial processing” utilization model of lignocellulose is still the main-
stream in some fields, such as furniture material, cotton, incineration power genera-
tion, and others. However, for this complex raw material, in order to meet the
requirements of raw materials for bio-based products, relatively pure chemicals
should be obtained by physicochemical or biological transformation, which can
replace petrochemical resources.
1.3.4 Current situation of lignocellulose utilization

Currently, the gradual depletion of fossil resources creates a serious resource crisis for
the development of the chemical industry (Himmel et al., 2007; Chen and Liu, 2014).
Meanwhile, nonbiodegradable petrochemical products seriously pollute the environ-
ment. Due to the dual pressures of resource depletion and environmental degradation,
there is an urgent need to find renewable resources to replace fossil resources.
Lignocellulose is a renewable resource of organic substances, including agricultural
products, agricultural waste, wood waste, and animal waste, and so forth. Therefore,
bio-based products based on lignocellulosic resources have become a research hotspot.
Bio-based products take lignocellulose as a raw material and convert it into various
products by using physical, chemical, and biological conversion technologies. Bio-
based products include bio-based chemicals (such as furfural, levulinic acid, xylose,
xylitol, and oxalic acid, etc.), bio-based energy (such as fuel ethanol, bio-butanol alco-
hols, biogas, and biodiesel, etc.), and bio-based materials (such as plywood, lignin-
modified phenolic resin adhesive, lignin-modified phenolic resin foam insulation
board, and polyurethane foam, etc.).
Lignocellulosic biomass feedstock has a supramolecular structure from the inter-
weaving of cellulose, hemicellulose, lignin, and multicomponent material; variations
in this supramolecular structure determine the various lignocellulose-based products
that can be produced: i.e., bio-based energy, bio-based materials, and bio-based che-
micals (Figure 1.3).
Due to the depletion of coal, oil, and other nonrenewable resources, the extensive
use of fossil fuels, and the greenhouse effect caused by environmental pollution, bio-
based products are expected to replace petrochemical products, and their production is
now at the forefront of the world’s science and technology research.
1.4 Lignocellulose biorefinery engineering

1.4.1 Necessity for lignocellulose biorefining
Ever since fire was used by the earliest humans, lignocellulose has been involved in
the direct development and utilization of energy. Those ancient times opened the door
to the evolution of civilization. Early utilization of lignocellulose mainly created heat
by burning, and the heat was used for cooking and heating. Use patterns of traditional
An overview 11
Overall
utilization Artificial board
Lignin modified phenolic resin adhesive, lignin

Bio-based Lignin based modified phenolic resin foam insulation board,
materials material dye dispersants, concrete water reducing agent,
ceramic adhesive, etc.
Fertilizer Cellulose based Paper, cardboard, viscose fiber, carboxymethyl

material cellulose acetate, cellulose nitrate,...
Coumaric acid, ferulic acid, vanillin,

Feed Lignin platform vanillic acid, phenol, etc.
Agricultural straws
Industrial raw Bio-based Cellulose Glucose fermentation products, oxalic

materials chemicals platform acid, levulinic acid, sorbitol, etc.
Hemicellulose fermentation products,

Hemicellulose
Fuel xylose and arabinose, xylitol, mannitol,
platform
furfural, etc.
Mushroom Pyrolyzation Bio-oil

residue
Vaporization Bio-gas
Bio-based
fuels
Hydrogenolysis Lignin hydrogen, fuel oil
Fermentation Methane, bioethanol, biobutanol
Figure 1.3 Applications of agricultural straw lignocellulose.
lignocellulose were inefficient and uneconomical, but it is undeniable that lignocel-

lulose plays an irreplaceable role in the long history of human civilization. In fact, the
development and utilization of lignocellulose is ongoing, and lignocellulose is still
one of the most widely used energy forms in the world. Since the 1990s, in order
to promote agricultural development, alleviate energy insecurity, decrease climate
change, and protect the environment, more and more countries have developed spe-
cific policies of lignocellulose energy industry development. Currently, the develop-
ment of the modern lignocellulose energy industry is very rapid. Biogas can be
commercially developed, and lignocellulose power generation and lignocellulose
solid fuel is also beginning large-scale production. Lignocellulose gasification and
bioliquid fuel are on the rise. Diverse utilization patterns of lignocellulose energy
are emerging that will play a great role in the progress of society. The lignocellulose
industry has gradually become a strategic emerging industry (Han, 2013).
It is important for a successful modern petrochemical industry that each component
of the complex substrates (e.g., crude oil) be converted into different products by frac-
tional distillation and catalytic conversion technologies. Even residues (such as
asphalt) in industrial processing can also be converted into an appropriate product.
This is called refining.
As with fossil oil materials, lignocellulosic raw materials also have complex com-
ponents. Therefore, the development process of lignocellulosic feedstock is similar to
that of petroleum-based raw materials. The refining concept is introduced into the
development of lignocellulosic resources, forming the new biorefining concept. The

traditional concept of a single product from the original complex lignocellulose
should be replaced in the chemical industry so that lignocellulose is taken as feedstock
for multiple products. Each of the major components of the raw material is converted
into different products, achieving full utilization of the raw materials and creating the
maximum value of the product.
Due to the fact that any plant is comprised of multiple components, conversion of a
single component does not often generate significant economic benefits. Comprehen-
sive utilization of each component involves the design of production technology and
integrated refining processes based on the diverse characteristics of the lignocellulose
components. Therefore, all plant components are converted to a corresponding prod-
uct with no waste emissions, forming an ecological industry chain. Currently, ligno-
cellulosic feedstock has been widely used in the paper industry, the textile industry,
and herbal and organic chemical processing. However, there are various problems in
these processes, such as single-product production and single-conversion technology,
causing a great deal of resource waste and environmental pollution. Thus, a multilevel
conversion process for complete utilization of lignocellulose is required, which cre-
ates a clean production process, reduces production costs, and increases the applica-
tion scope of bio-based products.
Therefore, in order to create a new production model for lignocellulosic materials for
general industry, the key issues of lignocellulose biorefining should be understood. Due
to the fact that raw material refining is a new generation of biological and chemical
industry, breakthroughs in the solving of lignocellulose scientific problems from an
engineering perspective should also be studied. Grading the conversion of lignocellu-
losic materials into bio-based energy, bio-based chemicals, and bio-based materials
through structural and functional deconstruction should be conducted by means of basic
scientific research based on the thinking of engineering practice research and the circu-
lar economy concept. For raw materials, organizational homogeneity of lignocellulose
should be improved and direct structural deconstruction and conversion should also be
conducted. For technology and equipment, key technologies and equipment should be
understood and an integration process should be developed. In this way multiproduction
could be achieved, product performance could be improved, and production costs could
be reduced.
1.4.2 Key points of lignocellulose biorefinery engineering

1.4.2.1 Theoretical basis of lignocellulose biorefining
The homogeneity of lignocellulose organizational structure is poor, and the com-
position is varied. Meanwhile, hydrolysis of lignocellulose is difficult due to its
resistance to degradation, and structural deconstruction is also difficult. Therefore,
efficient conversion of lignocellulosic resources is a scientific and technological
problem worldwide. Lack of a mature technology and high capital cost results in
difficulties for lignocellulose industrialization. The main reason for this lies in the
complexity of the lignocellulosic material itself and the lack of systematic theoretical
support (Himmel et al., 2007).
An overview 13
1.4.2.2 Feedstock engineering for lignocellulose biorefining

A key reason for the difficulty of lignocellulose industrialization is the lack of an effi-
cient component separation technique. If the components of the lignocellulosic feed-
stock cannot be effectively separated, it is impossible to control the characteristics and
quality of the final product. Because the composition of lignocellulose is very com-
plex, conversion of components into a useful molecule is difficult. Therefore, the use
of lignocellulosic feedstock for industrial production plants – such as furfural plants,
paper plants, and xylitol plants – only emphasizes the use of single cellulose or hemi-
cellulose components, but other components are discarded as waste, causing a serious
waste of resources and environmental pollution. Therefore, the lignocellulose industry
has not yet played an important role in improving economic efficiency, but has
become a burden to economic development (Chen, 2014).
The purpose of refining lignocellulosic feedstock is to improve the homogeneity of
the raw material tissue structure based on material components and structural proper-
ties. Refining should also increase product demand through a variety of physical,
chemical, and biological methods to break the original composition and structure,
which facilitate subsequent treatment processes, such as bioconversion, chemical con-
version, products separation, and purification. Raw material pretreatment efficiency
directly impacts raw material utilization, production costs, and product performance.
For the saccharification and fermentation of lignocellulose, pretreatment dismantles
and removes the structures and components of the lignocellulose that impede sacchar-
ification and fermentation, and eliminate the protection that lignin gives to the cellu-
lose. Meanwhile, the dense crystal structure of cellulose is broken, and hence the
accessibility of the cellulase to the lignocellulose and the hydrolysis efficiency are
improved, resulting in a high sugar yield and providing sufficient carbon source for
fermentation. However, in order to increase the product yield and achieve high-
fermentation efficiency, the amount of inhibitors produced in the pretreatment pro-
cess, which inhibit microbial growth, should be controlled. Plant fibers are basic
industry materials for pulp and paper, in which the cells of the fibers being processed
are mainly used and lignin and hemicellulose should be removed according to the
intended end-use. Therefore, damage to the plant fiber cell should be minimized in
the pretreatment process of the raw material, to prevent the degradation of cellulose.
Pretreatment methods of raw materials are determined according to the complex
structure and components of lignocellulose and the different product categories
required. Because the components of lignocellulose are multiple, different compo-
nents have different values in the raw material conversion processes, and other tech-
niques should be integrated in the pretreatment process. In this way, each component
is efficiently utilized in an integrated biorefinery system (Figure 1.4).
1.4.2.3 Conversion engineering for lignocellulose biorefining

Lignocellulose properties are similar to those of coal and oil, which are both organic
compounds and contain a variety of components. Most of lignocellulose is from
plants, and hence it has the properties of plants, such as cells and tissues with different
functions. Thus, lignocellulose has multiple functions. According to the demands of
Ecological industry and circular economy
Multi-
Comprehensive
utilization products
Raw material
Pretreatment technology
properties
Single pretreament Determination
Biological–physical
Combination pretreatment
–chemical
Selective structure split
characteristics
Material
Lignocellulose Conversion Products
pretreatment
Intermediate Conversion Products

products technology Feed, basic material,
Hemicellulose sugar Bioconversion fertilizer, fuel,
platform Physical conversion biological energy,
Cellulose sugar Chemical conversion materials, and
platform Thermal chemical chemicals
Lignin platform, etc. conversion
Process
Lignocellulose Products
engineering
Figure 1.4 Lignocellulose biorefinery process engineering.
the end-product, the appropriate component or structure can be selected by using

appropriate technologies for conversion (Chen et al., 2014).
1.4.2.4 Product engineering for lignocellulose biorefining

Product engineering develops products to meet the end-use performance require-
ments. Currently, product engineering has become an important research field. Lig-
nocellulose product engineering is the design, processing, and production of
lignocellulose products based on the end-use requirements, making abundant use
of renewable lignocellulose resources.
Lignocellulosic feedstock has a supramolecular structure formed by the interweav-
ing of cellulose, hemicellulose, lignin, and other molecules. Its multicomponent
structure means that the bio-based products that can be produced are diverse, including
bio-based energy, bio-based materials, bio-based chemicals, etc.
1.4.2.5 Process engineering for lignocellulose biorefining

Lignocellulose is typically a porous media. The fluid flow in porous media is deter-
mined by three factors: the porous medium itself (pore structure and physicochemical
properties), the fluid (chemical composition and physical properties of the fluid), and
An overview 15
the flow condition (flow environment, conditions, and the interaction between fluids
and solids). Biorefinery processing of raw lignocellulose is mainly composed of a
three-phase system: porous medium, gas, and liquid; this can be seen as a typical
porous medium system and can be studied based on the porous media theory. Ligno-
cellulose biorefinery processing can be investigated as a porous media transfer process
involving heat and mass transfer, percolation theory, capillary diffusion theory, fluid
mechanics, and thermodynamics theory.
1.4.2.6 Modes of integrated industrial lignocellulose

biorefinery chains
Lignocellulosic materials are mainly composed of four basic chemical structures:
carbohydrates (sugar, starch, cellulose, and hemicellulose), lignin, lipids, and pro-
teins. In addition to these basic compounds, there are hundreds of organic bio-based
components that show important commercial value, including for biomedicine, nutri-
ents, and other industrial products. For example, alkaloids, glycosides, flavonoids, ter-
penoids, organic acids, and polysaccharide compounds are active herbal ingredients.
There are many other important industrial products, including lacquer, rosin, and
natural rubber.
Faced with such a complex plant material, which strategies should be developed
and employed? We must depart from the traditional concept of a single product from
lignocellulose, and move to a system where a variety of components are fully con-
verted into different products to achieve a lignocellulose biorefinery integration pro-
cess based on complete utilization of the lignocellulose, component separation, and
the idea of fractional utilization. Taking the “components fractionation of lignocellu-
lose, and fractional orientation conversion process” as the key technology, a new eco-
logical balance system can be created and a new industrial chain can also be built,
which opens the way to maximum lignocellulose utilization and provides a solution
to current environmental problems. There are many problems in traditional lignocel-
lulose industries, such as low utilization efficiency of resources, low-grade products,
high production costs, and environmental pollution; these provide a broad stage for
using high tech to transform traditional industries. The process engineering taking
solid-phase organic materials as feedstock is not only a country’s basic industry,
but also the root cause of current environmental pollution. New ideas of fractionation
are crucial for natural solid-phase stratified multistage recycling of organic materials.
To introduce this strategy, straw lignocellulosic ethanol is taken as an example
(Figure 1.5).
(1) Hemicellulose can be separated from cellulose and lignin by steam explosion. Following
water extraction, the product contains mainly monosaccharides, oligosaccharides, organic
acids, and other organic carbon substances. When it is mixed with cellulase fermentation
liquids, the complement of carbon and nitrogen in two liquids improves the stability and
biogas production from biogas fermentation.
(2) Fiber materials, after water extraction, are fractionated into long fibers and short fibers by
classification separation techniques. Long fibers are rich in fiber cells while short fibers are
Straw Chop Rehydration Steam explosion Water extraction
Extract
Solid
Fermentation Organic
Fermentation residue fertilizer Fractionator
biogas
Short Long
Dehydration fiber fiber
Alkaline
extraction
Desulfurization
Enzymatic Extract Coarse

pulp
Biogas
Fermentation Ethanol Digested Filter

Concentration purification
wastewater fermentation residue
Beating
Distill Biomass
boilers Concentrate
Dehydration Paper
making
Lignin -
modified
Fuel phenolic resin Unbleached
ethanol adhesive paper
Figure 1.5 Agricultural straw biorefinery process using steam explosion coupled with
fractionation.
rich in hybrid cells. Separation of long fibers and short fibers is helpful for achieving max-
imum functional conversion of the different fiber types.
(3) Short fiber is rich in hybrid cells, which need low enzyme loading and short enzymatic time
during enzymatic hydrolysis. Meanwhile, it has high sugar concentration and enzymatic
efficiency, which improves the ethanol concentration in the fermentation broth and reduces
the energy consumption in distillation.
(4) Short cellulose fibers are used for cellulase production by fermentation, which reduces the
cellulase cost during ethanol fermentation.
(5) Long fibers are rich in fiber cells, and cellulose can be separated from lignin by dilute alkali
extraction technology at low temperature.
(6) Cellulose is a good raw material for the paper industry after removal of lignin.
(7) Active groups of lignin increase after steam explosion, and these are helpful for modifica-
tion processing. Modified lignin can be used for the preparation of phenolic resin.
(8) Enzymatic hydrolysis residues of short fibers can be used to produce steam and electricity
by lignocellulose boilers, which provide electricity and steam for the entire production pro-
cess. This process achieves energy self-sufficiency.
An overview 17
Based on ecological engineering and clean production processes, the problem of con-
sumption of fossil energy in a traditional ethanol production technology framework
can be solved, and comprehensive utilization of straw can also be achieved. Mean-
while, environmental pollution is avoided and the production cost of the product is
reduced.
References
Chen, H.Z., 2008. Ecological Biochemical Engineering. Chemical Industry Press, Beijing.
Chen, H.Z., 2014. Biotechnology of Lignocellulose: Theory and Practice. Springer Press,
Berlin.
Chen, H.Z., Liu, Z.H., 2014. Multilevel composition fractionation process for high-value uti-
lizaton of wheat straw cellulose. Biotechnol. Biofuels 7, 137.
Chen, H.Z., Liu, Z.H., Dai, S.H., 2014. A novel solid state fermentation coupled with gas strip-
ping enhancing the sweet sorghum stalk conversion performance for bioethanol. Biotech-
nol. Biofuels 7, 53.
Han, W.K., 2013. R&D of China’s Strategic New Industries-Biomass Energy. Machinery
Industry Press, Beijing.
Himmel, M.E., Ding, S.Y., Johnson, D.K., Adney, W.S., Nimlos, M.R., Brady, J.W., Foust, T.D.,
2007. Biomass recalcitrance: engineering plants and enzymes for biofuels production.
Science 315, 804.
Zhou, Q.X., 2013. Introduction of Resource Recycling Science and Engineering. Chemical
Theoretical basis of lignocellulose
biorefining 2
2.1 Lignocellulose recalcitrance
2.1.1 Introduction to lignocellulose recalcitrance
The recalcitrance properties of lignocellulose have been widely used in industry and in
everyday life to resist the degradation of microbes from the surrounding natural
environment.
With the depletion of oil resources, severe environmental problems, and the
increasing gap between the rich and the poor, biomass has become a prominent area
of research involving renewable resources around the world (Chen and Qiu, 2010).
With the aim of biomass development, humanity has begun to think actively instead
of passively: how to obtain valuable resources from biomass, a proficient converter of
solar energy, as an alternative fuel to coal, oil, and natural gas (Chen, 2009). In
essence, coal, oil, and natural gas are formed by plants through long-term geological
changes. The coal formation process covered three main periods: the Paleozoic (570
million to 2.3 million years ago), the Mesozoic (230 million to 6500 million years
ago), and the new generation (6500 million years ago); oil formation needs at least
200 million years, and up to 500 million years; and oil formation is accompanied
by petroleum gas generation (Brooks and Smith, 1967). Although the formation pro-
cesses of coal, oil, and natural gas are different, they are all the result of the long-term
effects (up to hundreds of millions of years) of moisture, temperature, pressure, acidity
(carbonic substance), and microbial interaction.
Current lignocellulose conversion methods include acid, alkali, high temperature
or pressure, radiation, microwave, ionic liquids, and other physical, chemical, or bio-
logical methods. Because bioconversion technology is clean, gentle, efficient, and
controllable, it has become the focus of current lignocellulose conversion methods
(Chen and Qiu, 2007). With bioconversion technology, lignocellulose can be con-
verted into small molecules including methane, ethanol, and butanol. In order to
improve conversion efficiency, a simultaneous saccharification and fermentation pro-
cess has been widely used, particularly for the fermentation of ethanol and butanol.
Because further separation and purification are required after ethanol and butanol fer-
mentation to improve their concentration, increasing the concentration of the fermen-
tation product can reduce the energy costs of the purifying process. Especially for the
fermentation of ethanol, by calculating the distillation energy, the economic cost of
the distillation unit can be acceptable when the ethanol concentration after fermenta-
tion is higher than 4.0% (w/w). Moreover, the yeast growth rate could be reduced if
ethanol concentration was 4.0–10.0% (Brown et al., 1981; Okolo et al., 1987; Peinado
et al., 1989; Seo et al., 2009). Therefore, an appropriate concentration of the ethanol
fermentation could be 4%. Higher ethanol concentration would reduce the yeast growth
rate, while lower ethanol concentration would make the distillation unit uneconomical.
For ethanol concentrations of 4.0%, the glucose concentration should be 7.83% in the-
ory (the conversion of glucose into ethanol is calculated as 51.11%). If the conversion of
cellulose to glucose was 90%, the concentration of cellulose at the beginning of sacchar-
ification should be 8.69%. Assuming that the cellulose content of the lignocellulosic
feedstock is 30%, the initial concentration of lignocellulose should be 28.99%, when
the ratio of solid to liquid is 1:3. According to the maximum concentration of ethanol
that microorganisms can tolerate (12% (w/w)), the ratio of solids to liquid is calculated
to be 1:1. As for the hydroscopicity of lignocellulosic feedstock, such as corn stalk,
when the ratio of solid to liquid is 1:10, there is free water that could flow freely. To
achieve the required high concentration of sugar, while not increasing the amount of
enzyme addition and the enzymatic hydrolysis time, the content of the substrate must
be increased. However, it has been found that if the content of dry substrates increases,
the enzymatic hydrolysis rate would reduce (Ximenes et al., 2011). Therefore, in order
to improve the enzymatic hydrolysis efficiency and reduce enzyme costs, lignocellu-
lose recalcitrance should be analyzed first to establish effective deconstruction technol-
ogies and improve the efficiency of enzymatic hydrolysis.
The microbial degradation of lignocellulose is also achieved by enzymes. Therefore,
hydrolysis of the cellulose in lignocelluloses with cellulase is introduced here by sum-
marizing the research achievements in the past 20 years of the team of Hongzhang Chen
(Qiu and Chen, 2012; Sun and Chen, 2008; Yang et al., 2009; Yu and Chen, 2010). The
process of lignocellulose hydrolysis by cellulase is as follows: (1) cellulase comes into
contact with cellulose; (2) the cellulase bonds effectively to its active site, and begins to
degrade the crystalline and amorphous regions of cellulose; (3) cellulases and hydrolates
flow effectively to ensure that cellulase can act on other sites and the formation of inhi-
bition products can be avoided. Current studies focus on how cellulase hydrolyzes
cellulose; that is, the interaction between enzyme and substrate after cellulase arrives
at the substrate. However, it has not been reported how cellulose transfers through
the tight structure of the substrate to arrive at its active site and how cellulase and prod-
ucts leave after hydrolyzation. According to the three steps of the hydrolysis process
introduced above, it is clear that the characteristics of lignocellulose determine the
feasibility or speed of each step (Van Wordragen and Dons, 1992).
In order to hydrolyze lignocellulose, lignocellulose recalcitrance must be fully
understood first. The term ‘recalcitrant’ originated in 1843, and its original meaning
is “kicking back.” Around 1990, it was used to refer to the resistance of plants to deg-
radation (Schultz et al., 1994). The concept of lignocellulose recalcitrance was pro-
posed in 2007 in Science by Himmel (2009) as follows: “the natural resistance of
plant cell walls to microbial and enzymatic deconstruction.” Michael E. Himmel
explained lignocellulose recalcitrance (Himmel et al., 2005) in 2005 in a technical
report, and summarized the specific meaning of lignocellulose recalcitrance as used
to describe lignocellulose biomass:
Lignocellulosic biomass is often described as “recalcitrant.” This term is used

in several contexts that may reflect the same underlying structural elements. The
Theoretical basis of lignocellulose biorefining 21
observation that different corn stover lots with essentially identical chemical compo-
sitions are pretreated and hydrolyzed differently has been described in terms of recal-
citrance. The term “recalcitrance” is also used to highlight the substantial difference
in severity required for the dilute acid hydrolysis of lignocellulose and starch and to
explain why pretreated lignocellulose requires 100 times higher enzyme for complete
saccharification than pretreated starch does. Additionally, “recalcitrance” is used
when describing the kinetic phenomena in which the rate of cellulase digestion slows
during extended reaction; i.e., a portion of the substrate is more digestible early in the
reaction than that at the end of reaction. Recalcitrance is also used to describe the
phenomenon by which pretreatment yields both digestible and indigestible fractions
with essentially identical compositions.
The term recalcitrance also describes the resistance properties of lignocellulosic

feedstock in different stages of biorefining compared with starch: different effects
of the same pretreatment conditions, or different enzyme dosage to get the same
hydrolysis results. The concept of lignocellulose recalcitrance describes the resistance
of lignocellulosic materials to microbial degradation or enzymatic hydrolysis from the
perspective of biology and plant anatomy.
As discussed in the beginning of this section, in the process of lignocellulosic feed-
stock biorefining, the high sugar concentration requires a ratio of liquid to solid of 3:1.
In a reaction system with such a high ratio of solid to liquid, if the reaction rate of enzy-
matic hydrolysis is constant, the mass transfer rate is bound to become a limiting factor
for enzymatic hydrolysis. This phenomenon also applies to pretreatment, fermentation,
or even the product extraction process. That is to say, the mass transfer process is the
limiting factor in the process of lignocellulose biorefining. Therefore, Prof. Chen’s
team summarized the key issues of the whole lignocellulose biorefinery process from
the perspective of process engineering: the intrinsic characteristics of lignocellulose
that influence the efficiency of different refinery units are porous media properties.
2.1.2 Structural analysis of lignocellulose recalcitrance

Plant lignocellulose contains three main tissue systems (Sachs, 1875): the epidermal
tissue system, the vascular tissue system, and the ground tissue system. The epidermal
tissue system can be divided into the epidermis and periderm; the vascular tissue sys-
tem can be divided into xylem and phloem; and the ground tissue system can be
divided into parenchyma tissue, including the secretion and secretory tissue, collen-
chyma cells, and the sclerenchyma.
The primary function of the epidermal tissue system is to protect the tissues inside
against microorganisms, and prevent moisture evaporation and loss of nutrients. The
function is mainly due to the fact that epidermal tissue system forms a hydrophobic
layer of skin and peripheral skeleton wax, connecting with air through the air vents.
Vascular tissue systems are generally embedded in a ground tissue system, and are
responsible for the transfer of water and nutrients. The primary function of the ground
tissue system is to store nutrients, and to transfer nutrients between adjacent cells
through plasmodesmata and pits. Therefore, the plant biomass is a skeleton structure
with interconnecting channels. Adjacent cells connect with each other, and the inter-
cellular layer is mainly composed of lignin, which is difficult to degrade.
The main skeleton structure of plant biomass is composed of the cell wall. In the
process of cell wall synthesis, the biosynthetic cellulose and hemicellulose are depos-
ited in the form of lamellae. Apart from some parenchyma cells and sieve cells, most
cells have both a primary cell wall and a secondary cell wall. The secondary cell wall
precipitates inside the primary cell wall. There are aggregations inside the secondary
cell wall, such as vascular cells. Each aggregation is composed of a layer of granular
structure and an amorphous structure, presumably resistant to rumen microbial deg-
radation (Himmel, 2009).
Most primary cell wall contains mainly cellulose and hemicellulose, and together
with pectin and proteins form a reticular structure, and the aging cell walls contain lignin
precipitates. Because of the loose structure of cellulose in the primary cell, the concen-
tration of lignin in the primary cell wall is higher than that in the secondary cell wall
(Yang, 2001). Compared with the structure of cellulose in the primary cell wall, the
structure of cellulose in the secondary cell wall is much denser and, therefore, the con-
centration of lignin is lower. However, the majority of the secondary cell wall is thicker
than the primary cell wall, so the total lignin content in the secondary cell wall is higher
than that in the primary cell wall. Lignocellulose recalcitrance at the cell wall level could
be introduced by the following aspects: the crystalline structure of cellulose; the matrix
network structure of hemicellulose surrounding cellulose; for dicots, pectin polysaccha-
rides crosslink with hemicellulose polysaccharides to form a network of cellulose micro-
fibrils; a small amount of protein in the primary cell wall crosslinks with hemicellulose
polysaccharides to form a protective structure of cellulose; for aging cells, the primary
wall being lignified, hemicellulose, cellulose, lignin, and protein form a protection net-
work (Himmel, 2009); lignin fills spaces inside the cell wall structure, such as the sec-
ondary cell wall, intercellular layer, and cell corner to form a cellulose barrier.
Therefore, in the natural structure of the plant cell wall, the skeletal cellulose
microfibrils are protected by hemicellulose, lignin, protein, and pectin, as well as
the network structure formed between cellulose molecules. To make use of the cell
wall polysaccharides, it is necessary to overcome these barriers.
2.2 Lignocellulose porous medium

By analyzing the structures that result in lignocellulose recalcitrance in Section 2.1.2,
it is clear that plant biomass forms a skeleton from cell walls and intercellular layers.
There are different channels among plant cells to ensure mass transfer. This section
describes the intrinsic porous structure of lignocellulosic feedstock at tissue, cell, and
cell wall level, taking corn stover as an example.
2.2.1 Porous structure at the tissue level

The porous structure at the tissue level (Zhao and Chen, 2013) refers to the structure of
the cell lumen of various cells within the tissue. Vascular plants form a protective
layer by an epidermal tissue system, and the vascular tissue system is mainly
embedded in the ground tissue system. The cell lumen of various tissues forms a cavity
during natural storage, and the cell wall thickness is a few microns thick. Therefore,
the shapes of the different cells represent the size of the porous structure at the
tissue level.
The epidermal tissue system of corn stover is mainly located in the leaves and
stems. The epidermal tissue system of the stems is mainly composed of rectangular
cells with a length of 100–250 mm and a width of 20–35 mm. The shape of the rect-
angular cells in the leaves is similar to that of the stems.
On the leaves, the gap surrounded by the crescent stomata guard cells is called a
stoma. Stoma are mainly in the lower surface of the leaf, and there are few or none in
the upper surface. There are 100–300 stomata per square millimeter in the leaves of
many plants (Liu, 2010). The holes are 10–30 mm in length, 10 mm or less in width.
There is a cavity under the stomata called a gas chamber. The plant cells are connected
to each other by this cavity.
In the vascular tissue system, the vessel cells in vascular tissue connect with each
other to form a cavity with a diameter of 30–130 mm. The diameter of a parenchyma
cell is similar to that of a vessel cell. In the vascular tissue system, there are sieve cells
surrounding the vessel cell whose lumen diameter (10–50 mm) is smaller than that of
the parenchyma cell, but its longitudinal length is around 100–500 mm (Liu, 2010).
Around the vessel cell, there are fiber cells with an average width of 13 mm and an
average length of 0.99 mm (Li and Wu, 1993). There are spaces between different
tissue cells. The size of the cell corner of stem pith in corn stover is about 1 mm, which
is the same as that of the intercellular layer between adjacent cells.
2.2.2 Porous structure at the cell level

The porous structure at the cell level mainly refers to pits in the cell wall, including the
cell wall of the vessel cell. Mass transfer between different cells is mainly through pits.
There are both pit pairs and simple pits. The diameter of the pit in corn stover is
20–50 mm. In addition, the transfer of cytoplasm between adjacent cells is through
plasmodesmata, whose diameter is 30–60 nm.
The horizontal wall in the vessel cell usually disappears completely, leaving only a
lap passage way, called the perforated edge. The transverse wall with the perforation is
called the perforated plate. In corn stover, the width of pores in different catheter-
perforated plates is 1–20 mm and the length is 10–30 mm.
2.2.3 Porous structure at the cell wall level

The porous structure at the cell wall level refers to the pore structures among various
macromolecules of the cell wall. The cell wall of parenchyma cells and sieve cells is
mainly a primary cell wall, which contains mainly cellulose. In contrast, the cell wall
of fiber cells, epidermal cells, and vessel cells is composed of the primary cell wall and
the secondary cell wall; the secondary cell wall mainly contains lignin. The primary
cell wall thickness is generally 0.1 mm, and the thickness of the secondary cell wall is
generally 5–10 mm. Usually, the secondary cell wall is deposited inside the primary
cell wall, so there is no gap in theory, and no reports refer to such a gap. The primary
cell wall is mainly composed of 3–5 nm cellulose microfibrils (Figure 2.1) surrounded
by xyloglucan and pectin polysaccharides (Abud et al., 2013).
There are various glucan chains in the cellulose microfibril (Figure 2.1): 6 crystal-
line cellulose chains, 12 chains with slight crystallinity, and 18 surface chains. The
crystal structure of the cellulose chain is less than 1 nm. It can be speculated that a
glucose molecule is about 0.4 nm. Because the cellulose structure is also formed
by polymerization of the glucose monomers, there could be quaternary structures
in cellulose. The primary structure is the extended chain composed of the glucose mol-
ecules connected by b (1 ! 4) glycosidic bonds, where there is 180 rotation between
adjacent glucose molecules; the secondary structure is the fibrillar structure of 2 nm
which is composed of six extended chains (from the structure of the enzyme used to
synthesize cellulose, the fibrillar structure may be formed by 8 or 12 extended chains)
connected by hydrogen or hydrophobic interaction between the parallel chains of
glucose rings; the tertiary structure is the microfibril (3.5–10 nm width) composed
of six fibrillar chains, and the microfibrils of algae can reach 30 nm; the quaternary
structure is the spatial structure of microfibrils that rotates through space or interacts
with other microfibrils, hemicellulose, or lignin. The porous structure of plant biomass
is summarized in Table 2.1.
The porous structure of lignocellulose, as described at the tissue, cell, and cell wall
levels demonstrates that it is essentially a porous media. The skeleton begins to form
from a tight structure at the molecular level: cell wall polysaccharides and lignin inter-
twined by hydrogen bonding; hydrophobic interactions form a structure similar to
reinforced concrete; adjacent cells are bonded to each other through lignin which
is coated in an intercellular layer or cell corner; finally, the outside of the plant is
tightly wrapped by the waxy cuticle layer of the outer surface of the epidermal tissue
system, which is hydrophobic. Therefore, in the process of lignocellulosic feedstock
biorefining, to take full advantage of the different components, the tight structure must
be deconstructed.
Figure 2.1 Cell wall surface of the

parenchyma cells in sugarcane by
atomic force microscopy (Abud et al.,
2013).
Table 2.1 Porous structure analysis of corn stalks (Zhao and Chen,
2013)
Level Origin Width (mm) Level Origin Width (mm)
Tissue Rectangular 20–35 Cell Pit 0.5–50.0

cell
Stomata 2–10 Plasmodesma 0.030–0.060
Vessel cell 30–130 Cell wall Space between 0.001–0.100
Sieve tube 5–50 macrofibrils
Sieve cell 5–50 Space between 0.001–0.030
Fiber cell 13 micorofibrils
Intercellular <1 Lamellar 0.001–0.030
space gaps between
Cell corner 1 polyphenols
2.3 Mass transfer resistance of lignocellulose: seepage

recalcitrance
2.3.1 Lignocellulose transfer structure
In order to acclimate and resist the invasion of the surroundings, through long-term
evolution plant biomass has formed a highly ordered tissue system, in particular
the epidermal tissue system. Therefore, in the process of growth and metabolism,
how do plants exchange materials with the outside world? How do they transfer nutri-
ents and water? What prompted this exchange and transfer of nutrients and water?
Plants exchange material with the outside world mainly through channels in leaves
and roots, with roots being the main channels. Plant roots absorb water mainly through
root hairs, the dermis, and the endodermis, and then the water enters the vessels
through the stele parenchyma cells. There are two ways to transfer water in the roots:
the apoplastic and the symplastic pathways. The apoplastic pathway refers to the pro-
cess of moving water through the apoplastic part including the cell wall, the cell gap,
the intercellular cavity layer, and the lumen of the vessel with low hydraulic resistance
at fast velocity. However, the apoplast of roots is usually not continuous; it is sepa-
rated into two areas by the Kjeldahl band within the endodermis. The first area is the
outer layer of the endodermis and includes hairs, the intercellular layer in the epider-
mis, the cell wall, and cell corner; this is called the external apoplast. The second area
is the interior endodermis and includes sophisticated vessels and various cell walls in
the stele, which are called the internal apoplast. Water is transported from the external
apoplast into the internal apoplast through the apoplastic transportation of endodermis
cells. The symplast pathway refers to the process of moving water from the cytoplasm
of one cell into another cell’s cytoplasm. Symplasmic transfer is transmembrane, so
there is a strong mass transfer resistance. The above-ground parts of plants exchange
with the outside mainly through transpiration. The leaf is the main channel of the above-
ground part for exchanging with the external environment in the various growth stages
of the plant. For young plants, the entire surface of the above-ground parts could carry
out transpiration. As the plant matures, the surfaces of stems and branches are suberized
and the pores are blocked, so transpiration ability is lost. Transpiration is very limited in
other parts of the stems and branches without suberization, and in flowers and fruits.
There are two types of leaf transpiration: one is called cuticular transpiration; the other
is called stomatal transpiration. The cuticular layer itself is hard to pass through but
there is pectin in the cuticular layer, which is highly hydroscopic. Meanwhile, there
are pores in the cuticular layer that form a pathway for water. The ratio of cuticular tran-
spiration to stomatal transpiration is related to the ecological conditions and the age of the
plant. Normally, the cuticular transpiration of a leaf is only 3–5% of total transpiration.
What allows water to transfer from the roots to the leaves? There are two main forms
for water movement in plants (Wang, 2000): bulk flow and diffusion. Bulk flow refers to
the movement of groups of atoms or molecules in liquid (components of various sub-
stances in aqueous solution) at a pressure gradient (potential gradient). Bulk flow under
a pressure gradient is the main mechanism for long-distance transfer of water and salts
from roots upward to various organs through the xylem, as well as organic components
produced by photosynthesis from the leaf down to various organs through phloem. The
power of bulk flow is the pressure difference; namely, the water potential gradient
between the inside and outside of plant root cells. The water potential gradient results
from the root pressure gradient (positive pressure potential) and transpiration tension
(negative pressure potential). Root pressure is generally no more than 0.2 MPa, by
which the water can rise up to 20.4 m; therefore, the main power behind water rising
up is transpiration. When transpiration is strong, the top leaf could reduce the water
potential to about 3.0 MPa, while the water potential of a root vessel is generally from
0.2 to 0.4 MPa. Therefore, water in the root could rise to the top of the plant along the
potential gradient. Diffusion refers to the movement of molecules (including gas mol-
ecules, solute molecules, and water molecules) from a high concentration (high chem-
ical potential) area to a lower concentration (low chemical potential) area until the
molecules are evenly distributed. Osmosis is one kind of diffusion, which refers to
the diffusion of solvent molecules in solution through a semipermeable membrane.
For aqueous solutions, osmosis is the diffusion of water from a high potential area to
a low potential area through a semipermeable membrane. Due to the small resistance
to mass transfer in the xylem vessels of plant biomass, the water needed for metabolism
for plant growth travels mainly through vessels from the roots to the leaf.
If the water transfer from the roots of the plant along the vessel is simplified to the
conveying of water through pipelines, according to the Poiseuille equation the flow
volume of water in the pipe is calculated as follows (Sachs, 1875):
4
pr Dcp
Volume flow rate ¼ (2.1)
8 Dx
where, r is the radius of the pipe; is the viscosity coefficient of the water; and Dcp/Dx
is the pressure gradient. Equation (2.1) demonstrates that the volume flow rate of
water is a long-distance transmission that is proportional to the fourth power of the

radius of the delivery pipe. Therefore, the radius of the pores in the plant biomass,
especially the radius of the vessels and the sieve cells, has a direct relationship to
the mass transfer in the plant. In the process of lignocellulose biorefining, the fluid
would flow not only in the vessel and sieve cells, but also in all pores inside or outside
of cells to ensure the treatment medium can contact with the substrate adequately,
improving the conversion rate and efficiency. If the pressure Dcp and the viscosity
coefficient are the external factors for the lignocellulose biorefining process, the
radius r and Dx are the intrinsic characteristics of the raw material, especially r. Con-
sidering that the radius of the pores in a plant ranges from nanometers to micrometers
(such as plasmodesmata and the macromolecular gap in the cell wall), the character-
istics of the porous structure of the lignocellulosic feedstock has a significant impact
on biorefining processes.
2.3.2 Lignocellulose seepage recalcitrance

From the perspective of systems and engineering, the basic principle of mass transfer
in lignocellulosic feedstock is more important than the reaction mechanism between
the pretreatment medium and the substrate. Therefore, Prof. Chen’s team (Chen and
Qiu, 2007; Chen and Qiu, 2010; Qiu and Chen, 2012) proposed to analyze and
strengthen the biomass biorefining process in terms of mass transfer, heat transfer,
and transmission based on their research spanning 20 years.
Prof. Chen (Zhao and Chen, 2013) introduced porous media theory into the lig-
nocellulose biorefining process, and analyzed the porous structure characteristics and
related properties of lignocellulosic feedstock (Zhao and Chen, 2013). The percola-
tion and seepage mechanisms have been used in the lignocellulose biorefining pro-
cess. The porous structure can be described by parameters including pore size
distribution, surface area, pore volume, fractal dimension, tortuosity, and so forth.
These parameters can be analyzed in the lignocellulose biorefining process to deter-
mine their impact on mass transfer. The process of mass transfer in porous media
consists of three phases: the percolation stage, in which the fluid gradually reaches
saturation in the porous media; the transition stage, in which force reaches a thresh-
old pressure; and the seepage stage, in which fluid begins to flow in the saturated
porous media. By using multiple regression, the relationship between enzymatic
hydrolysis yield and the key parameters of these three stages has been analyzed:
i.e. percolation probability, threshold pressure, and permeability. It was found that
there was a significant correlation between the threshold pressure and enzymatic
hydrolysis yield, as concluded from studies of mass transfer in porous media. This
demonstrates that transferring porous media theory into the lignocellulose biorefin-
ery process is reasonable. In order to reveal this feature of lignocellulosic feedstock
biorefining, the authors put forward the concept of seepage recalcitrance: the
resistance of porous plant biomass to mass transfer (Zhao and Chen, 2013). The
concepts of seepage recalcitrance and lignocellulose recalcitrance are compared in
Table 2.2.
Table 2.2 Comparison of seepage recalcitrance and biomass

recalcitrance
Research Research
Definition Mass transport object area
Biomass The natural Transfer of Cell wall Biology,

recalcitrance resistance of microbes or botany
(Himmel plant cell walls enzymes to the
et al., 2007) to microbial substrate, e.g.
and enzymatic cellulose
deconstruction
Seepage The resistance The whole Porous Process
recalcitrance of porous plant transfer process structure of engineering
(Zhao and biomass to of accessing to plant biomass
Chen, 2013) mass transfer the substrate and at the tissue
leaving from the level, cell
substrate, mass level and cell
transfer velocity wall level
This concept will help to further analyze the relationship between the intrinsically
porous structure, the seepage properties of lignocellulosic feedstock, and biomass
biorefining, as well as the effect of pretreatment on the porous structures and mass
transfer. Finally, new ideas and ways of improving lignocellulose biorefinery effi-
ciency can be explored in terms of engineering.
Currently, there are almost no reports about the porous structure and mass transfer
properties of plant biomass. Despite a model of enzymatic hydrolysis related to pore
diameter having been established (Himmel et al., 2007) in terms of the reaction mech-
anism between cellulase and substrate, and the effect of pretreatment on enzymatic
hydrolysis having been proven to be related to structure changes, the basic parameters
of the porous structure of various plant biomasses and their mass transfer mechanisms
have barely been reported. Therefore, analyzing the porous media properties of ligno-
cellulose in the whole biorefinery process would be an effective method of improving
lignocellulose biorefinery efficiency.
2.3.3 Impact of lignocellulose interfacial properties on seepage

recalcitrance
In the process of enzymatic hydrolysis, cellulase should come into contact with cel-
lulose after arriving at the substrate. However, cellulose is coated with lignin and
hemicellulose. Lignin is hydrophobic, and the content as well as the structure of lignin
in different cells is also different. Therefore, whether the surface of the lignocellulose
could connect with cellulase is another basic issue that needs to be resolved for lig-
nocellulose biorefining. There are studies reporting that the interfacial contact angle of
lignocellulose changes after acid pretreatment at different concentrations.
2.4 Lignocellulose functional components

During the process of lignocellulose biorefining, it is necessary for the fluid to find a
suitable substrate among the various components after arriving at the substrate surface
through the porous structure. Therefore, the functional components of the lignocellu-
losic feedstock are not only the target of the biorefining process, but also the carrier in
the lignocellulose biorefining process.
Because lignocellulosic feedstock is mainly composed of polysaccharides and
lignin, which are heterogeneous, the first step is to convert the feedstock into separate
polysaccharides and lignin platforms to make the lignocellulosic feedstock an alterna-
tive to petroleum resources. On this basis, polysaccharides and lignin could be con-
verted into bio-based products (such as fuels, chemicals, materials, and food or feed)
through biofermentation, chemical, physical, and thermochemical methods.
Which features of the polysaccharides and lignin components in lignocellulosic
feedstock give them such functionality? First, the cellulose and hemicellulose can
be hydrolyzed into monosaccharides that could be used by microbes. A microbe is
a cell factory, and humans could get a variety of products using the different metabolic
systems of different microorganisms. Lignin is a polymer composed of different ben-
zene monomers. Polymer materials, especially those composed of benzene, have
played an important role in industry. Therefore, lignocellulosic feedstock provides
renewable polysaccharides and lignin products through photosynthesis, using water
and carbon dioxide as raw materials. Therefore, lignocellulosic feedstock will play
an important role in the future.
2.5 Changes in composition and structure during the

lignocellulose biorefining process
The author found that the hydrolysis rate of steam-exploded corn stover and the final
conversion rate decreased with increasing intensity of the steam explosion, which has
been initially proved to be the results of pseudo-lignin generated from pretreatment.
When wheat straw is pretreated by crude glycerol, the enzymatic hydrolysis yield of
dry weight is lower than that of wet weight (Sun and Chen, 2008), suggesting that the
residual lignin and polysaccharide material forms a lignin–polysaccharide complex
that prevents interaction between cellulase and the substrate.
The biorefining process of lignocellulosic materials generates new compositions
and structures that will bring new properties. The inhomogeneity of lignocellulosic
material determines that biorefining oriented towards multiple products is necessary
to improve the economics of the final industrialization process (Chen and Zhao,
2013b). Multiple products orientation requires multiple technologies integration
(Chen and Zhao, 2013a). Therefore, it is necessary to consider the effect of new com-
positions, new structures, and the related new properties on subsequent biorefinery
process technology and the final products.
To avoid the influence of new components and structures generated during biore-
fining, the following research might be carried out:
1. New components generated from cellulose at high temperature or with catalysts:
5-hydroxymethyl furfural, 5-hydroxymethylfurfural, and levulinic acid.
2. New components generated from hemicellulose at high temperature or with catalysts:
5-hydroxymethyl furfural, furfural, levulinic acid, formic acid, acetic acid.
3. Small molecule phenols generated from lignin at high temperature or with catalysts.
4. New benzene components generated from cellulose at high temperature or with catalysts
(Sannigrahi et al., 2011).
5. Polymers generated by cellulose and lignin combinations: lignin–cellulose complexes.
6. Interaction between new components and original components or among new
components only.
7. Due to the dissolution or degradation of one of the original components, hydrogen bonds
were rearranged and then formed new structures, which would influence the interfacial
properties and porous properties.
8. Owing to the interaction between new components or between new components and orig-
inal components, the interfacial properties and porous properties are affected.
9. Changes of components and structure: properties of the lignocellulosic materials in differ-
ent operation units were different, such as capillary force, saturated water content, and mass
transfer properties, heat transfer performance, momentum transfer, and so on.
10. Changes in the components and structure result in different rheological properties in dif-
ferent operating units, or even at different stages of the same operating unit, and strength-
ening measures should be also taken into consideration.
11. Due to the changes of the components and structure, the mechanical properties may be dif-
ferent, requiring different equipment and process parameters.
Comprehensive analysis is necessary to understand the influence of new compositions

and structure. First of all, the change of one component or structure could lead to
changes in other structures and properties. Secondly, the effects of new components
and structures on different operating units will be different. Therefore, even if changes
in an operating unit are beneficial to the subsequent operation unit, this does not mean
that all the changes in the first operation unit will be beneficial to subsequent opera-
tions units. There may be adverse factors. If these adverse factors were avoided, the
beneficial effect would be more obvious. Conversely, if an operating unit has a det-
rimental effect on the subsequent operating unit, this does not mean that all changes in
this operation unit will have an adverse effect on for the subsequent operating unit.
There might also be positive factors. If these positive factors are strengthened, the neg-
ative effect might be offset or even replaced by a positive effect.
It should be noted that the biorefining process for lignocellulosic material is a
dynamic process, so the key factors of the entire process should be established in order
to achieve control of the products.
2.6 Analysis methods in lignocellulose biorefining

For any kind of lignocellulosic material, its feasibility for biorefining or biorefining
processes depends on detection of its composition, structure, and characteristics. For
the evaluation of a biorefinery technology, not only should the products, by-products,
and residuals be detected, but also the effect on the environment should be analyzed.
Finally, to control the process, the related parameters should be established. This sec-
tion introduces analytical methods for lignocellulosic materials, products, and the
biorefinery process. The advantages and disadvantages of the different analytical
methods are discussed.
2.6.1 Analysis methods for lignocellulosic materials

Analytical methods for lignocellulosic materials include methods for determining
composition, structure, and properties. Detecting the composition of the lignocellu-
losic material mainly refers to the detection of cellulose, hemicellulose, lignin, ash
content, and the monomers of polymers (hemicellulose and lignin). There are two
main ways to detect component content: one is the detection method that was
improved by Wang and Xu (1987) and the other is the detection method from National
Renewable Energy Laboratory (Sluiter et al., 2008). The first method is carried out
step by step with different washing detergents, and the contents are calculated by dry-
ing and weighing the residuals. Therefore, the measurement error is large, and the
measurement cycle is longer. The second method uses high-performance liquid chro-
matography (HPLC). Because the accuracy of this method is high and the cycle is
short, it is commonly used. The hemicellulose monomer can be detected while detect-
ing the hemicellulose content with HPLC by using standards of different monomers.
To detect the lignin monomer, lignin should be hydrolyzed first to get the monomers,
and then they can be detected with HPLC using relevant national standards. The type
and content of metal ions in ash can generally be detected using inductively coupled
plasma-atomic emission spectrometry (Yu and Chen, 2010). Other minor components
in lignocellulosic materials (including lipids, pectin, flavonoids, and tannins) should
also be detected in the large-scale biorefinery system. They could be separated as by-
products or be excluded to reduce their inhibition effects on the biorefining process.
The detection method can refer to relevant national standards or the related literature
(Chen and Liu, 2007).
The detection of the lignocellulosic material structure refers to two main aspects:
(1) detection of the morphology and anatomy of different tissues, the distribution of
cells, as well as cell wall structure (primary cell wall and secondary cell wall); and
(2) the detection of the porous structure, that is, the porous structure with the cell wall
and intercellular substances as the skeleton. The structure and components of ligno-
cellulosic materials determine the biorefinery techniques and the biorefinery strength
at different biorefinery stages. For example, for lignocellulosic materials with a large
amount of parenchyma tissue, pretreatment strength should be weak to avoid inhibitor
generation; while for materials with thick epidermal tissues, pretreatment strength
should be strong. This is not only helpful to improve the economic feasibility of bio-
refining, but also helps to decrease the generation of negative products. The methods
used to establish the morphology and anatomy are introduced next.
A microscope can be used for observations at the cellular level, and the cell wall
structure can be observed in frozen sections. A scanning electron microscope (SEM)
can observe at the cell wall level, and the SEM images are three-dimensional with
a resolution up to 1 nm. Moreover, a higher-resolution device has been reported.
A laser scanning confocal microscope has been reported to have high resolution up
to 200 nm. Atomic force microscopy can observe the cellulose microfibrils of the
cell wall with the transverse resolution of 0.1 nm and vertical resolution of
0.01 nm (Ding et al., 2012). Detection of the porous structure of lignocellulosic
materials can be used to determine the mass transfer properties of the lignocellulose
biorefinery process (detection methods for mass transfer parameters are introduced
below), and can also be used to analyze or improve the lignocellulose biorefining
process. Detection of the porous structure is especially important for biorefinery pro-
cesses in which enzyme transfer properties are determined by the porous structure.
Therefore, detection of the porous structure helps not only to understand the mass
transfer of the biorefinery process, but also provides a direct basis for finding suit-
able equipment and methods to enhance mass transfer. Porous structure is generally
detected by the mercury intrusion method and the nitrogen adsorption method. The
mercury intrusion method can detect pores from 3 nm to 400 mm, and the nitrogen
adsorption method can detect pores from 0.4 to 100 nm in size. Therefore, micropores
(<2 nm) and mesopores (2–50 nm) should be detected by the nitrogen adsorption
method, while macropores (>50 nm) should be detected by the mercury porosimetry
method. In the process of lignocellulosic material biorefining, mass transfer is as
important as the reactions themselves. Mass transfer is primarily associated with
the macro- and mesopores, while the reaction is mainly related to the micropores.
Therefore, both of the detection methods are required to determine the porous struc-
ture of lignocellulosic materials. Meanwhile, the detection of particle size and fractal
dimension is also part of lignocellulosic materials structural analysis because they are
important parameters for engineering design and analysis of the lignocellulosic mate-
rials biorefinery process (Duan et al., 2012; Zhao and Chen, 2013).
There are various property parameters used to describe lignocellulosic materials.
However, there has not been systematic research. For different industries, the relevant
properties are detected according to their respective needs. For example, property
parameters detected in the timber industry include fiber saturation point, tensile
strength, compressive strength, shear strength, and bending nature. These parameters
are helpful for the design of lignocellulose biorefinery processes and equipment, such
as the design of the grinding process and the mixing process. For lignocellulose bior-
efining, property analysis could be considered from the following aspects:
1. Mass transfer parameters. This refers to fluid transfer in lignocellulosic materials at different
stages of the biorefinery process, such as penetration rate, permeability, as well as mass
transfer resistance. Mass transfer parameters are important for the control and strengthening
of the lignocellulose biorefinery process. Mass transfer parameters can be detected with the
mercury intrusion method directly or be calculated based on the detection of structural
parameters. Meanwhile, related detection methods used in soil science and geology could
also be taken into consideration.
2. Analysis of the mechanical properties. Mechanical properties are the mechanical properties
of lignocellulosic materials at different stages of lignocellulose biorefining, including com-
pressive strength, shear strength, tensile strength, and so on. Related methods used in the
wood industry and the pulp and paper industry could be used as references.
3. Rheological properties. This refers to the rheological characteristics of the mixture of orig-
inal lignocellulosic materials and liquid in different biorefinery processes. These parameters
are the references used to select stirring equipment and control the reaction process.
4. Interfacial properties. This refers to the hydrophilicity of lignocellulosic materials, and the
corresponding functional groups. Interfacial properties influence the lignocellulose biorefin-
ery process in terms of contact of the catalyst with the substrate and the fluid properties in the
substrate. Hydrophilicity could be detected by the contact method or calculated indirectly
from other parameters.
2.6.2 Analysis methods for the biorefinery process

Lignocellulose biorefining mainly includes chemical methods, thermochemical
methods, physical methods, biological methods, and a combination of different methods.
There are different detection methods for different biorefinery technologies. This section
describes the common detection methods used in most biorefinery technologies.
First is the temperature detection method as used in the process of lignocellulosic
materials biorefining. To realize clean production, a higher ratio of solid to liquid is
the usual measure. However, if the liquid cannot form a continuous phase, the tem-
perature of different parts of the material will be different and this temperature differ-
ence makes the detection of temperature difficult; however, it is necessary to improve
product quality. In particular, if the lignocellulose biorefinery process is operated at
high temperature, high pressure, high humidity and requires such processing as steam
explosion pretreatment and anaerobic solid-state fermentation, the temperature
detecting apparatus requires higher and multiple functions. Therefore, temperature
detection is a challenging aspect of lignocellulose biorefining. These challenges
include: How do you determine the representative measuring points? What kind of
measurements should be taken to collect the information from the temperature distri-
bution in the reaction system? Which kind of measuring devices should be selected or
designed? This device may be used at high temperature, high pressure, high humidity,
or even in a closed environment and must report accurately and in a timely manner for
different locations (three-dimensional space point). At present, there are few reports
describing temperature detection for lignocellulose biorefineries. Therefore, it is nec-
essary to carry out the related research for the lignocellulose biorefinery industry.
The second detection method is related to the detection of morphological and struc-
tural features during the lignocellulose biorefinery process. Process detection is the
basis for process control. During lignocellulose biorefinery processes with a high
solid-liquid ratio, the challenges include: how to get information about the macro-
structure and microstructure changes during different operating units; and how to
get helpful information from the morphological changes, especially the key parame-
ters of the operation unit. Prof. Chen established a method for collecting morpholog-
ical and structural information, and analyzed the information with digital image
processing techniques to detect the solid-state fermentation process in fungi (Qiu
and Chen, 2012). By exploring the relationship between this digital information
and the key parameters of the operating unit, the final aim is to control the process
by the models established. This technology has been applied in solid-state fermenta-
tion, which requires a high solid-liquid ratio. Other parameters including humidity,
pressure, fluid transfer rate, fluid state, pH, ionic strength, and so on, play different
roles in different lignocellulose biorefining processes. The key is to establish an online
detection and control system by using modern detection methods to realize the indus-
trialization of lignocellulose biorefining.
2.6.3 Analysis methods for products

Various products could be prepared from lignocellulosic materials, for reasons that
include: (1) lignocellulosic materials are composed of more functional components;
(2) different polymer components could be hydrolyzed into different monomers;
(3) with the platform of sugar, different products could be prepared by fermentation;
and (4) for different lignocellulosic materials, there are different kinds of biorefinery
technologies. However, for now, to solve energy and environment problems, lignocel-
lulosic feedstock is mainly converted into monosaccharides, ethanol, butanol, lactic
acid, hydrogen, methane and other small molecules, and lignin-related products.
Monosaccharides are usually detected by high-performance liquid chromatogra-
phy. When the content of cellobiose, glucose, xylose, arabinose, and lactic acid is
detected, their peaks could be separated by using a Biorad Aminex HPX-87H column
and a differential detector. However, xylose and mannose require an additional sep-
aration column (Wang and Chen, 2013). Ethanol and butanol can be determined by
gas chromatography, wherein the capillary column is Innowax 19095N-123 (Wang
and Chen, 2011). Hydrogen can be detected by a Packard gas chromatograph equipped
with a thermal conductivity detector and the column RVS MolSieve 5A
(Panagiotopoulos et al., 2013). Methane (carbon dioxide, and hydrogen sulfide) con-
tent could be measured by a SRI 8610C gas chromatography system (MacLellan
et al., 2013).
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feedstock engineering 3
3.1 Overview
Lignocellulose is an aggregate of supramolecular structure—i.e. a combination of
cellulose, hemicellulose, lignin, ash, and others—wherein cellulose is wrapped by
the dense structure formed by hemicellulose and lignin, thus forming a complex spatial
structure with a three-dimensional network (Zhang, 2008). The diversity of lignocel-
lulosic feedstock composition determines that the engineering development processes
differ for the agricultural and forestry products processing industry, the fermentation
industry with food as raw materials, and traditional cellulose industries. Lignocellu-
lose biorefinery engineering should be the process of “refining” with pluralistic,
multifunctional conversion. Its purpose is not only to transfer the lignocellulose for
biofuel or bio-based materials production, but also to make lignocellulose a general
industrial raw material for the production of bio-based energy, materials, and chemi-
cals. The dense spatial structure of lignocellulosic material makes it difficult to use it
directly, hence feedstock pretreatment is necessary to achieve efficient conversion
(Eggeman and Elander, 2005). However, from the perspective of full utilization of
lignocellulose, the end-result of existing feedstock pretreatment technologies is still
cellulose hydrolysis and fermentation, while high-value utilization of hemicellulose
and lignin is rarely considered, and this seriously affects the healthy development
of lignocellulosic feedstock utilization. Therefore, the term ‘pretreatment’ must first
be given a new meaning and second, a new effective multicomponent utilization tech-
nology should be established to deal with the complexity of lignocellulosic feedstock;
namely, the component separation technique. Component separation and directional
conversion – further enhancing raw material pretreatment and achieving the conver-
sion of cellulose, hemicelluloses, and lignin – is currently the most important high-
value lignocellulose utilization concept, and has made much significant research
progress both at home and abroad (Jin and Chen, 2007; Kim and Lee, 2006; Sun
and Chen, 2008). However, the idea of lignocellulose component separation and
directional conversion is still hard to sell because of the problems of technical and
economic efficiency in large-scale clean and efficient industrialization when lignocel-
lulose is used as an industrial raw material. First of all, lignocellulose itself is a high-
energy macromolecular structure, and all the existing component separation and
directional conversion circuits need to first consume a certain amount of energy in
order to break down the lignocellulose structure before conversion. This method
does not take the functional needs of the product into account, and simply separates
the components of the raw materials, which, for some products, increases its energy
consumption and leads to a low atom economy of the raw material. Thus, if lignocel-
lulosic resources are to become universal biological and chemical raw materials, the
Lignocellulose Biorefinery Engineering. http://dx.doi.org/10.1016/B978-0-08-100135-6.00003-X
Table 3.1 Comparison of three development stages of primary

lignocellulosic material refining
Development
stage Forms of technology Goals of products
Pretreatment Single conversion technology of Single product

pretreatment
Components Integration of various conversion Full use of each
separation technologies component, and
polygeneration
Selective Low-power and high-efficiency Maximum value of the
structure split conversion technology according to the products and cleaner
structure and function characteristics of production
the raw material
refining process and technology of high-value utilization that maintains the original
structure of lignocellulose need to be developed (Chen et al., 2009).
Faced with the fact that lignocellulose is a macromolecule of complex chemical
composition and structure, Prof. Chen found that the biorefining process should be
based on the requirements of the target end products and the structural characteristics
of the materials; pretreatment of lignocellulosic feedstock, component separation and
the selective structure deconstruction process should all be carried out according to
product functional requirements. With energy consumption kept at a minimum,
and optimum efficiency, maximum value, and clean conversion as the goals, we
can achieve universal use of lignocellulose as the main raw material for a new gen-
eration of biological and chemical industries. Table 3.1 compares the technologies and
product goals in the three development stages of primary lignocellulosic material
refining. Hereinafter, the concepts of preprocessing, separation of components, and
the selective structure deconstruction are described in detail (Chen, 2014).
3.2 Technologies of components fractionation

3.2.1 Molecular level selective fractionation technology
Lignocellulosic feedstock is composed of cellulose, hemicellulose, and lignin. Cellu-
lose connects with hemicellulose and lignin by hydrogen bonds, while hemicellulose
and lignin connect with each other by covalent bonds. Therefore, the structure of
the cell wall is tight and complex. Cellulose, lignin, and hemicellulose are composed
of glucose, phenyl propane units, and pentose, respectively. It is obvious that the
three main components are different from each other. Cellulose and hemicellulose
are carbohydrates, while lignin is an aromatic polymer.
The heterogeneous bioconversion of corn stalk at a component level involves two
processes: hydrolysis and fermentation. In the hydrolysis process, hemicellulose and
cellulose could be hydrolyzed by cellulase. However, lignin is regarded as recalcitrant
Feedstock engineering 39
to cellulase enzymatic hydrolysis (Himmel et al., 2007). On the one hand, lignin
prevents cellulase contacting with the substrate. On the other hand, lignin absorbs
cellulase nonproductively.
In the fermentation process, glucose from cellulose could be used as the main car-
bon source. Pentose from hemicellulose could also be used by several kinds of micro-
organisms (Hahn-Hägerdal et al., 2007). However, the hydrolysate of lignin,
especially a small molecular one, has been proven to be an inhibitor for fermentation
(Larsson et al., 2001). Therefore, if corn stalk is converted as a whole, the cellulose
conversion rate would be low due to the lignin effect. It would be necessary to frac-
tionate the stalk into different components and then convert them, respectively. For
pulping, cellulose is extracted with different chemicals during the pretreatment pro-
cess. It is worth noting that lignin is removed to improve the properties of the pulp. The
chemical structures of cellulose, hemicellulose, and lignin change in different ways
during pulping.
3.2.2 Cell-level selective fractionation technology

Cells in lignocellulosic material can be classified into two categories according to the
thickness of the cell wall. The first category is the cell that only has a primary cell wall,
such as parenchyma tissue cells, sieve cells, and companion cells. The second type is
the cell that has both a primary cell wall and a secondary cell wall, such as scleren-
chyma cells (including fiber and hardened cells), vessel cells, tracheids, and collen-
chyma cells. Although cellulose exists in both the primary cell wall and the secondary
cell wall, the lignin content in the secondary cell wall is high. Lignin is regarded as the
cause of the recalcitrance of cornstalk to hydrolysis (Himmel et al., 2007). For bio-
conversion of cornstalk, the properties of these two kinds of cells are therefore
different.
In addition, there are special cells with different cell wall structures (Evert, 2006).
In some cells, the cell wall is often silicified. And the cell wall of dermal cells may
undergo hornification. There are also secretory tissue cells including secretory cells,
glandular hair, nectar, and secretory sacs. Secretory cells belong to parenchyma cells,
and so their cell walls are rich in cellulose. Although there are few special cells in
vascular plants, they can affect the bioconversion process. For example, hornification
can result in recalcitrance to enzymatic hydrolysis (Himmel et al., 2007). Therefore,
stalk is heterogeneous at the cell level because of the different components of the cell
wall. Hence, it is necessary to study the different conversion properties of the different
components.
When corn stalk is pretreated with steam explosion integrated with Bauer screen-
ing, two fractions can result. The fraction bigger than a 28 mesh contains more than
89% fiber cells and the fraction smaller than a 200 mesh contains 64% parenchyma
cells. Therefore, these two fractions are chosen to analyze the hydrolysis properties of
fiber cells and parenchyma cells. The fraction bigger than 28 mesh is first crushed to
smaller than a 200 mesh to remove the effects of particle size. When the two fractions
are hydrolyzed for 48 h, the glucose concentration is 5.15 g/L for parenchyma cells,
which is two times higher than that of fiber cells. In addition, the hydrolysis rate of
parenchyma cells can reach 70%.
If corn stalk is fractionated with steam explosion integrated with super grinding, a
powder fraction and a residues fraction can be derived. The parenchyma cell content in
the powder fraction is 26.6% higher than that in the residues fraction (area percentage).
And the fiber cell content in the residue fraction is 26.4% higher than that in the powder
fraction (Jin and Chen, 2006). The epidermal cell content is also different in the two
fractions. Therefore, the two fractions derived from corn stalk pretreated by steam
explosion integrated with super grinding can be used to analyze the hydrolysis prop-
erties of different cells. After hydrolysis for 24 h, reducing sugar content is 61.4% for
the powder fraction, which is 3.8 times higher than that in the residues fraction (Jin and
Chen, 2006).
The cell content before and after 48 h of hydrolysis for the powder fraction has
been analyzed. Results show that fiber cell content reduces by 22.8% after hydrolysis.
Parenchyma cell percentage reduces from 54.2% to 7.3%, while epidermal cell per-
centage increases from 10.4% to 80.9%. These changes demonstrate that different
cells have different hydrolysis properties. The enzyme hydrolysis properties could
be arranged, from high to low, as parenchyma cell, fiber cell, and epidermal cell
(Jin and Chen, 2006).
In the process of pretreatment with steam explosion integrated with super grinding,
moisture content could affect fractionation results. If the moisture content of the
steam-exploded material is 40%, the fiber cell content in the residue fraction would
be more than 60%. Therefore, the residue fraction could be used to analyze fiber cell
conversion properties.
The ethanol autocatalysis method is applied for pulping. The pulping process is
carried out at 180 C for 2 h with 50% ethanol concentration and solid to liquid ratio
of 0.8/10 (g/ml). This reveals that the crude pulp yield of the residue fraction could
reach 61.4%. However, pulp yields of steam-exploded rice straw and untreated rice
straw are 35.5% and 32.1%, respectively. So, it demonstrates that there is a positive
correlation between fiber cell content and pulping properties. Therefore, an effective
biorefinery method would be to fractionate different cells and then convert them.
3.2.3 Tissue-level selective fractionation technology

According to Sachs’s convenient classification (Sachs et al., 2011), the body of a vas-
cular plant is composed of three tissue systems: the dermal, the vascular, and the fun-
damental (or ground). The dermal tissue system comprises the epidermis and the
periderm. The vascular tissue system contains two kinds of conducting tissues: the
phloem (food conduction) and the xylem (water conduction). The fundamental tissue
system (or ground tissue system) includes parenchyma tissue, secretory tissue, collen-
chyma tissue, and sclerenchyma tissue.
There is a cutin layer on the outside of the dermal tissue system (Evert, 2006) which
is composed of cutin and wax. Cutin is mostly polymers composed of C16 and C18
monomers. The parenchyma cells under the dermal system are hardened, leading to a
high lignin content. For the vascular tissue system, the vessel cells in the xylem are
thickened so that the lignin content is high too. There are mainly parenchyma tissue
cells in the ground tissue system. For parenchyma tissue cells, there is only primary
cell wall, which is composed of cellulose. In terms of mass content, the vascular plant
is mainly composed of the ground tissue system and the vascular tissue system. There-
fore, vascular plants could be simply fractioned into a vascular tissue fraction, which
is rich in lignin, and a ground tissue fraction, which is rich in cellulose.
Corn stalk could be manually fractionated into a vascular tissue fraction and a
parenchyma tissue fraction. The vascular tissue fraction includes fiber cells around
vascular bundles because fiber cells are tightly connected with xylem and phloem.
When both fractions are hydrolyzed with enzymes for 48 h, the glucose content from
parenchyma tissue is 22.5% higher than that from vascular tissue. Corn stalk could be
fractionated into vascular tissue and parenchyma tissue fractions using steam explo-
sion integrated with mechanical carding. For rind and leaf, the enzyme hydrolysis
rates of the parenchyma tissue fraction are 1.77 and 1.37 times higher than for the
vascular tissue fraction, respectively.
The vascular tissue fraction from corn stalk is tested by pulping with ethanol auto-
catalysis. The result reveals that pulp yields could reach 57.6% while pulp whiteness
reaches 65.9% when the catalysis time is 2.0 h at 160 C (ethanol concentration 50%
and solid to liquid ratio is 1:10). The whiteness could meet the requirement of printing
paper (Chen and Liu, 2007b).
Corn stalk has not been used in pulping because there are many nonfiber cells. Non-
fiber cells are mainly parenchyma cells and dermal cells. Also, the fiber cell content in
corn stalk is low. Moreover, the ratio of length to width for corn stalk fiber cells is
smaller than that of other pulping materials. Therefore, if the whole corn stalk is
applied for pulping, the pulp yield and the quality of paper could hardly meet require-
ments. If nonfiber cells could be removed and the fiber cell content was high, corn
stalk would become another resource for pulping.
3.3 Technologies of selective structure deconstruction

3.3.1 Introduction to selective structure deconstruction
technologies
Lignocellulose is a carbon-rich organic resource, and can be used to develop recycled
and reclaimed functional products (such as bio-based materials, liquid fuels, organic
chemicals, etc.). Although the existing idea of lignocellulose component separation
and orientation conversion can help to solve the problem of efficient use of lignocel-
lulosic resources to a certain extent, it is still difficult to achieve economic and tech-
nical efficiency in large-scale, clean, and efficient industrial processes with
lignocellulose as the raw material. Lignocellulose itself is a high-energy macromolec-
ular structure, and the existing utilization routes of component separation and direc-
tional conversion need to consume a certain amount of energy prior to the destruction
of the lignocellulose structure, this approach also does not take the functional require-
ments of the product into account. Therefore, the approach increases the energy
consumption for some products, and results in a low atom economy of the raw mate-
rial. In addition, the process is made more complicated by a higher risk of contami-
nation. The root cause of this problem is the lack of full understanding of the
structure–activity relationship between the complex structure and the functional
use of lignocellulosic feedstock, resulting in the lack of both effective research ideas
and an efficient conversion technology system.
Therefore, the refining process and technology for maintaining the functional and
high-value use of the original lignocellulose structure must be further improved and
developed. Component separation proposed for raw material feedstock project
development should be promoted to achieve selective degradation of components
according to the product features, which should be based on the structural charac-
teristics of the raw material and the requirements of target products. The purpose of
this process is not only to obtain several products, but to achieve versatility of straw
as the main raw material in biological and chemical industries with minimum
energy consumption, optimum efficiency, maximum value, and clean conversion.
Thus, if lignocellulosic resources are to become universal raw materials in the next
generation of biological and chemical industries, an in-depth understanding of the
following aspects must be achieved: first, the relationship between selective struc-
ture deconstruction of the raw material feedstock and functional utilization must be
proven, which is the premise of refining lignocellulosic feedstock; second, the equa-
tions governing materials structural components and biological and chemical cata-
lytic reactions must be revealed; and finally, new methods must be developed for
refining and processing lignocellulosic raw materials with high efficiency and low
cost to achieve process optimization and coupled integration (Chen and Qiu, 2009).
3.3.2 The history of the development of selective structure

deconstruction technologies
3.3.2.1 Overall conversion of functionality
Lignocellulose utilization has a long history, and the emergence of papermaking and
charcoal manufacturing in ancient Egypt are successful examples of raw materials uti-
lization. China is a typical agricultural country, which has long carried out straw-
based recycling of lignocellulosic resources, including composting, returning to field,
use as feed, fuel, and so on. However, due to technological limitations, lignocellulose
conversion technology has been confined to simple and modest utilization for a long
time. For example, burning stoves is the most primitive lignocellulose utilization
method, and also the most common way in which lignocellulose is used, but its uti-
lization rate is only 15–20%. With the development and improvement of conversion
technology, the conversion rate is increasing. In the late twentieth century, helped by
the energy crisis, research into lignocellulose utilization developed quickly, and new
technologies of lignocellulose gasification and liquidation have been developed. The
technologies of direct combustion, gasification, pyrolysis, and liquidation are all uti-
lization processes that emphasize the entire functional conversion of lignocellulosic
materials. However, lignocellulosic feedstock has a functional supramolecular body
of complex structure; it is impossible to realize the maximum value of lignocellulosic

material unless the entire functional conversion method is used for the primary refin-
ing of lignocellulose.
3.3.2.2 Complete conversion of functionality

Lignocellulosic materials consist of cellulose, hemicellulose, and lignin. In addition to
entire functional conversion such as direct combustion, and in order to realize more
complete and full utilization, there has been some progress in the separate utilization
of the three components. The separate conversion of the three components at the same
time is a typical process of entire functional conversion. Nowadays, the papermaking
industry mainly uses the cellulose in lignocellulose, and makes use of various methods
to remove the other components in the materials (such as hemicellulose and lignin), as
a result of which the other components cannot be utilized, thereby generating waste.
Meanwhile, in the lignocellulose research of bioethanol, in order to obtain fermenta-
tive sugar, different pretreatment methods are taken to get high-purity cellulose and
there is little consideration given to hemicellulose and lignin. Therefore, such pretreat-
ment technologies are only halfway to being primary refining methods for lignocel-
lulosic materials, and only realize the utilization of one or two main components,
while other components are destroyed or wasted.
In order to realize the entire utilization of lignocellulose in lignocellulosic mate-
rials, a set of effective comprehensive utilization technologies for multicomponent
materials should be established. Component separation and oriented conversion is
a refining technology for the comprehensive utilization of the three components; it
is a further improvement of primary lignocellulosic material refining, i.e. not only
a pretreatment method, but also a resource distribution process for the macromolec-
ular components in lignocellulosic materials. It can realize the separate conversion
and utilization of the three components, and is the main concept for high-value use
of lignocellulosic resources.
3.3.2.3 Deconstruction and conversion of partial functionality

The process of component separation and oriented conversion in the complete func-
tion conversion requires a certain level of energy to break the tight structure of lig-
nocellulose prior to conversion. This method doesn’t consider the functional needs
of the products, the breakdown of the material increases energy consumption for cer-
tain products, and the atom economy is low. Therefore, the idea of component sep-
aration and oriented conversion still can’t break through the inherent difficulties of
economic and technical efficiency and other issues in large-scale, clean, and effi-
cient industrialization with lignocellulose as the industrial raw material. Therefore,
on the basis of summarizing the research results of the “973” Project numbered
2004CB719702 (China), Prof. Chen proposed that the pretreatment and components
separation of lignocellulosic raw materials should be promoted to a selective struc-
ture deconstruction process according to the structural features and needs of target
products, making lignocellulose a general industrial material for lignocellulose
energy, materials, and chemicals in the future. The product engineering takes the
product requirements as direction, and tries to develop a product satisfying the ulti-
mate features of usability. Product engineering is currently an important research
area. Lignocellulose product engineering is a process that can design, process, and
produce lignocellulose products with abundant recycled lignocellulose resources
as materials and taking the needs of people’s lives and production in the region as
direction. The production process of lignocellulose product engineering refers to
the lignocellulose refining process designed by one or several functional molecules
in the lignocellulosic raw materials from the perspective of product function, which is
the selective deconstruction process of lignocellulosic raw materials (Chen, 2014).
3.3.3 Current situation for selective structure

deconstruction technologies
Biomass feedstock, such as lignocelluloses, are supramolecules consisting of cellu-
lose, hemicellulose, and lignin, and the multicomponent structure determines that
the products using lignocellulose as raw materials are diverse: e.g. lignocellulose
energy, materials, and chemicals. Nowadays, some basic technologies using selective
structure deconstruction theory have been developed for the lignocellulosic raw mate-
rials refining process, and preferable research results have been obtained (Chen and
Qiu, 2009).
3.3.3.1 Partial structure deconstruction of hemp material

to improve spinning function
Hemp is a type of lignocellulose in abundant supply; in order to make the hemp fiber
spinnable, a degumming process must first be carried out. The traditional chemical
degumming method causes several environmental pollution problems. What’s more,
the low efficiency and high cost of microbial degumming can not meet the needs of
industrial production. Considering the entire structure of hemp material, Prof. Chen’s
research group came up with a selective structure deconstruction technology with
steam explosion at its core according to the functional needs of the products. The
steam explosion process can degrade 80% of hemicellulose and pectin to realize
the goal of hemp spinnability; with further processing, high-count pure yarn and
blended yarn with high spinning performance can be obtained. The steam explosion
method can not only advance the spinnability rate but also improve physical mechan-
ical properties, dyeing properties, and serviceability, and the whole industrialization
process does not contribute to environmental pollution.
3.3.3.2 Functional modification of whole straw to prepare

ecological board
The common method for making strawboard is to first conduct a simple heat treat-
ment, followed by thermocuring molding, during which the appropriate adhesive must
be added to obtain good products; however, the process leads to high costs and
pollution. Considering straw structural features and product function, Prof. Chen’s
research group utilized the active group with similar characteristics to polyphenol
by lignin degradation during steam explosion, which leads to a cross-linking reaction
with furfural produced from hemicellulose degradation, generating properties similar
to phenolic resin. Thus, no extra adhesive is needed. The changes of straw aggregation
structure during steam explosion can be fully utilized to hot-press the denaturized
structure after treatment. Through controlling the moisture content during the process
of hot-press forming, the hydrogen bonds of cellulose can be rearranged to produce
ecological board with high mechanical strength. This method not only solves the pol-
lution problems of the traditional method, but also maximizes the atom utilization of
straw materials and results in a simple operation and a clean craft process.
3.3.3.3 Multifunction realized by partial structure deconstruction

of straw
Lignocellulosic feedstock such as straw consists of various components, each of
which has different functional utilization methods to obtain various products. How-
ever, the current idea of component separation and conversion can not realize the
efficient, low-cost, and clean conversion of straw materials. Through intensive stud-
ies, Prof. Chen’s research group found that the functional characteristics of different
kinds of fibrocytes in different cellulose components were diverse. For example,
the fiber structure of the fiber bundle tissue can compete with wood fiber, hence
it can be used to replace a certain amount of wood for pulping. The pulping yield
can reach 45% with macrofiber using ethanol, and the lignin content of the pulp
is as low as 3.5%; while the parenchyma cell tissue has good fermentation proper-
ties, and the cellulase yield can reach 194.18 FPU/g dry substrate. Among other
components, in addition to cellulose in straw, hemicellulose can be degraded during
steam explosion, resulting in an excellent material for producing xylose and newtol;
the separated lignin is high in purity and a widely used material; and the ash can
further be used to prepare nanosilica. Therefore, full utilization of straw can be real-
ized in a clean and pollution-free method.
It is clear from the results above that selective structure deconstruction can not only
realize maximum atom economy of materials, but also is the simplest technical
method according to functional features of products, thus realizing low-cost, low
energy-consumption, and clean production (Chen and Qiu, 2009).
3.3.4 Development trends of selective structure deconstruction

technologies
China imports and consumes a large number of fossil resources, even though it already
has abundant lignocellulosic resources. The biorefinery industry, international acade-
mia, and the industrial community in general should focus on and exploit theory and
technology for the increased use and conversion of lignocellulose resources, and the
development of a lignocellulose resource refining process for biological and chemical
industries.
In order to build up a new industrial mode with lignocellulose as a general raw

material, the key refining problems must be resolved from the perspective of engineer-
ing that inhibit lignocellulose from becoming the new generation of biological and
chemical general industrial materials. With basic science as the research method
and the ecological recycling economic concept as a guide, it is necessary to develop
lignocellulose refining technology to conserve the original structure and function and
build a simple functional utilization process with the highest atom economy and the
lowest energy consumption. In order to realize this target, the following three key
scientific problems need to be solved:
(1) Research into the relationship between material aggregation structures deconstruction and
functional components utilization. Lignocellulosic feedstock is a functional resource with
the characteristics of low carbon content, low energy density, and high inhomogeneity, and
different ways of structural deconstruction produce different functional components.
Therefore, to clarify the relationship between supramolecular structure deconstruction of
raw materials aggregation state and functional utilization, and to improve the high-value
utilization level of raw materials, has become one of the key scientific problems to make
lignocellulose a common industrial raw material.
(2) The relationship between the structural components of raw materials and the intrinsic char-
acteristics of heterogeneous catalytic reactions. Lignocellulose biomass has a dense and
impervious structure containing crystals, where direct catalytic conversion is difficult or
affects the performance of the conversion products. Selective structural deconstruction
can avoid the problems of high cost and environmental pollution in the existing process
of “first component separation and then reconversion.” However, the relationship between
material structure components and selective catalytic reaction must be recognized, and the
reaction laws of catalytic conversion in components deconstruction should be represented;
this is the key scientific issue in developing a refining system on the road to developing a
new generation of biological and chemical industries based on lignocellulose material.
(3) Optimization principles of an efficient and low-cost raw material refining process. Due to
both the complex structure and high nonuniformity, the functional utilization of straw must
be a reaction system and a flow path with multiple steps, bulk treatment, and utilization
distinguished by pathway, in a cluster reaction system. In the lignocellulose biorefinery
process, low energy consumption and high efficiency and value should be the goal.
Although the selective structure deconstruction and product functional conversion is the
most economic and efficient method, the cluster reaction system within the material refin-
ing system must be recognized. To analyze the refining system, focusing on a complex solid
substrate and identifying the principle during each process is the third key problem to real-
ize the high-efficiency refining of lignocellulosic feedstock.
The cellulose, hemicellulose, and lignin in lignocellulosic raw materials form a three-
dimensional network structure with cross-linking. There are essential differences in
the reactions between chemical catalysis of single-composition materials, even pure
cellulose, and solid complex lignocellulosic raw materials. The selective deconstruc-
tion and interaction among components and the control of target products in a ligno-
cellulose complex structure are completely new areas of chemical research. Therefore,
recognition of the relationship between the structural features of complex lignocellu-
lose and biological conversion is the basic key to realizing the refining process.
The high-value functions of lignocellulose belong to the reaction system of raw
material cluster refining, which requires the most economical and effective steps
and methods to achieve the conversion of raw materials. Therefore, understanding the
cluster reaction mechanism of the lignocellulose stratified multistage directional con-
version refining system for each process, resolving a complex three-dimensional
resource utilization refining system of comprehensive solid-phase materials for ligno-
cellulose, and matching the coupling principle of each process are the keys to achieve
efficient refining of the raw material feedstock.
With bioethanol as the product model, it is necessary to study: the refined ligno-
cellulose material, the coupling effect, and the principle of optimality during the pro-
cess of hydrolysis and biological degradation; the mass and heat transfer, the reaction
principle, and rules of multifield coupling – including material, energy, phase change,
and chemical reaction in the bioreactor; and to establish a continuous technology sys-
tem with the integration of straw enzymolysis, fermentation, product online adsorp-
tion, and separation.
3.4 Steam explosion treatment technology

3.4.1 Principles and equipment of steam explosion technology
Biorefining using lignocellulose as the main material needs pretreatment to break
the complex compact structure and to realize structure deconstruction and functional
components utilization, in order to strengthen the efficient and high-value conversion
of the lignocellulose resource. Among the existing pretreatment methods, steam
explosion technology is one with a long history and good performance. Steam explo-
sion technology dates back to 1928, when steam explosion pulping technology was
invented by W. H. Mason in the United States for fiberboard production. Since the
1970s, this technology had been widely used in the production of animal feed and
the extraction of ethanol and other chemicals from wood fiber. In the late 1980s, this
technology was further improved, when the Stake Technology Company in Canada
developed continuous water vapor explosion technology and its associated equipment,
and applied this technology to the pulping industry. Canadians E. A. Delong and G. S.
Ritchie patented the use of saturation water vapor to explode wood chips with chem-
ical pretreatment (DeLong and Ritchie, 1990). San Martin et al. (1995) and
Moniruzzaman (1996) used pine tree and bagasse, respectively, as steam explosion
materials, and concluded that steam explosion pretreatment was beneficial to enzymo-
lysis. Research by Morjanoff and Gray (1987) showed that when the material under-
went steam explosion, the hemicellulose hydrolysis rate could be improved with the
addition of H2SO4 or by treatment with SO2 or H2SO4 before steam explosion, which
released the enzymolysis inhibitors. Prof. Chen began to apply steam explosion tech-
nology to the straw treatment field. Because of the differences between straw and
wood in terms of chemical composition and structure, Prof. Chen proposed a low-
pressure and no-pollutant steam explosion technology without any chemical addi-
tions, exploiting a series of innovative methods such as clean pulp, clean hemp
degumming, humic acid prepared by straw, activated xylooligosaccharide, and so
on, and applied for several patents.
3.4.1.1 Principles of steam explosion technology

Steam explosion technology, after decades of research, has been widely used in fields
such as food processing, pharmaceuticals, bioenergy, materials, chemicals, and envi-
ronmental protection; the last of which having application prospects and advantages
that are becoming more and more obvious. In a steam explosion process, plant mate-
rials (with the cell structure having undergone a re-watering treatment vapor phase) are
stewed at high temperature and pressure where high-pressure steam penetrates into the
pores of the materials. Under the physical and chemical effects of high temperature and
pressure, hemicellulose is partially hydrolyzed into soluble sugars, and lignin between
the composite layers is softened and partially degraded, reducing fiber coupling
strength and softening. When the pressure is suddenly released, media and materials
work together to complete the physical energy releasing process. The gas media within
the materials expand rapidly at the moment of ejection while the high-temperature liq-
uid water within the material quickly explodes, completing the instantaneous adiabatic
expansion, thus fragmenting the material into tiny fiber bundles. In the process of
explosion, the expanding gas forms a shock wave, forming a shear deformation move-
ment under the conditions of softening materials, in order to achieve the components
separation of the raw material and structural changes. According to the research of
Zhang and Chen (2012), through theoretical analysis and calculation, the steam explo-
sion should be carried out at the cellular level in order to achieve the best explosion
performance, indicating that each cell can be treated as a “micro steam explosion
chamber” to establish the multilevel model at the phase of instantaneous pressure
release at the cellular level (Figure 3.1).
The breakage of physical and chemical structures during steam explosion mainly
includes the following:
(1) Similar acid hydrolysis and thermal degradation. During the process of steam explosion, the
high temperature and pressure go into the cellulose materials and penetrate into the inner
core of the cellulose. Because of the joint function of vapor and heat, cellulose and part of
the active components undergo similar acid degradation and heat hydrolysis, and the low
molecular material digests with the degree of polymerization of the cellulose decreased.
(2) Similar mechanical breakage function. When the high pressure is released, the superheated
vapor that has already penetrated into the cellulose releases rapidly and instantly from the
closed space in the form of airflow. In this way, cellulose is mechanically broken to a
State 1 Intermediate state State 2

ms,v2
v3
Pa,Ta
P1,T1, r1,m0 Pa,T2
P3,T2, r3,m0+mw . q Pw,T2, r2,m0+mw,v1
d
Flash evaporation
mw
ms
Cell model
Figure 3.1 Simple model for steam explosion at the cellular level (Zhang and Chen, 2012).
certain degree. Such breakage shows not only bond rupture, increased reducing groups, and
internal hydrogen bond damage of cellulose in the cellulose macromolecule, but also the
breakage of the amorphous region and part of the crystalline regions.
(3) The breakage of hydrogen bonds. During steam explosion, vapor penetrates into the pores of
the cellulose and forms hydrogen bonds with part of the hydroxyl on the cellulose chains.
Meanwhile, high temperature, high pressure, and high moisture content conditions will increase
the breakage of hydrogen bonds inside the cellulose, dissociating new hydroxyl and strength-
ening the hydrogen bonds in the cellulose. Meanwhile, cellulose cools down to room
temperature, freezing the super molecule structure, and only a small proportion of the hydrogen
bonds recombine. Then the solvent can easily enter, breaking the hydrogen bonds that are left
and accelerating the total breakage of other crystalline regions until total dissolution.
(4) The function of structural rearrangement. Under high temperature and pressure, the hydrogen
bonds inside the cellulose molecule are broken to varying degrees, and the mobility of cellu-
lose chains increases, which is beneficial to the ordered structure changes of the cellulose.
Meanwhile, the breakage of the cellulose chain makes the rearrangement of the cellulose
chain easier.
Generally speaking, during steam explosion, hemicellulose is partly autohydrolyzed

to generate monosaccharide and oligomer, while lignin is partly degraded. Under the
high temperature conditions, the acetyl hydrolyzed from the hemicellulose chains
forms acetic acid that can strengthen the hydrolysis of glucosidic bonds from hemi-
cellulose and ester bonds from lignin. Therefore, within limits, the stronger the pro-
cessing strength, the stronger the degree of hemicellulose hydrolysis and lignin
degradation, and the more obvious the component separation effect is.
Drawn from previous studies, steam explosion is not only a single chemical reac-
tion process, but also the result of its relation to physics and chemistry, as noted below.
(1) The impact on the three components. In studies by Sun et al. (2005) and Li et al. (2007), the
sugar, acid, and furfural degradation product categories were regarded as degradation prod-
ucts of hemicellulose, and the phenolic degradation was regarded as the product of lignin
degradation. Also, the degradation rate of hemicellulose and lignin with steam explosion
improved with the enhancement of explosion conditions (temperature and pressure). Under
high temperature and pressure, as a plasticizer, water rearranges part of the cellulose crys-
talline regions by heating, and a portion of the amorphous region converts to a crystalline
region, thus improving the crystallinity of cellulose (Chen and Li, 1999).
(2) The material characteristics of porosity and permeability. Chen (He and Chen, 2013) and
Kohler (Kohler and Nebel, 2006), through comparisons of SEM pictures, specific surface,
and Mercury Injection Apparatus before and after steam explosion, drew the conclusion
that compared with straw without steam explosion, the porosity and permeability was
improved, the pore area increased, and the total pore volume of the straw decreased through
steam explosion. Cellulose is the skeleton of cell walls, and hemicellulose and lignin are
the filler, with lignin and hemicellulose apparently degraded after steam explosion. With
the degradation of fillers, the skeleton is exposed, the porosity of the cell increases, and the
original mesopores (100–10,000 nm) and micropores (5–100 nm) turn into a macropore
(10,000–100,000 nm) structure. Because the area of macropores (100,000–400,000 nm)
is small and the total area content of mesopores and micropores is over 90%, the area of
total pores decreases.
(3) The enzymolysis rate of the material. The removal of hemicellulose after steam explosion
and the increase of specific surface area improves the accessibility of enzymes to cellulose
(Piccolo et al., 2010). Hendriks and Zeeman (2009) reported that the enzymolysis rate was
improved by six times after steam explosion. Adding acid and alkali (Li et al., 2005),
removing lignin degradation inhibitor (Wang and Chen, 2011), or adopting a two-stage
steam explosion technology can inhibit the degradation of hemicellulose, improving the
enzymolysis rate.
(4) The extraction rate of active ingredients. Yuan and Chen (2006) utilized vapor-coupled
steam explosion to treat Ephedra to extract ephedrine, and the extraction rate was improved
by 3.5 times compared to steam explosion alone, and the yield of raw materials was only
0.35%. Chen et al. studied the effect of steam explosion on the flavones extraction rate of
Rhus fruit, and the extraction rate can reach 19.65 mg/g of dry material under steam explo-
sion of 220 C for 5 min (Chen and Chen, 2011). Compared with untreated materials, the
extraction rate was improved by eight times, and it can be stopped within 15 min, shorten-
ing the extraction time by 180 min. This is because the plant structure was broken after
steam explosion and the protective cell wall was separated, reducing mass transfer resis-
tance during the internal diffusion. The actively effective constituents could contact, dis-
solve, and spread fully with the solvent, reaching the high extraction rate in a short time.
For the choice of steam explosion conditions, the main factors are explosion pressure
and maintaining time, so the main expression equation is still the equations proposed
by Overend et al. in 1987 (Overend et al., 1987). However, the one-sided equations do
not generalize all the factors impacting pretreatment performance. Therefore, Chum
et al. (1990), Belkacemi et al. (1991), Abatzoglou et al. (1992), Montané et al.
(1998), Hosseini and Shah (2009), and Zhang and Chen (2012) further enriched the
steam explosion strength equation considering the properties of materials, vapor, and
the tank. During the actual process of steam explosion, the results are correlated with
material variety, application of the exploded material, and tank properties. For instance,
the explosion conditions for wheat straw and wood are different. The requirements for
pulping, chemical fiber, and biological conversion are different for plant materials. In
order to obtain high-yield pulp, related measures should be taken to avoid composition
degradation. From the total utilization of lignocellulose, the goal is to obtain the three
components with the lowest costs. Considering the steam explosion conditions from the
prospective of engineering, it is mainly the homogeneity of the gas stewing and gas
transfer property, which is related to the initial water content of material, particle size,
bulk density, and coefficient of charge. The physical properties of the explosion tank
have a great effect on the process. For example, the ratio of the discharge port diameter
of the steam explosion tank and tank diameter, decompression speed, pipe shape of
discharge hole, and stabilization tank volume have an effect on explosion results.
3.4.1.2 Steam explosion equipment

Batch steam explosion equipment
Batch steam explosion equipment (Figure 3.2) consists of a vapor generator, a steam
explosion tank, and a stabilization tank. Under some conditions, there is a cooler after
the stabilization tank. Based on these, our group designed steam explosion equipment
at the lab level, which was used for the detection and analysis of data during explosion.
There are pressure sensors, temperature sensors, and a sight glass window on the
pressure-maintained tank; and a solid flow meter on the discharge hole, equipped with
20 2
19 5
6
22
11
21
7
8
9
1 17 18
3
4
12
10 16
13
14
15
Figure 3.2 Batch steam explosion equipment. (1) Steam valve; (2) inlet ball valve;
(3) discharge ball valve; (4) solids flow meters; (5, 8, 12) pressure sensor; (6, 9, 13) temperature
sensor; (7) pH sensor; (10) pipe buffer; (11) sight glass; (14) buffer tank; (15) valve; (16) gas
condensation system; (17) dynamic data acquisition and analysis system; (18) computer;
(19) thermometer; (20) pressure gauge; (21) pressure maintaining tank; (22) image acquisition
device.
a computer for dynamic data acquisition and analysis. The data provided by these
devices are convenient for the calculation. The devices gather the necessary data dur-
ing steam explosion and the kinetic model can be used to assess the steam explosion
effects and other parameters; this is beneficial for the engineering enlargement design
and development of application ranges of the steam explosion devices.
Steam explosion equipment has been gradually magnified to the scale of industrial
application, from 0.5 L to 1, 5, and 50 m3 (Figure 3.3). The steam explosion tank
Figure 3.3 Amplifying 0.5,

5, and 50 m3 steam explosion
vessels.
designed by Prof. Chen includes the tank body, cover, feeding port, and the discharge
port slip. The layout of the steam distribution pipes is optimized using heat distribu-
tion; a quick-opening door steam explosion vessel is established and pneumatic con-
trol valves are used instead of a manual ball valve (Chen and Liu, 2007a). In the course
of processing, the tank can ensure the desired pressure, and vapor explosion temper-
ature can be controlled within a certain range. As a result, the vapor explosion with
pneumatic control can quickly open jars using a cylinder control lever, to ensure
enough gas pressure to meet production requirements and improve production effi-
ciency. For the processing of Chinese herbal medicine, agricultural waste, and other
products, compared with ordinary vapor explosion, steam explosion can achieve pro-
duction characteristics of high-pressure with a cryogenic tank and rapid valve open-
ing. Based on the different optimum temperatures of the lignocellulosic feedstock and
the different requirements of steam explosion, the steam explosion method of a mixed
atmosphere instead of water vapor, and in situ methods and corresponding equipment
are proposed for steam explosion and materials.
Figure 3.4 shows a thin-walled steel tube (5) welded on the top of the steam explo-
sion tank (13) with dual intake and a quick-opening door; a cover (14) is on the top of
1
3
4 11
2 5
14
6
13
12
10
15
Figure 3.4 Structure diagram of dual intake and quick-opening door steam explosion vessel.
(1) Feed port; (2) feed valve; (3) push rod; (4) double-acting cylinder; (5) pipe; (6) lugs; (7, 15)
nozzle; (8) discharging port; (9) residue discharging port; (10) ring; (11) wheel; (12) manhole;
(13) steam explosion tank; (14) cover.
the quick-opening door, and two lugs (6) for fixing the tank and a ring (10) are welded
on the body of the tank (13). The shell of the gas explosion tank can withstand bursting
pressure of 1–1.7 MPa, and the temperature of the gas inside the tank can be controlled
in the range of 180–206 C. Vapor explosion material is added by hopper (1) into the
vapor explosion tank (14), and the feed valve (2) opens or closes by pushing the rod
(3) and a small wheel (11) and double-acting cylinder (4). The action of the push rod
(3) to the cylinder (4) is push and pull, and the small wheel (11) on the end of the rod (4)
can slide a valve (2), making the valve open or close, and there are two sets of valve
seals. The saturated steam goes through pipe (5) and the nozzle (7) into the steam
explosion tank, and the nozzle is full of high-pressure gas mixture, to ensure that
the reaction system has the desired reaction temperature and pressure. The resulting
vapor explosion materials flow out through the discharge port (8), while the discharge
reaction residue and other waste materials discharge through the slag port (9). After a
certain reaction time, the tank can be inspected through the manhole (12).
Continuous steam explosion equipment

Stake Technology Company has conducted in-depth research and developed the tech-
nology related to equipment for vapor-phase steam explosion, and has applied for a
number of patents. For example, the key equipment feeding system, antispray devices,
and unloading devices all have many unique properties.
Feeding system. Two spiral feeding systems (Co-Ax-Model) are used for steam
explosion and are driven by piston hydraulic drive devices (Brown, 1980). There
are four kinds of approved shape products, and the specific standards are listed in
Table 3.2 (Chen and Liu, 2007a).
Stake Technology Digester. Stake Technology has four kinds of technology
digesters for industrial production, and the specific standards are shown in Table 3.3
(Chen and Liu, 2007a). The discharge system of water steam explosion pulping tech-
nology is also critical, and Stake Technology Company has successfully designed and
developed a pulp discharge system to adapt to this technology. Figure 3.5 is a cross-
sectional view of the discharge system, and Figure 3.6 is a side view of the valve of
the discharge system.
Table 3.2 Technical characteristics of the feeding systems (Chen and

Liu, 2007a)
Capacity for
Capacity for treating Transporting Transporting
treating wood wheat straw concentration pressure
Standards (ODT/h) (ODT/h) (%) (kg/cm2)
6¢¢(Ф150) 0.75 0.45 35–90 45

8¢¢(Ф200) 2.0 1.2
10¢¢(Ф250) 5.0 3.0
14¢¢(Ф300) 15.0 9.0
Table 3.3 Production capacity of different digesters (Chen and Liu,

2007a)
Capacity for Capacity for Transporting Transporting
treating wood treating wheat concentration temperature
Standards (ODT/h) straw (ODT/h) (%) ( C)
12¢¢(Ф150) 0.75 0.45 45 233

24¢¢(Ф200) 2.0 1.2
36¢¢(Ф250) 5.0 3.0
96¢¢(Ф300) 15.0 9.0
Figure 3.5 Cross-sectional view of the discharge system (Brown, 1980).
Figure 3.6 Side view of the valve of the

discharge system (Brown, 1980).
The explosion devices are divided into one-section types and two-section types.
The highest vapor pressure during the explosion process is up to 6.0 MPa, and the
maximum steam temperature can reach 275 C. A muffler is on the bottom of the reac-
tor, and the noise caused by pressure release can be partially eliminated. The specific
operation is as follows: a certain amount of wood chips is put into the reactor, under a
high pressure for a time, and the ball valve installed at the bottom of the reactor is
opened instantaneously. Drastic changes in pressure both inside and outside of the
tank produced by the explosion crush the wood chips into fibers or filaments, and then
the fibers and filaments fall into the cyclone receiver and divide into gas-, liquid-, and
solid-phase materials. The gas-phase material is condensed for recovery, and the
liquid- and solid-phase material is mashing material. The two-section explosion
device type is modified from the one-section type for the purpose of suppressing
the heat loss of a segment-type device, in order to reduce power consumption.
3.4.1.3 Steam explosion-related devices

The main processing equipment required for straw and other nonwood fiber raw mate-
rials before and after steam explosion is shown in Figure 3.7. Cutting equipment for
nonwood raw materials can be roughly divided into two categories: knife rolls and
knife discs. The preferred cutting device for straw, wheat straw, and other materials
has been the grass cutting machine of knife rolls, which consists of a knife roller, bot-
tom knives, feed roller, tape used in delivering materials, and gearing. In a forced
mechanical feed process, the raw material is sent into the cutting mechanism. The
material entering is sent into a feeding port consisting of a feed roller with one roller
on a vertically disposed axis and the other on a horizontal axis. The latter suppresses
forage and constantly turns the forage to the second and third levels of the feed roller.
Materials are then cut into certain lengths by the knife on the knife roller and the knife
on the bottom of the feeding machine, then sent out by the material tape, and finally
sent to the dust filtering system for packaging (Himmel et al., 2007).
The straw baler is an environmentally friendly piece of equipment that compresses
straw, rice straw, and other materials into blocks, which will help reduce transporta-
tion costs and are easy to use. Currently, there are many types of straw balers, mainly
screw balers and hydraulic balers. In a screw baler, the nut sleeve is driven by a motor
Straw raw materials
Straw cutting Straw packing Transformation Straw powder

Straw crusher Conveyor
machine machine machine
Rehydration Dehydration Steam explosion The carding

equipment equipment equipment equipment
Figure 3.7 Main processing equipment for steam explosion.

and rotates, while the screw is consistent with the sleeve and does not rotate, thus gen-
erating a force by moving up and down to press the materials. By comparison, in a
hydraulic packer, the travel switch is pushed by the hydraulic pump driven by the
motor and this compacts and packs the materials. After packing, the material is trans-
ported to be processed, overcoming the disadvantages of high transportation costs of
bulk materials, inventory storage, exposure to fire, and possible air pollution.
Straw bales, after entering the processing site, need to be bulk packaged, and arti-
ficial bulk packaging is a low-productivity, high labor-intensity activity, with often
poor results. Therefore, bulk packaging machinery is necessary for larger-scale straw
treatment. This machinery can improve work efficiency and lower labor costs with
better loosening of the straw bag. The machine mainly consists of a feeding frame,
feed section, bulk bag roll, and out-feed conveyor parts. The material bag is packaged
on the conveyor to transport to the feed tank, and after two feed rollers the feed bag is
initially evacuated and then delivered forward. After a high-speed rotation of the bulk
bag roll, the straw bag is completely loose, and the spread material is passed down to
the belt and sent out by the conveyor.
Screw conveyors can be generally divided into one-part and two-part forms. The
one-part screw conveyor with a large span has a wider range of applications in forage
transfer, for example the spiral presoaking equipment for herbage material in the pro-
cess of pulping, and spiral discharge equipment with large volume, and so on. The diam-
eter of the spiral leaf is mainly 400–800 mm, with a span in the 6–13 mm range. The
spiral conveyor is mainly used for tablet presoak, which mixes the forage pieces with
chemicals after cutting the materials and before entering the digester and transport, in
order to increase the material bulk density, harvest rate, and quantity of the chamber,
while reducing dust in the process of delivery and reducing air pollution. It will convey
the material by rotating spiral blade, and materials are moved along the screw axis, as
with a nonrotating nut sleeve. The force that does not make the material rotate with the
spiral leaf is the weight of the material itself and the friction resistance of the material to
the shell. Compared with multistage screw conveyors, there is no suspending screw axis
in a one-part conveyor and the materials are not plugged, owing to its better adaptability
to a variety of materials and thus broader application prospects.
Raw materials usually need pretreatment before steam explosion, including water
pretreatment, acid leaching pretreatment, and alkali leaching (including liquid ammo-
nia and dilute NaOH) pretreatment; the same pretreatment equipment can be used in
each case. For larger materials, a cutting or crushing device is needed in the pretreat-
ment. Pretreatment is done to improve the steam explosion effect on the material, and
to enhance the separation of the components. The general process involves delivering
the straw materials to the dip tank and wetting them by a nozzle according to the mois-
ture content of the material. If the material contains more impurities such as dust, more
water can be injected to clean the material. The acid- or alkali-leaching process is sim-
ilar to water leaching, during which the material is sprayed with acid or alkali and sent
to the steam explosion chamber directly after stirring for steam explosion. The acid
and alkali concentration needed for a specific processing situation is determined by
the processing effect and the purpose. It is worth pointing out that water catalytic
hydrolysis without adding any acid or alkali is now a promising treatment method.
If less presoak liquid is added during the material presoak treatment process, steam
explosion can be carried out directly without dehydration. If the amount of leaching
liquid used in the material presoak treatment process is excessive, as in total immer-
sion stirring processing, the excess liquid needs to be removed in advance before it is
sent into the steam explosion chamber. The equipment for removing preimpregnation
liquid can be either simple or complex, according to the actual production situation.
The main types are twin wire extrusion machines, roller pulp dehydration units, press-
type dryers, and others. In the twin wire extrusion machine, the wet slurry material is
dehydrated by gravity, then sent into the dual network for preliminary squeeze dewa-
tering, and finally dehydrated through a mechanical pressure device, which can
increase the slurry concentration to 30%. This machine has the advantages of large
production capacity, compact structure, small floor space, and high work efficiency
(Chen and Liu, 2007a). For a roller dehydration unit, the material is dehydrated by
a squeezing roller before entering the roller, and this machine is suitable for batch pro-
duction of small quantities. The press-type dryer, just as its name implies, squeezes out
the moisture from the slurry through hydraulic extrusion. The device can lower the
moisture content of presoak material to 45–48%, with low investment cost, simple
structure, easy operation, small maintenance workload, and higher dehydration effi-
ciency, which is suitable for larger factories.
Steam explosion is helpful for separation of the fibrous tissue in materials, and
through carding processing, the material can be used according to its fiber length
or particle size classification, to improve the comprehensive utilization of raw mate-
rials. At present the equipment used for material carding processing after steam explo-
sion mainly includes the Paul fiber screening instrument and airflow classified
equipment. Of these, the Paul fiber screening instrument uses liquid flow to transfer
the material across sieves with different meshes, and after a certain period of time,
collects fiber in various screening slots separately. It is widely used in processing,
quality control and research in wood fiber production and also in the production of
other industrial materials such as glass fiber or natural synthetic fiber. An airflow
grading device is a commonly used gradation method depending on the materials
used, in which a grading machine, cyclone separator, dust collector, and induced draft
fan form a hierarchical system. When particles and air are mixed in certain proportions
and sent into the sizing chamber, according to a certain speed, the particle is affected
by the three-dimensional force of the turbine blade’s centrifugal force, air resistance,
and gravity. By changing parameters such as turbine speed and system air volume to
adjust its classification, the separation of fine and coarse particle materials is realized.
It is suitable for the detailed classification of dry micron-grade products, including
spherical particles, flake, and irregularly shaped particles. The device can also classify
particles of different densities. In addition, Prof. Chen proposed the dry classification
method and its corresponding equipment for short- and long-fiber lignocellulose
(Figure 3.8). The mechanical combing classification device consists of a high-speed
rotating drum and a fixed arc concave board, where the materials move between the
cylinder and concave plate, and are loosened by hitting, kneading, rolling, and comb
brushing. Material is fed from one end of the roller, moving along the cylinder axis,
and thrown from the other end of the cylinder, which explains why the device is called
Figure 3.8 Short- and long-fiber dry classification equipment.
an axial flow device. Because the separation device uses centrifugal force to separate
short or long fibers, it can be made of a drum of axial flow and sieve plate or concave
plate to realize the two functions of loosening and separating, thereby simplifying the
structure. The main factors influencing the effect of carding points include the water
content of the gas phase explosion material and drum rotational speed. Fiber bundle
tissues and cells can be obtained after combing classification, and the long fiber
obtained from the combination of steam explosion, mechanical combing, organiza-
tion, and classification can be used for papermaking, textiles, and other industrial
applications of high-quality fiber raw materials. Small fibers consisting of paren-
chyma cells can also be used for the production of fertilizer, feed protein, or enzyme
fermentation to produce a series of biological chemical products such as ethanol and
butanol, so as to realize the component fractionation, cleaning, and high-value use of
lignocellulose fiber (Wang and Chen, 2013c).
3.4.2 Steam explosion technology types

3.4.2.1 Low pressure and nonpolluting steam explosion
technology
Natural resources from agricultural production include food, fruits and vegetables,
nonstaple crops, agricultural waste straw, and so on. At present, the processing tech-
nology used for agricultural products is at a basic level with outdated equipment; for
agricultural waste such as agricultural products, straw, and others, mechanical crush-
ing or acid and alkali treatment is often used as pretreatment, and practical high-value
utilization technologies are rare. This not only leads to high energy and material con-
sumption, and wastewater pollution from the production process, but also results in the
low utilization of resources and less variety from a single product form, from which it
is difficult to form high-value products.
Prof. Chen assessed the differences in chemical composition and structure for straw
and wood; based on this assessment he improved the previous steam explosion tech-
nology and proposed a steam explosion technology with low pressure and no pollu-
tion. Chen also developed 3- and 5-m3 water vapor explosion tanks with quick-open
doors, and applied for a number of national patents (Chen, 2013). The technology is
under low pressure (usually <3 MPa), with saturated steam as the heat transfer media
material, and after a period of time, it breaks down the material structure through quick
evaporation of water by instantaneous explosion within these materials, in order to
realize component separation. The novel steam explosion technology has the follow-
ing features:
(1) Compared with the traditional mechanical crushing and chemical reagent treatment, there is
no need to add any chemical reagents during the process of explosion, which is beneficial
for processing and can eliminate pollution.
(2) The low steam pressure required lowers energy consumption, with generally 0.2–0.5 tons
steam consumption per ton. Also, the reagent consumption cost and the human cost are sig-
nificantly lower than those of other pretreatment technologies. More importantly, there is
no pollution control cost for this technology.
(3) The hemicellulose degraded in the process of steam explosion can produce high value-
added dichotomous growth factor and realize the goal of beneficial utilization. Therefore,
it can fundamentally solve the pollution problem of the steam explosion process and greatly
reduce the production cost. Currently, the nonpollutant steam explosion technology has
broad application prospects in industry, such as comprehensive utilization of straw, tobacco
processing, paper production, Chinese herbal medicine extraction, and clean hemp
degumming.
This production process is a batch-type explosion process. The device consists of a

steam generator, steam explosion tank, feeding valve, and receiver. The specific oper-
ation process used for components separation of wheat straw is shown in Figure 3.9.
After dust removal, the wheat straw and other straws are sent into the steam work-
shop. Materials are first given a presoak treatment because differences in starting mate-
rial moisture content will influence the time needed to reach the highest cooking
temperature, which also affects steam explosion performance. Experiments proved that
when the material moisture content was 34%, the steam explosion effect was better,
with the highest hemicellulose recovery rate, and this was also conducive to the
improvement of the performance of the pulping and paper pulp. Presoak processed
materials are sent into a steam tank, and the ventilation is heated to the required pressure
and temperature with high-pressure steam after the presoaked processed materials are
sent into the steam tank, and after a certain pressure time, the outlet is quickly opened to
release the pressure for explosion. In the actual process of steam explosion, adjustments
can be made according to the properties and usages of the exploded materials and dif-
ferent steam explosion devices, in order to meet the required demands.
The straw with 34% moisture content, after heat preservation for 4.5 min at
1.5 MPa pressure, undergoes steam explosion. Electron microscopy pictures of mate-
rials before and after steam explosion are shown in Figure 3.10. Extraction conditions
Steam explosion Wheat straw

1.5 MPa, 4.5 min (water content: 34%)
Countercurrent extraction
for times
Washing Purification Fermentation

Liquid
Filtration Decoloration: D412 resin
Temperature: 75 °C
Solid/liquid =15/100
Sizing
agent Ethanol recycle
Ethanol extraction
Temperature: 160 °C; Time: 1h
Precipitate
Ethanol: 70% Filtration Liquid Cryogenic distillation
0.3 mol/l HCl pH = 4.0
Solid/liquid = 1:50
Sizing
agent
Lignin purification
Andors Bjirkman Method
Cellulose
Figure 3.9 Components of the wheat straw separation process.
Figure 3.10 Surface fiber (a) (b) and fiber bundle (c) (d) of the Ephedra herb before (a) (c) and
after (b) (d) steam explosion (Chen and Liu, 2007a).
of hemicellulose sugar degradation after steam explosion are as follows: the solid to
liquid ratio is 15/100 (w/w), the temperature is 75 C, the materials are extracted coun-
tercurrent for three times, and the hemicellulose recovery rate is over 80%. Recycled
hemicellulose monosaccharides and polysaccharides can be further purified for fer-
mentation or as a product for sale. The remaining solid materials after extraction
can react with 70% ethanol under 160 C for 1 h (solid to liquid ratio is 1:50), resulting
in recycled alcohol-soluble lignin and high-purity pulp. Ethanol can be recycled, and
lignin after further purification can be used in the synthesis of chemical products.
Under these conditions, the lignin recovery rate can reach 75%. The obtained pulp
can become higher-quality paper after subsequent processing such as bleaching,
and it can also be directly used in sugar enzymolysis for liquid fuel ethanol fermen-
tation, where the digestion rate can reach over 90%.
Low-pressure and pollution-free steam explosion technology, which has been suc-
cessfully amplified to an industrial scale (50 m3), has a good adaptability for straw
with low raw material lignin and high acetyl content, and it has characteristics such
as no chemical reagent presoak, low vapor pressure, low energy consumption, and no
pollution. Thus, it fundamentally solves the problem of steam explosion pollution, not
only by realizing comprehensive utilization of straw with no pollution, but also by
being successfully applied in tobacco processing, the paper industry, Chinese herbal
medicine extraction, and the clean degumming hemp industry, which helps to improve
the environmental credentials of these industries.
3.4.2.2 Gas-phase explosion technology of mixed media

When water is used as a medium for steam explosion, the two forms of water (namely
gaseous and liquid water), are regarded as heat transfer media. The water mainly
includes the moisture of materials, water derived from rehydration, and water con-
densed from steam. High temperature steam seeps into the organization and pores
of materials to heat both the material and the liquid inside, and then forms a high-
temperature and high-pressure water cooking environment to soften and degrade
the components of materials. Rapid evaporation of water caused by the sudden release
of pressure damages the compact structure of wood fiber, so as to achieve the aim of
component separation and improve the utilization rate of the effective components.
During this process, as well as being the transfer media, water is also the reaction
media and causes many changes under high temperature and high pressure environ-
ments. However, such reactions result in the decomposition of target active ingredi-
ents in addition to the destruction of the wall-like barrier. Therefore, in dealing with
materials with heat-sensitive composition, or material that is easily hydrolyzed in the
presence of high-temperature and high-pressure water, the steam explosion medium
needs to change correspondingly in order to achieve the desired treatment effect. The
explosion medium is no longer purely the water in the steam explosion technology, but
includes “gas explosion” collectively with steam explosion. Prof. Chen came up with
the idea of putting air, carbon dioxide, ozone, liquid nitrogen, nitrogen, steam, super-
critical CO2, and other media such as ethanol into the steam explosion medium, and
for the first time put forward the concept of “gas explosion” and expanded the scope of
steam explosion operational conditions, broadening the application field of steam
explosion.
Mixed media gas phase explosion technology allows a gas medium of nonaqueous
vapor, or bubbles into the nonaqueous gas medium first, and then allows steam to enter
after reaching a certain pressure. After maintaining the pressure and temperature for a
certain time, the pressure is reduced instantaneously. This gas phase explosion method
has the following features: (1) under the original pressure condition, the operation
temperature is lower, especially applicable for heat sensitive materials, such as Ephe-
dra (Yuan and Chen, 2006), Eucommia, and other medicinal plants (Chen, 2010); (2)
it avoids the presence of water on the target component, eliminating the hydrolysis in
the process of steam explosion; (3) the use of low temperature and constant pressure
breaks down lignocellulose components, reducing the high temperature and high pres-
sure as well as the production of enzyme inhibitor, thus aiding enzymatic hydrolysis
and fermentation (Zhang et al., 2013); and (4) some gas can be used as the pressure
source for the explosion, also as a solvent gas for the extraction of target components
or products in the process of steam explosion.
Ephedra spp. are important in Chinese traditional medicine. Its chemical composition
contains more than 10 kinds of alkaloids, mainly 1-ephedrine and d-pseudoephedrine.
Its effects are numerous: soothes wheezing, antitussive, expectorant, diaphoresis, and
diuretic. Ephedrine is mainly distributed inside the cortex fiber, and its extraction must
overcome the mass transfer resistance of the epidermis, the fibrous layer, and especially
the cell walls. The compact structure of cell walls is the main obstacle to the extraction of
effective components, resulting in an ephedrine extraction rate that is not high by current
industrial extraction methods. By using steam explosion treatments the plant cell walls
can be broken, which is beneficial to the release of active ingredients. In the steam explo-
sion process of Ephedra spp. for ephedrine extraction, the plant materials are stewed at
high temperature (150–210 C). However, ephedrine is volatile and is easy to lose along
with steam under high temperature conditions.
To avoid volatilization and improve the extraction efficiency and extraction yield of
ephedrine at the same time, our group carried out research on steam explosion pretreat-
ment of air mixed with steam for ephedrine extraction from the Ephedra herb. This new
steam explosion method reduces the steam temperature while keeping the same pressure
during steam explosion. The steam explosion condition for the Ephedra herb is as
follows: the pressure is 0.8 MPa with air inletting, then is quickly increased to
1.5 MPa, and then released for explosion after holding the pressure for 3 min. Under
these conditions, the ephedrine extraction yield reached 0.345%; higher than that of
direct extraction by 243%. By electron microscopy, organization changes of Ephedra
before and after explosion steam were observed. The surface of the Ephedra herb with-
out steam explosion was small and thin, while the holes on the surface of the Ephedra
herb after steam explosion treatment were large and dense. Surface fiber and fiber
bundles of the Ephedra herb after steam explosion were curly, folding, and becoming
soft, and some fibers were fractured as shown in Figure 3.10. This was the root cause of
steam explosion promoting the active ingredient extraction rate.
3.4.2.3 Two-phase steam explosion technology

For lignocellulose raw materials, especially crop straws, the organizational structure is
extremely uneven, causing significant differences in the physical chemistry of different
organizational structures occurring in the process of steam explosion. For example, corn
stover contains leaves, pulp, and skins; the mechanical properties of leaves and pulp are
weak, easily broken, while the skin mainly contains mechanical organization with strong
mechanical performance that is not easily broken. In addition, leaves and pulp mainly
contain miscellaneous cells with much more cell content, the chemical reaction is strong
in the steam explosion process, and it is easier to generate inhibitors to subsequent sugar
platform construction. Therefore, based on the mechanical property differences of dif-
ferent structures within the raw material itself and the differences in the stability of dif-
ferent organizational structures under the acid environment of high temperature and high
pressure, Prof. Chen put forward a two-phase steam explosion and carding process
(Chen, 2013). In the first stage of the process under the lower steam explosion strength,
the structures with weaker mechanical properties are crushed first, while the crushing
effects on the parts of the plant with strong organizational structure are not obvious.
According to the different material forms after steam explosion, separation can be
achieved through mechanical combing equipment. Because the first stage of steam
explosion is a low-strength steam explosion, the production of inhibitor is low. At the
same time, the first stage of the process achieves even rehydration of materials, as well
as mechanical tearing effects, increasing the material porosity and fluffing out the orga-
nizational structure.
The material used in the second explosion stage has no obvious effects from the
first explosion process, and the second process is also under low-strength steam explo-
sion. Because of the even rehydration of materials and the effects of mechanical tear-
ing in the first stage of the process, the materials used in the second stage have an even
water content and loose tissue, and the even explosion of materials can be realized
under lower steam explosion strength. The two-phase steam explosion with carding
process for corn stalk is expounded below as an example.
(1) The feasibility analysis of two-phase steam explosion with a carding process.
The nonuniformity of natural cellulose raw materials leads to differences in the
ways of utilization and pretreatment. In the process of steam explosion, the extent
of steam (as the solvent in the process of high-temperature cooking as well as the
power source of the physical process of tearing) penetration into the cells inside
raw materials and the resistance of the cell tearing strength can both affect steam
explosion effects.
Beyond the interference of external factors such as particle size and filling coeffi-
cient, the cell wall thickness of the materials and cell cavity size are the main factors
influencing the steam infiltration, and the cell wall thickness is the main factor
influencing the tearing strength of the cell. In view of the fact that the morphological
structure of the thick cavity of fiber cell walls is small and the morphological structure
of the thin cavity of the parenchyma cell walls is big, it can be shown that there are
differences in the steam permeability of fiber cells and parenchyma cells.
As can be seen from Figure 3.11a, in the process of maintaining pressure, the rehy-
dration properties of fiber cells and parenchyma cells are different: parenchyma cells
have better rehydration properties than fiber cells, they absorb more and achieve ear-
lier equilibrium. As can be seen from Figure 3.11b, the moisture contents of the two
cells after the explosion of the steam are inconsistent, and the moisture content of
parenchyma cells is higher than that of fiber cells. It can be seen from Figure 3.11 that,
because the thick cavity of fiber cell walls is small and the thin cavity of parenchyma
cells is big, the vapor permeability of fiber cells and parenchyma cells do not match,
and steam, as a heat carrier in the process of steam explosion and a power source, is
bound to affect the extent of the degradation and the degree of tearing of fiber cells and
parenchyma cells.
Therefore, without getting involved in organization and classification, if whole
plant straw is regarded as the raw material, steam explosion pretreatment conditions
can be varied to achieve a high hemicellulose degradation rate, a low entrainment rate,
an increasing raw material specific surface area, and this may cause some excessive
0.8 Figure 3.11 Comparison of

Moisture content (mass percentage)
rehydration conditions of
0.7 fiber cells and parenchyma
0.6 cells after the water blasting
process. (a) The moisture
0.5 content of fiber cells and
0.4 hybrid cells under different
steam admission times; (b)
0.3 The moisture content of fiber
0.2 cells and hybrid cells after
Parenchyma cells water vapor blasting and
0.1 Fiber cells carding (Zhang et al., 2012).
0.0
0 1 2 3 4
(a) Steam entering time (min)
Parenchyma cells after carding

Moisture content (mass percentage)
0.7
Fiber cells after carding
0.6
0.5
0.4
0.3
0.2
0.4 0.6 0.8 1.0 1.2 1.4 1.6
(b) Holding pressure (MPa)
parenchyma degradation, which increases the likelihood of inhibitor production.

Therefore, appropriate steam explosion conditions can be chosen based on fiber cells
and parenchyma cells, respectively, to achieve their best pretreatment effect.
It can be seen from Figure 3.11 that steam explosion helps to achieve even rehy-
dration of fiber cells and parenchyma cells. Zhang et al. found that steam explosion
was beneficial in improving the degree of materials isolation, for example fiber cells
and parenchyma cells (Zhang et al., 2012). Using this method, in the first period of
steam explosion, milder conditions were taken to realize even rehydration, and based
on the principle of centrifugal air weight classification to separate the parenchyma
cells of high moisture content and the fiber cells of low moisture content, the fiber
cells were isolated and taken to the second period of steam explosion in more mod-
erate conditions. Therefore, reasonable design of this method is feasible.
(2) The effect of two-phase steam explosion with a carding process on inhibitor
content. It can be seen from Figure 3.12 that the inhibitor content of parenchyma cells
after the first period of carding was higher than that of fiber cells, and the inhibitor
content after the first period of steam explosion without combing is in between, which
shows that under the same steam explosion conditions, the extent of degradation of
parenchyma cells is greater than that of fiber cells. As a result, the lignocellulose non-
uniformity of the organizational structure itself determines the diversity and selectiv-
ity of the pretreatment conditions, and the result also indicates the necessity of
classification and selective pretreatment.
In steam explosion, the materials obtained from the second stage had lower inhib-
itor contents had lower than the control group, with the lowest content at 1.1 MPa
holding pressure (Figure 3.12). (The exception to this was the material held at
0.06
0.05
Conversion of inhibitor (%)
0.04
0.03 Fiber cells after ISFC

Parenchyma cells after ISFC
Control group (1.2 MPa/8 min)
0.02
First-step steam explosion
Second-step steam explosion
0.01 Integrated process
0.4 0.6 0.8 1.0 1.2 1.4 1.6

Holding pressure (MPa)
Figure 3.12 Effect of the two-phase steam explosion carding process on inhibitor content
(Zhang et al., 2012). ISFC, intermediate separation of fiber cells.
1.5 MPa which had higher inhibitor contents than the control group (control group:
steam explosion conditions of 1.2 MPa and 8 min)). The reason for the lowest inhibitor
content at 1.1 MPa may be that the fiber cells and parenchyma cells can achieve the best
degree of separation (Figure 3.13) at 1.1 MPa, and after carding the amount of paren-
chyma cells in the materials at the second stage of steam explosion is the least with
the lowest inhibitor content. In the holding pressure range from 0.5 to 0.9 MPa, the
inhibitor content increases. This is firstly because the steam explosion strength is
increasing, and the material degradation rate increases with more by-products; and sec-
ondly, because the degree of degradation of the raw materials is poor within the pressure
range of 0.5–0.9 MPa, fiber cells and parenchyma cells do not achieve good separation.
At pressures of 1.3–1.5 MPa, the degree of degradation of fiber cells and parenchyma
cells is good, but because its strength is relatively violent, the inhibitor content
increases. Combining with Figure 3.11, the best degree of separation is 1.6 when the
inhibitor content of corn straw by pretreatment is the lowest under this condition.
(3) The effect of the two-phase steam explosion with carding process on cellulose
enzymolysis rate. It can be seen from Figure 3.14 that the enzymatic rate of paren-
chyma cells was higher than that of fiber cells after the first period of carding, and
the digestion rate of the materials from the first-step steam explosion without combing
was in between, which also suggests that under the same steam explosion conditions,
the degree of degradation of parenchyma cells was greater than that of fiber cells.
Compared with the control group, in the steam explosion materials obtained from
the first step, the digestion rate was higher than the control group at 1.1 MPa holding
pressure. In the steam explosion materials obtained from the second-step, apart from
the 0.5 MPa holding pressure condition, the digestion rates of the other groups were
higher than that of the control group, and with the increase of steam explosion
strength, the digestion rate increased.
Degree of seperation (fiber cells/parenchyma cells)
6
Experiment groups
Control group (1.2 MPa/8 min)
5
0.4 0.6 0.8 1.0 1.2 1.4 1.6

Figure 3.13 Degree of separation of fibers under different steam explosion conditions (Zhang
et al., 2012).
Enzymatic hydrolyzation of materials (%) 0.9
0.8
0.7
0.6 Control group (1.2 MPa/8 min)

First-step steam explosion
Parenchyma cells after ISFC
0.5 Fiber cells after ISFC
Second-step steam explosion
Integrated process
0.4
0.4 0.6 0.8 1.0 1.2 1.4 1.6
Figure 3.14 Effect of different steam explosion methods on the digestion rate of materials
(Zhang et al., 2012).
Based on Figures 3.12–3.14, the optimal process conditions of steam explosion

with carding is 1.1 MPa\4 min-carding–1.2 MPa\4 min, when the fiber had moderate
degradation and reduced to avoid excessive degradation of parenchyma tissue with the
lowest inhibitor content by pretreatment (Zhang, 2012).
(4) The effect of the two-phase steam explosion with carding process on 2,3-
butanediol yield. It can be seen from Figure 3.15 that the inhibitor content of the
experimental group was the lowest while the content of 2,3-butanediol was the high-
est. Compared with one-phase steam explosion (1.2 MPa/8 min), the inhibitor content
was reduced by 33%, and fermentation product 2,3-butanediol content increased by
209%. Compared with the 2,3-butanediol fermentation with only sugar as the carbon
source, the 2,3-butanediol content of the experimental group was higher than that
of the control group of sugar, while the sugar content of other groups was lower than
the control group, which showed that inhibitor produced under the pretreatment con-
dition of the experimental group not only had no inhibition to the production of
2,3-butanediol, but also promoted the conversion of 2,3-butanediol; while the inhi-
bitors produced under the pretreatment condition in other groups inhibited the gene-
ration of 2,3-butanediol.
3.4.3 Technical evaluation of steam explosion technology

Prof. Chen established the steam explosion and component separation technology
based on 10 years of research, which formed the lignocellulose refining technology
platform. Based on this platform, a series of cost-effective lignocellulose refining pro-
cesses were developed and bio-based energy, bio-based chemicals, and bio-based
materials and many other products were produced.
0.45
0.40
0.35
Inhibitor
Conversion (%)
0.30 2,3-BD
2,3-BD in fermentation control group
0.25 (using glucose as the only carbon source)
0.20
0.15
0.10
0.05
1.1(4)–ISFC–1.2(4) 1.2(8) 1.1(4)–1.2(4) 1.5(4)
Conditions
Figure 3.15 Effect of the two-phase steam explosion carding method on 2,3-butanediol (Zhang
et al., 2012). 1.1(4)-ISFC-1.2(4) indicates 1.1 MPa, 4 min-ISFC-1.2 MPa, 4 min, etc.
Lignocellulose refining has various advantages based on steam explosion as the

core technology:
(1) Steam explosion can be applied to a variety of plant lignocellulosic raw materials, and pre-
treatment conditions are easy to control.
(2) Three components (i.e. hemicellulose, lignin, and cellulose) can be separated in three dif-
ferent separation processes to give water-soluble components, alkali-soluble components,
and alkali-insoluble components, respectively.
(3) Cellulose conversion rates in hydrolysis can reach the theoretical maximum.
(4) After the steam explosion lignin can still be used for the production of other chemical
products.
(5) Sugars from hemicellulose can be completely used, and can be converted into liquid fuels.
(6) Fermentation inhibitors generated in steam explosion pretreatment can be reduced by con-
trolling the pretreatment conditions.
(7) The temperature and pressure of the steam explosion process can be controlled separately.
(8) In situ steam explosion of hemp material can be achieved, which avoids the entanglement
and knotting of the material.
(9) The costs of steam explosion pretreatment are relatively low compared with other
pretreatments.
3.4.3.1 Comparison of different pretreatments

As shown in Table 3.4, based on the existing pretreatment techniques, the following
conclusions can be drawn:
Table 3.4 Comparison of different pretreatment technologies

Pretreatment
methods Advantages Disadvantages
Mechanical Decrease of particle size, High energy consumption, high

grinding increase of specific surface area, operating costs
decrease of degree of
crystallinity, increase of water-
soluble material
Pyrolysis Using zinc chloride or sodium Complex products; difficulty of
carbonate as a catalyst, pure separation; when the temperature
cellulose can be obtained at low reduces to low value, the
temperature decomposition rate slows down;
the generation of volatile
byproducts
Liquid hot Hemicelluloses recovery is above Low solid loading; high energy
water 80%; cellulose conversion can consumption; low production
reach 90% efficiency
High-energy No swelling of cellulosic Radiation doses higher than
radiation materials; enhanced accessibility 100 Mrad; high processing costs;
and reactivity; high sugars difficult to industrialize;
concentration; shortened time environmental pollution
Dilute acid High hemicellulose yield, low Hydrolysis is slow; the presence
catalytic cost of acid recovery and other issues;
severe equipment corrosion;
by-products production
Dilute alkali Cellulose swelling; reduced High alkali consumption;
cleanliness; higher sugar yields difficulty of reagent recycling;
after enzymatic hydrolysis neutralization, washing, and
other issues; not suitable for mass
production
Ozone Efficient removal of lignin; low Requires a large amount of
toxic compounds concentration; ozone; high production costs
low temperature and atmospheric
pressure
Organic Low capital costs; low inhibitors Presence of corrosion and
solvent production for obstruction of toxicity issues; causes
microbial growth, acidification environmental pollution
hydrolysis, and fermentation
Biodegradation Low energy consumption; Long processing time and long
environmentally friendly production cycle
Steam Shortened pretreatment time; Washing unit reduced the sugar
explosion high enzymatic hydrolysis yields; inhibitors production
conversion; low energy
consumption; wide applications;
no need for size reduction
(1) Traditional chemical treatment and mechanical pretreatment technologies consume more
energy and result in environmental pollution, and so are not suitable for modern industrial
production processes.
(2) Although biological pretreatment is environmentally friendly and has low power cons-
umption, its longer pretreatment time and production cycle limit its application in
engineering.
(3) Compared with other pretreatment methods, steam explosion pretreatment has various
advantages such as low energy consumption and environmental friendliness, which is a
favorable direction in the development of pretreatment technologies. However, its high
temperature and long cooking time result in low pretreatment efficiency. Meanwhile, pre-
treatment conditions should be varied for the different feedstocks.
3.4.3.2 Pretreatment economy

The costs of steam explosion pretreatment are lower compared with other pretreat-
ments. For example, the steam consumption of general materials is 0.2–0.5 tons steam
per ton of feedstock, which indicates the low costs of energy and reagent consumption
in steam explosion. Meanwhile, the labor costs are significantly lower than other pre-
treatment techniques. The capital costs of pretreatment are shown in Figure 3.16.
Based on the structural characteristics of lignocellulosic feedstock and the require-
ments of the target product, lignocellulose utilization in modern industrial production
processes can be achieved by introducing steam explosion pretreatment and selective
Pollution
SE-4
Maintenance
SE-3 Solvent
Energy consumption
SE-2 Manpower
SE-1
SE-acid-2
SE-acid-1
SE-ammonia
Mechanical milling
0 100 200 300 400 500

Pretreatment cost (tty RMB/year)
Figure 3.16 Capital costs of different pretreatment technologies. The conditions of steam
explosion (SE): 1/2/3, temperature 167 C, time 5 min, initial moisture content 0.7/0.5/0.3,
charge coefficient 80 kg/m3; 4, temperature 167 C, time 5 min, initial moisture content 0.3,
charge coefficient 87.6 kg/m3. The conditions of steam explosion with acid addition (SE-acid):
1/2, the ratio of SO2 to feedstock (dry weight) 1.6%, temperature 164 C, time 5 min, initial
moisture content 0.5/0.3, charge coefficient 80 kg/m3. The conditions of steam explosion with
ammonia addition (SE-ammonia): the ratio of SO2 to feedstock (dry weight) 1:10 (w/w),
temperature 164 C, time 5 min, initial moisture content 0.5/0.3, charge coefficient 80 kg/m3.
tty RMB/year stands for ten thousand yuan per year.
Cellulose
screening
grinding
Polyether
Fiber cells
glycol
Cellulose
Parenchymal Enzymatic
hydrolysis
Fermentation Bioenergy
cells
Steam Enzymatic Chemical

Biomass explosion Hemicellulose hydrolysis
Fermentation
products
Solid
Pyrolysis
residues
Washing
liquid
Bio-oil
Lignin Phenolic resin
Xylo-
oligosaccharide
Figure 3.17 Schematic flow chart of steam explosion technology as the core technology in
lignocellulose biorefining.
component deconstruction into the conversion process, which also results in minimal
energy consumption, optimum conversion efficiency, and the maximum amount of
clean production. Such an idea is the core concept for the lignocellulose biorefining
process using steam explosion pretreatment technology, and aims to achieve the max-
imum economic benefits from lignocellulosic resources. A schematic diagram of raw
material utilization after steam explosion is given in Figure 3.17.
3.5 Establishment of the sugar platform

The establishment of sugar platforms is the process whereby the constituents of ligno-
cellulosic feedstock (including hemicellulose, cellulose, pectin, soluble sugars, and
other ingredients) can be directly converted into sugar, which can then be used in
an industrial process or as the basis for further conversion.
Sucrose and starch are generally used directly as raw sugars for industrial produc-
tion because they are easy to obtain and ferment, and are fit for industrial production.
However, the current supply of sucrose and starch cannot meet the needs of modern
industry. Cellulose, hemicellulose, and other lignocellulose components can be con-
verted to sugar for industrial utilization due to their abundant reserves and renewabil-
ity, and this will help to ensure food security.
3.5.1 Hemicellulose platform

3.5.1.1 Introduction
Hemicellulose is a general term for a group of complex polysaccharides in plant
cell walls; it is the second largest category of plant cell wall polysaccharides, and
mainly exists in the primary walls and secondary walls of the plant cell walls. The
structure of hemicellulose is complicated, and is primarily composed of several dif-

ferent types of pentoses (b-D-xylose, a-L-arabinose), hexoses (b-D-glucose, b-D-man-
nose, a-D-galactose, a-L-rhamnose, and a-L-fucose), and glycolytic acid (a-D-glucose
fermentation acid, a-D-4-O-methyl-glucose acid, and a-D-galacturonic acid). Hemi-
cellulose is formed by a glycosidic bond between the monosaccharide groups.
Hemicellulose is closely attached to cellulose through an oxygen–hydrogen bond
linkage and van der Waals forces, which is considered to be a bridge between the
fiber fines. Hemicellulose and lignin form the hemicellulose–ferulic acid–ether
bond–lignin bridge structure with ferulic acid. Some hemicellulose polysaccharide
chains have two ferulic acid molecules, or even have a side chain connecting with
coumaric acid molecules. In addition, there are also connections between hemicellu-
lose and protein, most generally the hydroxyproline residue in the 3- or 4-position con-
necting to arabinose in hemicellulose. Compared with cellulose, hemicellulose has a
naturally low molecular weight and is also multibranched. The average degree of
polymerization (DP) of hemicellulose is 80–200. Hemicellulose has different struc-
tures according to its different biological origins.
3.5.1.2 Methods of establishing a hemicellulose platform

Alkali method
The traditional separation of components is primarily achieved by industrial pulping.
In the alkaline pulping process, more complete cellulose can be obtained, but hemi-
cellulose and lignin are degraded into small molecules and discharged into the black
liquor. The alkali method is the most common separation method for hemicellulose;
the method not only swells the cellulose, but also breaks the connecting bonds (ester
bonds, ether bonds) between hemicellulose, lignin, and hydroxy cinnamic acid, and
hence dissolves hemicellulose from the cell wall.
Acid method
Acid hydrolysis can be used for the preparation of monosaccharide. Hydrochloric
acid, sulfuric acid, trifluoroacetic acid, formic acid, and nitric acid are commonly used
in acid hydrolysis. Compared with other methods, acid hydrolysis results in a higher
sugar yield and good reproducibility. However, acid hydrolysis will produce large
amounts of degradation products from monosaccharides such as furfural generated
from pentose and hydroxymethylfurfural produced from hexose (which further
degrades into formic acid and levulinic acid). Therefore, the type of acid, pH, reaction
temperature, and reaction time should be considered carefully in acid hydrolysis.
Autohydrolysis method
The autohydrolysis method is also called the liquid hot water method, and is most
commonly used in the production of oligosaccharides. Under conditions of high tem-
perature and pressure, hydration oxygen ions in water and acetic acid generated from
acetyl in hemicellulose cause the cleavage of glycosidic bonds, which are the back-
bone of hemicellulose, the degree of polymerization of hemicellulose reduces, and the
desired products dissolve into the hydrolysis solution. Most of the cellulose and lignin
are retained in the residue. Then the hydrolyzate is separated and purified, by-products
and nonsugar components are removed, and high-purity oligosaccharides are
obtained. The autohydrolysis method has many advantages including not requiring
any chemicals other than water, noncorrosivity to equipment, higher enzymatic reac-
tion rate, milder reaction conditions, and less degradation of the cellulose-rich residue.
However, the hydrothermal treatment will produce degradation products from the
monosaccharide, including formic acid, acetic acid, levulinic acid, furfural, and a
few lignin degradation products.
3.5.1.3 Product development of the hemicellulose sugar platform

Hexoses from hemicellulose can be used for ethanol production by fermentation and
sorbitol preparation by reduction; these have important applications in the food, tooth-
paste, cosmetics, explosives manufacturing, and papermaking fields. Five-carbon
sugars are used to produce multifeed yeast, bran acid, xylose, and xylitol. Xylitol
can be produced from xylose by using a chemical method of oxygen catalysis under
high-pressure.
3.5.2 Cellulose platform

Cellulose is the largest component of plant cell walls, and is composed of homoge-
neous b-1,4-glycosidic bonds. Commonly used conversion methods for cellulose
include acid hydrolysis and enzymatic hydrolysis.
3.5.2.1 Methods of establishing a cellulose platform

Acid hydrolysis
Acid hydrolysis includes both concentrated acid hydrolysis and dilute acid hydrolysis.
Concentrated acid hydrolysis was first reported in 1883. The principle of concentrated
acid hydrolysis is that crystalline cellulose can be completely dissolved in 72%
sulfuric acid or 42% hydrochloric acid or 77–83% phosphoric acid at a lower temper-
ature, resulting in the homogeneous hydrolysis of cellulose. During this process, cel-
lulose can be converted into several oligosaccharides containing glucose units, mainly
cellotetraose (four-glucose polymers). With further dilution by water and heating for
a certain time, cellotetraose is hydrolyzed to glucose. Concentrated sulfuric acid
hydrolysis technology is more mature than other concentrated acid methods, and
about 90% of sugars converted from cellulose and hemicellulose can be recycled.
Two hundred grams of dry pulverized raw material is mixed with 500 g sulfuric acid,
and then diluted to 20–33% sulfuric acid. The hydrolysis is conducted at 100 C for
30–120 min and the corresponding yield of sugar is 78–82%. The most obvious advan-
tage of concentrated acid hydrolysis is its higher sugar yield. However, concentrated
acid hydrolysis needs a long reaction time, and high concentrations of acid, which
results in serious corrosion of the equipment. Meanwhile, high acid concentrations
will lead to environment pollution which is difficult to recycle, further limiting the
development of concentrated acid hydrolysis.
Dilute acid hydrolysis is a process in which cellulose is hydrolyzed to glucose

monosaccharide by using an inorganic acid such as sulfuric acid or hydrochloric acid
as the catalyst, generally under a 10% (w/w) load. The hydrolysis reaction temperature
is usually between 100 and 240 C, and the pressure is usually more than 1 MPa,
which is above the saturated vapor pressure of the liquid. Dilute acid hydrolysis
put forward by the Frenchman Mel Parsons in 1856, is a simple process. Dilute acid
hydrolysis has the advantages of low acid concentration, low impact on the environ-
ment, simple waste processing, and low raw material costs. However, because the
hydrolysis process requires an environment with high temperature and pressure,
the development of the dilute acid hydrolysis process was initially very slow. With
the development of chemicals and equipment, and the appearance of a variety of
new materials that can tolerate violent temperature, pressure, and acid, dilute acid
hydrolysis has developed quickly. Because the dilute acid hydrolysis process produces
by-products such as formic acid, acetic acid, 5-hydroxymethylfurfural (5-HMF), and
phenolic compounds, researchers should continue to study various physical, chemical,
and biological methods to remove cellulose hydrolyzate and fermentation inhibitors to
improve fermentation yield.
Factors influencing dilute acid hydrolysis include the degree of grinding of the
cellulosic feedstock, liquid-to-solid ratio, reaction temperature, reaction time, acid
concentrations, and co-catalyst type and concentration. The higher the degree of
grinding of the cellulosic feedstock the greater the contact area for the acid catalyst,
resulting in better hydrolysis performance. When the reaction rate is fast, mono-
saccharide can be removed from the solid surface in a timely manner, which is favor-
able for the reaction. The liquid-to-solid ratio is the ratio of the volume of water
to the quality of solid material. Generally, with an increase in the liquid-to-solid
ratio, sugar yield from the cellulosic feedstock also increases. But the cost of hydro-
lysis increases, and the sugar concentration decreases, increasing the cost of the
subsequent fermentation and distillation processes. The liquid-to-solid ratio of
5–20 mL/g is usually chosen for the conversion process. Temperature is an impor-
tant factor affecting the rate of hydrolysis. Generally, when the temperature rises by
10 C, the hydrolysis rate will increase by 0.5–1 times. However, high temperature
will accelerate the decomposition rate of the monosaccharide. Therefore, when high
temperature hydrolysis is used, the reaction residence time should be reduced. The-
oretically, if the other conditions remain unchanged, the concentration is double, and
the acid hydrolysis time can be shortened by one-third to one-half. The increases of
acid concentration lead to increased process costs, while the corrosion-resistance
requirements of the equipment will increase, resulting in increased equipment costs,
which is not suitable for industrial production. Generally, the acid concentration
should not exceed 10%.
Previous studies of acid hydrolysis focused on inorganic acids including hydro-
chloric acid and sulfuric acid. The efficiency of hydrochloric acid hydrolysis is supe-
rior to sulfuric acid, but the treatment of waste is more difficult than with sulfuric acid.
Meanwhile, hydrochloric acid is more expensive than sulfuric acid and requires equip-
ment with greater corrosion resistance.
Enzymatic hydrolysis
Enzymatic hydrolysis has been used since the 1950s. With the new interest in cellu-
lose hydrolysis in biology, it has attracted increasing attention. Cellulose can be
hydrolyzed to sugar using cellulase at 45–50 C and pH 4.8. Cellulase is not a single
substance; it comprises three main components, i.e., endoglucanase, exoglucanase,
and b-glucanase. Endoglucanase cuts the b-1,4 glycosidic bonds randomly, and the
cellulose long strand is cracked, with the broken molecular chains having a reducing
end and a nonreducing end; exoglucanase comprises two components, which cut glu-
cose and cellobiose from the reducing end of the long chain, respectively; and the role
of b-glucanase is to convert cellobiose and short-chain oligosaccharides into glucose.
Enzyme hydrolysis can be carried out at normal temperature and pressure, reducing
the energy consumption of the process. The enzyme has a high selectivity to produce a
single product from the substrate, and a high yield of glucose (>95%) can be obtained.
Because the cellulase has to enter the inner part of cellulose and then convert it into
sugar, pretreatment should be done to remove hemicellulose and lignin or destroy the
crystalline structure of cellulose. Typically, in order to facilitate enzymatic hydrolysis,
the acid hydrolysis and enzymatic hydrolysis are combined with a pretreatment.
3.5.2.2 Products from cellulose sugar platforms

Cellulose is composed of glucose, so the cellulose platform can meet the needs for
conversion of glucose to industrial products, such as sorbitol, ethylene glycol, 1,2-
propanediol, and various fermented products.
3.6 Establishment of the lignin platform

3.6.1 Introduction
Lignin is the cheapest raw material on earth that can provide aromatic compounds.
Currently, in the industries using plant fiber as raw materials (such as papermaking,
fiber textile, wood hydrolysis, and bio-fuels), lignin is discharged as waste; this is not
only a waste of resources, but also an environmental pollutant. Therefore, with the
increasingly short supply of petrochemical resources and worsening environmental
pollution, recycling of natural lignin to replace oil and other nonrenewable resources
can not only alleviate the situation of overreliance on petrochemicals, but also reduce
environmental pollution. However, due to the complex structure and the wide range of
molecular weights of lignin, it is unstable in its physical and chemical properties,
which results in an inability to obtain products with costs comparable to those from
petrochemicals. Therefore, lignin can only act as a partial replacement for fossil-based
resources, taking advantage of its low price to make up for the deficiencies in product
performance. It is not able to achieve the goal of high-value utilization due to the
issues mentioned above. The first step toward changing the inefficient use of lignin
is to overcome the unstable nature of lignin itself and to create relatively homogeneous
and stable active products; this is also the most important step to achieve high-value
utilization of lignin.
Lignin, hemicellulose, and cellulose are the three main components of plant cell
walls, and are widely present in vascular plants. The total amount of lignin on earth
is exceeded only by cellulose. The chemical structure of lignin differs from cellulose
and hemicellulose: it is a polymer formed by a three-dimensional network structure
mainly taking aromatic benzene propane as monomer by connecting with the
CdC bond or ether bond. Because of its differences from the other two kinds of poly-
saccharides, the development and utilization of lignin has often not been as good as the
more highly valued cellulose and hemicellulose. However, because the lignin content
in lignocellulosic feedstock is up to 30% and the energy content is as much as 40%,
more attention should be paid to lignin in the lignocellulose biorefining process.
We must have a comprehensive and detailed understanding of lignin before using
it. In 1838, P. Payen in France isolated cellulose from wood, and he also found a com-
pound that had a higher carbon content, which he called “real wood material” (the true
woody material). After that, F. Schulze carefully isolated this compound, and it was
named lignin, which was derived from the word for timber in Latin. However, due to
the paucity of lignin applications, initial lignin chemical research made no great pro-
gress for decades. In the 1870s, with the industrialization of sulfite pulping, people
became interested in chemical reactions in pulping, which led to an upsurge in
research on lignin. Thereafter, due to the value of its research applications, lignin
research developed rapidly. Although a variety of modern sophisticated analytical
instruments have been gradually applied to lignin structure analysis, including two-
dimensional and three-dimensional nuclear magnetic resonance analysis, electron
spin resonance absorption spectroscopy, and HPLC, there is no full understanding
of its complicated structure.
Based on current knowledge, the structure of lignin is generally composed of three
benzene propane monomers, and a three-dimensional network polymer is built
through CdC bonds and ether linkages bonds. The three monomers include guaiacyl
propane (G), syringyl (S), and p-hydroxyphenyl (H) (Figure 3.18). Meanwhile, there
are differences in the content of these three monomers in different plants. Lignin in
softwood is mainly constructed by the guaiacyl structural unit; lignin in angiosperms
is composed of guaiacyl structural and syringyl; and lignin in grassy plants is com-
posed of guaiacyl, syringyl, and p-hydroxyphenyl. Covalently, bonds connecting
the structural units include b-O-4 aryl ether; b-1, b-5, b-b, a-O-4 aryl ether; and diphe-
nyl ether linkages. Due to the complex combination, there are significant differences
in the structure of the lignin polymer molecules, leading to instability of subsequent
products from lignin; this is an important reason for the difficulties in achieving high-
value utilization of lignin.
3.6.2 Methods of establishing a lignin platform

As mentioned above, the natural lignin in different plant cell walls has large differ-
ences, and the different separation methods will make the already complex polymer
have even greater differences, and this determines its application in different fields.
HO γ Lignin Lignin
OCH3 Lignin Lignin
R OH OH
α β O γ γ Oα
OCH3 β H3CO OCH3
α O β β O O
α γ
OCH3 O OH
Lignin O
O HO
Lignin OCH3
OCH3
(a) (b) (c) (d)
O OH
Lignin γ
Lignin Lignin OH OH
OH β
α
6 2
6 2 6 2
5
OCH3 H3CO OCH3
Lignin Lignin
Lignin Lignin
(e) (f) (g) (h)

Figure 3.18 Structures of lignin monomers and their linkages.
In fact, research on lignin is currently focused on two aspects. One is the analysis of
lignin, including structural analysis in the separation process, reaction activity anal-
ysis of different lignin types, and analysis of the relationship between the structure of
lignin and its physical and chemical properties. The second aspect is the application
of lignin, which is the ultimate goal of theoretical lignin research. Here, the different
lignin types are briefly introduced (shown in Table 3.5) based on structure, perfor-
mance, and major applications.
Table 3.5 Separation reagents and applications of different

lignin types
Reagent Applications
Analytical Milling wood Water/dioxane Lignin structure analysis

lignin lignin
Klason lignin Sulfuric acid Lignin quantitative analysis
Industrial Kraft lignin NaOH/NaS Burned for energy recovery

lignin Alkali lignin NaOH/ Filler/binder/fertilizer
anthraquinone
Lignosulfonate NaHSO3/Na2SO3 Binder/dispersant/retarder/
emulsifier
Organosolv lignin Organic solvent Filler/phenol substitute
Hydrolysis lignin NaOH/organic Filler/sorbent/phenol
solvent substitute
Steam-exploded NaOH/organic Filler/phenol substitute
lignin solvent
3.6.2.1 Analytical lignin

The reason for the relatively backward research situation of lignin is due to lack of
clarity regarding lignin applications. Lignin’s complex structure is another main rea-
son. Even so, researchers have proposed two commonly used separation methods to
produce analytical lignin materials. Lignin obtained from these two methods is milling
wood lignin and Klason lignin. The former is used for lignin structure (qualitative)
analysis, and the latter is mainly used for the quantitative analysis of lignin.
Milling wood lignin

One important reason why structural research of lignin has been impeded is the dif-
ficulty of lignin separation. Even today, it is not feasible to successfully isolate non-
deteriorated lignin from plant tissues. This is because the lignin itself contains reactive
groups that are prone to be degraded or self-condensed in the separation process.
Almost pure natural cellulose is found on cottonseed cotton fibers, which advances
the study of cellulose. If nearly pure lignin existed in plant organs, lignin research
would be relatively easy to carry out. But because newly grown tissues in plants
do not contain lignin, which only begins to appear after a certain period of time, such
hopes of lignin acquisition are dashed. Therefore, in the study of the lignin structure in
plant tissues, there are no analytic techniques that do not involve components sepa-
ration. In 1957, Björkman separated lignin from vibration milling wood flour with
aqueous dioxane, and the lignin obtained was called milling wood lignin
(Björkman, 1956). Because the structural changes are relatively small in the separa-
tion process, milling wood lignin is currently suitable for lignin research.
Klason lignin
Klason lignin is the insoluble residue portion after removing the ash by concentrated
acid hydrolysis of the plant tissues, which is also an intuitive method for the determi-
nation of lignin content in plants. After the proposed determination methods of Klason
lignin, a lot of research work was carried out to study the treatment conditions, and it
was considered to be the most direct and the most reliable method for quantitative
lignin analysis and was used as the standard method for lignin determination. The
main steps are as follows: the lignocellulosic feedstock is extracted by benzene and
ethanol, then 72% concentrated sulfuric acid is added and the reaction is conducted
at 30 C for 4 h; the sulfuric acid is then diluted to 3% and reacted for 2 h with reflux,
and the insoluble substrate is weighed as lignin (Sluiter et al., 2008).
3.6.2.2 Lignin for industrial applications

Industrial lignin consists of large quantities of lignin obtained from lignocellulosic
feedstock by different treatments; applications include paper pulp, fiber textile, wood
hydrolysis, and lignocellulose energy. Currently, in the field of lignocellulosic feed-
stock pulp, different lignin raw materials can be obtained according to different pulp
methods, including Kraft lignin from Kraft pulping, lignosulfonate from sulfite pulp-
ing, alkali lignin from alkali pulp, and organic solvents lignin from organic solvent
pulping. In recent years, due to the pressures regarding environmental protection and
the shortage of petrochemical resources, bioconversion of lignocellulose for energy
production has been a hot topic. Lignin from enzymatic hydrolysis residues of
lignocellulose biomass has better prospects because it has more active groups due
to the mild action of enzymatic hydrolysis. With the expanding application of steam
explosion pretreatment in energy, textile materials, paper materials, and other fields,
steam explosion lignin, whose structure is similar to the lignin generated from acid
hydrolysis of wood, will be widely used in industry. Due to the effect of pretreatment
on the removal of sugar, its sugar content is significantly lower than other industrial
lignin materials.
Kraft lignin
Kraft lignin is a kind of industrial lignin obtained from Kraft pulp, which accounts for
about 85% of the total lignin production in the world. The Kraft pulp method is the
main method for converting coniferous wood to pulp; the pulping yield is higher than
other alkaline pulping methods. In the Kraft cooking process, about 90–95% of the
lignin is dissolved into the cooking liquor containing sodium hydroxide and sodium
sulfide. In the pulping process, the lignin macromolecules are fractured, the molecular
weight is decreased, the lignin is dissolved in alkaline solution, making the solution
turn dark brown. Currently, production of Kraft lignin is about 630,000 tons per year,
it is mainly used in the form of combustion for heat recovery, resulting in low-value
utilization. Although high-value utilization of Kraft lignin has been reported, there has
been no good progress in industrialization.
Alkali lignin
Alkali lignin is the lignin obtained from soda-anthraquinone pulping, during which
grasses such as wheat straw, bagasse, and others are used as raw materials. The main
difference between soda-anthraquinone pulping and Kraft pulping is that the lignin
from the former does not contain sulfur. Owing to the characteristics of raw materials,
both the viscosity of the black liquor of alkaline pulping and its silicon content is
high, which adversely affects combustion and evaporation in the recovery system.
However, higher purity lignin from the black liquor of alkaline pulping can
be recovered by the acid precipitation method with repeated washing.
Lignosulfonate
Lignosulfonate comes mainly from traditional sulfite pulping and other modified sul-
fite pulping processes. In the sulfite pulping process, sulfite ions are substituted for
phenyl propane on the functional groups of side chains. The introduced sulfonate
groups dissolve lignin, while most of the cellulose does not change and can be sep-
arated for paper and other fiber products. Meanwhile, there is a small amount of fiber
and hemicellulose dissolved in the solution to form water-soluble monosaccharides
and other substances, which are generally referred to as sulfite pulp waste. After clas-
sification by membrane filtration, high-purity lignosulfonate and small-molecule oli-
gosaccharides or monosaccharides can be obtained by acid hydrolysis, and the former
may be spray dried to obtain a solid product – lignosulfonate. Because lignosulfonate

has prime sulfonic acid groups and is water soluble, it is widely used in industrial lig-
nin utilization.
Organic solvent lignin

Lignin extraction by organic solvents was adopted in the nineteenth century. Because
the lignin in lignocellulose is removed using this method, it can be used in the pulp.
However, the recovery rate of organic solvents is low, resulting in the high costs of this
process. These results lead to this pulping technology not being widely used. Later,
due to its low environmental pollution compared with other pulping processes and
the high purity and activity of the lignin derived, organic solvent extraction has
become a hot research area in recent years. Currently, there are two main organic sol-
vent pulping methods. One is the ethanol method, during which the acetic acid gen-
erated from the cooking of raw materials is used as a catalyst, resulting in the
depolymerization of lignin. The generated lignin is called ethanol lignin. The other
method is the high-boiling point ethanol method, which is mainly based on the high
boiling point of solvents and can be cooked at normal pressure, resulting in a high
recycling yield. This lignin is called high-boiling solvent lignin.
Enzymatic hydrolysis lignin

Enzymatic hydrolysis lignin is separated from lignocellulosic raw materials after
enzymatic hydrolysis. The extraction methods used include aqueous alkaline extrac-
tion and organic solvent extraction. Because the reaction conditions of enzymatic
hydrolysis are mild, enzymatic hydrolysis lignin has more active groups compared
with pulp lignin, which can be used as green materials in polymer modification. Enzy-
matic hydrolysis lignin also helps to improve the economic efficiency of the enzy-
matic conversion process of lignocellulose.
Steam exploded lignin

Steam exploded lignin is from lignocellulosic feedstock after steam explosion
pretreatment. Some ether bonds are cracked, molecular weight is reduced, and
the activity of phenolic hydroxyl groups is increased by weak acid hydrolysis
in the high-temperature steam explosion process (Wang and Chen, 2013b).
Accompanied by the hydrolysis of hemicellulose, the purity of lignin increases.
At present, because steam explosion pretreatment of lignocellulosic feedstock is
widely used in lignocellulose refining, steam exploded lignin as an additional
product has also attracted a lot of attention (Wang and Chen, 2014).
3.6.3 Product development of the lignin platform

Lignin applications are important for lignocellulose refining. Due to the differences
in the complex structure and the various extraction methods used for lignin, the
chemical properties of the separated lignin are different, resulting in various
utilization methods, low utilization efficiency, and difficulties of high-value utiliza-

tion (Wang and Chen, 2013a).
3.6.3.1 Applications in agriculture

Fertilizer modifier
Lignin contains many active groups and can be slowly degraded by microorganisms in
the soil, and converted to humus. Humus has a certain effect on the activity of soil
urease, which improves soil quality and promotes fertilizer efficiency. With the
change in agricultural production methods and the reduction of compost and manure
application rates, farmland eventually becomes barren. Thus, the demand for organic
and inorganic compound fertilizers is greatly increased. As a natural polymer com-
pound, lignin will be widely applied in terms of improving agricultural fertilizers.
Slow-release nitrogen fertilizer can be obtained by using ammoniated oxide-modified
alkali lignin. Lignosulfonate can also be used as slow-release nitrogen fertilizer raw
material; for example, calcium lignosulfonate has a certain inhibiting effect on urease
activity, as well as nitrification and denitrification effects, and it can reduce the loss
of ammonia volatilization (Clay et al., 1990). Chelate fertilizer or fertilizer can be
prepared with lignin and other fertilizers as raw materials, such as lignin compound
fertilizer and lignin chelate fertilizer.
Pesticide release agent

Lignin has the natural property of inhibiting the release of agricultural chemicals.
Based on the network structure of lignin, insecticides, herbicides, and biocides can
be easily introduced into the lignin structure by physical or chemical methods. Pes-
ticide formulation ingredients gradually spread from the base to the surface of the
preparation, which plays the role of relieving the release of efficacy. Compared with
ordinary particle pesticides, sustained-release pesticides made from strong polar pes-
ticides had a long-lasting function during indoor rice control experiments. The releas-
ing agent pesticides produced from lignin can provide a cost benefit of 200 Yuan per
ton. It has many advantages including high efficacy, long-term efficacy, the saving of
the number of chemicals used, and the reduction of pesticide loss (Yang, 2001).
Feed binding agent

Lignin can be added to granular compound feed, which can play the role of binder and
improve the granularity, reduce the powder in granular feedstuffs and the return rate of
the powder, and reduce the production cost of the feed.
Liquid film
Polyethylene plastic film has been widely used in agricultural production, but it cannot
be degraded. It generates white pollution, which is a problem that needs to be
addressed. Lignin is a soluble natural polymer. The film can be obtained by adding
alkali, which also has certain strength. If a small amount of formaldehyde is added
to the lignin solution as the cross-linking agent, the molecular weight and the strength
of the film increase. In addition, a small amount of short fibers or other soluble
polymer compound can be added to further increase the strength of the film. The
advantages of this film include the fact that the film forms on the surface of the soil
and that labor intensity is reduced due to the self-bursting effect. It will gradually
degrade into humic acid fertilizer, and can improve the granular structure of soil.
Before it degrades, the film covering on the soil surface prevents the evaporation
of soil moisture and the growth of weeds. Because lignin has antimicrobial actions
and the ability to absorb ultraviolet light, it can increase soil temperature and help
the crops improve their resistance to disease. Pesticides and fertilizers can be added
to this film to generate multifunctional composite film, and the cost is less than some
synthetic mulches.
Soil ameliorant
In recent decades, a large quantity of nitrogen has been used, and the content of phos-
phorus and potassium in the soil has become seriously unbalanced, combined with a
lack of knowledge about the use of organic fertilizers and farm manures. These factors
result in soil degradation, and hence some of the granular structure of the soil is
severely damaged. Lignin can be slowly degraded into humic acid in the soil, so that
the granular structure is regenerated or enhanced, which improves soil structure and
ameliorates the effects of over-farming. For example, the ratio of lignin, NaOH, and
hexamethylene tetramine of (100–120):(10–12):(20–30) (dry weight) can be used to
prepare the soil conditioner, and it can be applied to many types of soils, such as forest
tundra, sandy soils, or solid soils. Lignin’s molecular structure contains a hydroxyl
group and a sulfonic acid group, which may bind the sand particles. Zaslavsky and
Rozenberg reported on soil improver preparation methods that used lignosulfonate
and graft copolymerization of vinyl monomers, and pointed out that the modified
products can also be used to resist wind erosion (Zaslavsky and Rozenberg, 1981).
3.6.3.2 Applications in high polymer materials

Polymerization reactions with monomer/polymer materials
Applications of lignin in the field of polymer materials include primarily two methods.
One is reactions of lignin with monomers to generate polymer materials, and the other
is mixing lignin with polymer materials directly. Because lignin has many reactive
groups, which are capable of reacting to polymers with a higher activity – such as
some monomeric formaldehydes, propylene oxide, and isocyanate – it can be used
to prepare some modified wood polymer products. Research has been conducted to
replace part of the phenol by lignin in the preparation of thermosetting phenolic resins.
Lignin plays a similar role to the wood adhesive in plants, so the main application of
the modified lignin phenolic resin is in the wood adhesives field. Its main purpose is to
replace part of the relatively high-priced phenol in order to reduce the overall price of
resin without reducing its adhesive properties. However, due to the complexity of the
structure of lignin and the low reactivity of formaldehyde, the replacement rate of
lignin is low. In addition, the modified lignin phenolic adhesives have a darker color,
higher viscosity, and shorter storage time, and are subject to market price fluctuations
of phenol; this results in poor market efficiency in the application of lignin as a phenol
substitute in industrial adhesives. Recently, due to the excellent insulation and flame
retardant performance of phenolic foam, increased use of lignin-modified phenolic

foam materials has been reported. At the same time, the use of urea-formaldehyde
resins and melamine resins modified by lignin in wood adhesives has been reported.
The lignin can react with the free formaldehyde in adhesives, reducing the content of
formaldehyde and increasing the market acceptance.
Lignin-based polymer blends

Lignin is a natural macromolecule. Modified products can be directly formed by mix-
ing lignin with a number of thermoplastic resins. Lignin, as a bio-based material, is
renewable, which helps to reduce dependence on oil and other nonrenewable
resources. Lignin has good resistance to oxidation and UV radiation, is flame retar-
dant, nontoxic, and reduces microbial degradation. Polymeric materials prepared
by mixing lignin with other polymers include polyethylene, polyvinyl chloride, poly-
propylene, polystyrene, and polyvinyl alcohol. The main problems of such blends are
the compatibility issues of the two different polymer systems. The main solution to
these problems is to improve the compatibility or increase the co-solvent through lig-
nin modification.
Lignin can be mixed with rubber, and replaces part of the carbon black. It can be used
as a reinforcing agent, which is an important field of lignin applications. Preparation of
lignin latex sediment rubber usually involves dissolving the lignin in alkali, and then
adding the mixture to the rubber latex followed by heating with stirring. After the injec-
tion of acid, precipitated coprecipitated gel is prepared. Lignin is not easy to coalesce
into wet particles in the latex dispersion. Under the action of the electrolyte, lignin can
coprecipitate with the rubber. After removing the supernatant, the precipitate is dried,
and then the lignin master batch is obtained. In order to improve the reinforcing effect of
lignin on the rubber, an initiator can be added to induce polymerization between the
lignin and rubber molecules, similar to the process of graft polymerization.
3.6.3.3 Applications in carbon materials

Activated carbon
The carbon content of lignin is up to 50%, so it is a suitable raw material to produce
carbon materials. Preparation of activated carbon includes physical activation and
chemical activation methods. During the physical activation process, material is car-
bonized, and then reacted with vapor and carbon dioxide at a certain temperature to
develop the pores. The prepared activated carbon usually does not require a postopera-
tion to remove impurities. However, the desired carbonization temperature is higher—
greater than 800 C. During the chemical activation process, the activating agents
such as phosphoric acid and zinc chloride are mixed at different temperatures and
the activated carbon obtained needs cleaning by washing. The activation temperature
is low, and the activated carbon pores are more developed.
Carbon fiber
Carbon fiber has the properties of high strength, high modulus, high temperature resis-
tance, corrosion resistance, fatigue and creep resistance, electrical conductivity, and
thermal conductivity. It is mainly used for the preparation of composite materials.
Currently, there are three main raw materials: polyacrylonitrile-based carbon fibers,
pitch-based carbon fibers, and viscose-based carbon fibers. Because of the high carbon
content of lignin, lignin can be used as the starting material for preparing carbon fibers.
The preparation process is to first spin the lignin and the fibers form carbon fibers with
a series of preoxidation, carbonization, and surface treatments.
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conversion engineering 4
4.1 Lignocellulose bioconversion technologies
4.1.1 Characteristics of lignocellulose conversion technologies
The conversion of lignocellulose is widespread in nature, for example wood corrosion
and food spoilage, and is part of the microbial conversion process (Chen, 2013).
Lignocellulosic biomass conversion technology is one of the earliest technologies
exploited by humans. During food storage, natural bioconversion is occurring. For
example, sugar in apples can produce alcohol through microbe fermentation and
the alcohol can further produce acid via oxidative metabolism. Also, Chinese herbal
medicinal materials easily mildew during storage, resulting in changes of drug prop-
erties. The natural fermentation of Chinese herbal medicine occurs due to the various
changes caused by different kinds of microbes. Interestingly, most of the natural
fermentation processes belong to solid-state fermentation. Even fermentation in water
must employ stone as a substrate carrier. Several years ago, people consciously
preserved some excess fruits after the harvest and the fruits began to ferment if the
environment was suitable. Consequently, a natural bioconversion occurs. During
the bioconversion process, sugars in the fruits are first fermented into ethanol by
microbial metabolism, and then the ethanol is partially transformed into acetic acid.
The reaction of ethanol with acetic acid produced some special flavor substances, for
example, ethyl acetate, which adds an interesting taste. In fact, this is similar to solid-
state fermentation, which occurs during the storage process of Chinese herbs. The herb
would be invaded by some microbes, especially molds such as Penicillium sp. and
Aspergillus sp., which produce enzymes and secondary metabolites by using the herb
as a carbon and nitrogen source.
Bioconversion is a process in which the catabolism, anabolism, and formation of
secondary metabolites occurs under anaerobic or aerobic conditions. During the pro-
cess, lignocellulose is transformed into new products to meet market demands. The
bioconversion process requires three elements, namely, the target product, the produc-
tion strain, and the culture environment (nutrition, temperature, humidity, oxygen,
etc.) to meet the needs of the strain (Chen, 2013). Lignocellulose bioconversion is
closely related to people’s daily lives, providing a number of delicious foods such
as bread, fermented bean curd, wine, tea, and others.
The features of bioconversion technology can be summarized as follows:
(1) Mild conditions. Fermentation proceeds under relatively mild conditions (room tempera-
ture and atmospheric pressure), so bioconversion can protect the ingredients from
destruction.

(2) Formation of new metabolites. During the bioconversion process, microorganisms interact
with lignocellulose. Lignocellulose provides nutrition for the microorganisms to promote
microbial growth and metabolism of the microorganisms, while on the other hand new sub-
stances are formed by the modification of the lignocellulose.
(3) Some new small molecules may be formed after bioconversion, which are more easily used
by humans.
(4) Multilevel utilization of lignocellulose. Ingredients in lignocellulose are complex. During
the bioconversion process, lignocellulose is repeatedly utilized and most of the nutrients
can be converted, which is beneficial to the comprehensive utilization of lignocellulose.
4.1.2 Applicability of lignocellulose used in bioconversion

4.1.2.1 Rich in nutrients
Nutrition is the process in which microorganisms get energy and nutrients from the
external environment, which provides structural substances, energy metabolism reg-
ulation substances, and the necessary physiological environment for metabolism
(Zhou, 2004). The basic nutritional elements for microorganisms can be divided into
six categories: carbon sources, nitrogen sources, energy, mineral, water, and growth
factors. The carbon sources are the major nutrients for microorganisms, including
organic carbon sources and inorganic carbon sources. Various sugars, petroleum com-
pounds, and agricultural straw substances are all carbon sources. In the solid-state fer-
mentation process, the carbon source substances often can be used as nutrients as well
as inertia carrier materials that maintain the microorganisms’ growth.
4.1.2.2 Water binding capacity

Substrate water is a basic requirement for the growth of microorganisms. The micro-
organisms could not absorb nutrients without a water solvent. Meanwhile, changes in
the moisture content also affect the aeration and temperature conditions of the sub-
strate, and water will be enriched and consumed around the cells, and then evaporated
to the upper air above the mycelium for heat and mass exchange. The bacterial cell
contains water, known as intracellular water; moisture outside of the bacteria is called
extracellular external water, including the water in the water film and materials.
Water is a necessary nutrient for microbes as well as an important part of the micro-
organism body. Therefore, maintaining the moisture content is of great importance to
the whole conversion process and the characteristics of products during the biocon-
version process. The term water binding capacity refers to the water absorbed by
the unit weight of dry lignocellulose. The porous structure among macromolecular
organics can hold water via capillary effects and surface tension, resulting in the
bound water of lignocellulose that is crucial to microbes’ growth and fermentation
acting as free water. Lots of hydrogen bonds exist between the cellulose macromol-
ecules, cellulose and water molecules, and the interior of the cellulose molecules. The
hydrogen bonds within the cellulose molecules will be unfolded during the water
absorption and swelling of the lignocellulose, and this is conducive to the degradation
and conversion of substrate for microbes. And in this process, the crystalline region
Conversion engineering 89
cannot absorb water. Hydrogen bonds in the amorphous region are unfolded con-
stantly during the moisture absorption process of dry cellulose, leading to the displace-
ment of hydrogen bonds within cellulose molecules by the bonds between cellulose
and water molecules. Although new hydrogen bonds are formed, part of the hydrogen
bonds within the cellulose molecules still remains. Due to internal resistance during
desorption, hydrogen bonds between the cellulose and water molecules cannot unfold
in the reverse direction, resulting in the hysteresis phenomenon. Part of the cellulose-
absorbed water is formed by the hydrogen bond and the hydroxyl within the amor-
phous region and cellulose molecules, which is called bound water. The molecules
of bound water are attracted by the cellulose hydroxyl and thus are arranged in a cer-
tain direction and result in a high density, which leads to the swelling of cellulose and
finally causes a thermal effect. After the cellulose fiber moisture content reaches its
saturation point, water molecules keep going into the cell cavities and pores within the
cellulose to form a multilayer of absorbed water or capillary water, and water of this
kind is called unbound water. Absorbing unbound water does not cause a thermal
effect, or the swelling of cellulose. After solid bodies absorb liquid, though their shape
uniformity does not change, the cohesion within the solid decreases and the volume
increases. As a result, solid materials become soft, which is called swelling (Wexler
et al., 2005).
4.1.2.3 The unique interface property of lignocellulose

Growth of microbes and lignocellulose, water, and heat are mutually affected and thus
a balance is maintained between the four. Shapes and properties of lignocellulose
affect the growth of microbes, while the growth of microbes will, in turn, change
the lignocellulose properties. The growth of microbes produces metabolic heat and
changes the thermal distribution of lignocellulose, and the metabolic heat leads to
a regional heat gradient in lignocellulose. The utilization of water results in an imbal-
ance of water distribution, which leads to a partial water gradient. The effects of tem-
perature on water show up as the evaporation of water and the difference of water
density caused by temperature changes, which will lead to moisture movement and
changes of the physicochemical properties of the water (e.g., glutinousness, density,
and surface tension). Different water contents will affect the growth distribution of
microbes, and further impact the water utilization of microbes and the generation
of metabolic heat. The nonuniformity of water distribution results in water movement
and evaporation. Water evaporation will take away the regional heat and thus regu-
lates the temperature distribution.
The particle size and moisture of the substrate are important factors affecting the
growth and activity of microbes during the lignocellulose conversion process. If fun-
gal hyphae take up the whole particle surface, the biomass won’t increase even
though the nutrients inside the particles remain unused. Small substrate particles pro-
vide greater superficial growth area for microbes and could improve the bioconversion
efficiency dramatically. However, the microbes’ growth will result in substrate clus-
ters when the substrate particles are too small, leading to a decrease of void ratio
within particles and an increase of resistance. In this case, heat and mass transfer
are affected as well as the aeration of microbes, which causes a failure of the microbes
to thrive. At the same time, large particles are conducive to improving heat and
mass transfer and thus provide better aeration conditions due to more space within
particles. But with the increase of hyphae, the space will decrease during the reaction,
leading to a decrease of the effective diffusion coefficients of oxygen and carbon
dioxide.
4.1.3 Classifications of lignocellulose bioconversion technologies

4.1.3.1 Liquid bioconversion technology of lignocellulose
Lignocellulose mainly exists in the solid form. Therefore, it needs to be turned into
soluble materials using a liquid bioconversion technology before effective utilization.
In such a process, cellulose and hemicellulose inside the lignocellulose are converted
into xylose, glucose, and arabinose. The most frequently used hydrolysis methods are
acid-catalyzed hydrolysis and enzymatic hydrolysis.
Acid-catalyzed hydrolysis refers to dilute acid-catalyzed hydrolysis, such as 4%
sulfuric acid or hydrochloric acid hydrolysis. Cellulose and hemicellulose can gener-
ate monosaccharides via dilute acid at certain temperatures. To our knowledge, dilute
acid-catalyzed hydrolysis has been widely used and studied. Reports indicate that the
dilute acid-catalyzed hydrolysis process could dramatically improve the hydrolysis
efficiency of cellulose and hemicellulose. Disadvantages of acid-catalyzed hydrolysis
are that it causes severe pollution to the environment, is highly corrosive to equipment,
and generates inhibitors that impact the bioconversion process. Enzymatic hydrolysis
refers to the process of generating monosaccharides via enzymatic catalysis of cellu-
lose and hemicellulose. Conditions of enzymatic hydrolysis are moderate and no
inhibitor is produced, thus it has become the main direction of application and
research. However, enzymatic hydrolysis is time-consuming and the conversion ratio
is low, which severely hinders its application.
The production of fuel ethanol and butanol via liquid conversion technology is an
important direction of research, and is briefly introduced here. Separate hydrolysis
fermentation (SHF) and simultaneous saccharification and fermentation (SISF) are
two kinds of ethanol preparation technologies that are widely studied. In the SHF pro-
cess, hydrolysis and fermentation proceed sequentially; while in the SISF process,
hydrolysis and fermentation proceed consecutively. Takagi first proposed SSF tech-
nology of cellulose, in which cellulose hydrolysis and ethanol fermentation were per-
formed in one fermentation tank. Compared with SHF, firstly, sugars produced via
cellulose hydrolysis can be used by yeasts in time and turned into ethanol via fermen-
tation, and the glucose concentration is low during the whole fermentation process,
which has relatively weak inhibition on cellulase. Secondly, the metabolic detoxifi-
cation of microbes can reduce the inhibitors of cellulase generated in the pretreatment
phase, and thus improves the enzymatic efficiency and reduces the amount of cellulase
utilization. Lastly, SISF has the advantages of simple equipment and low risk of
microbial pollution. However, in the SSF process, the optimal reaction temperature
of cellulase is 50 C while that of yeasts is 30 C. Therefore, in order to balance
the temperature difference, 38 C is widely used in research. Because of this compro-

mise, the enzyme activity and fermentation efficiency cannot reach the maximal value
during the whole process (Chen and Li, 2013).
4.1.3.2 Solid-state bioconversion technology of lignocellulose

Solid-state bioconversion technology of lignocellulose refers to the triphase system
where gas is the continuous phase while the liquid film and the solid phase under the
film is the stationary phase. It should be pointed out that there are no necessary links
between substrate moisture content and free water content. The unique characteristic
of solid-state bioconversion technology is that the substrate is solid, but contains a
little free water just to satisfy the microbes’ requirements for growth and metabo-
lism. Therefore, for a solid substrate with high retention ability such as plants
and sugar beet, free water is still low within the solid phase even though the water
content of the fermentation substrate is more than 80%. That is to say, moisture con-
tent is not the only criteria on which to define solid-state bioconversion. The most
essential characteristic of lignocellulose is its solid-state property, which makes it
more suitable for a solid-state bioconversion process. For solid-state fermentation,
substrate requirements include the following aspects. The solid substrate not only
provides the nutrients needed by microbes, but also acts as the fixture for the cells.
As a porous supportive carrier formed by biomacromolecules, lignocellulose is an
excellent solid-state fermentation substrate. Meanwhile, the supporting role and
porous structure of solid materials provide good conditions for microbial growth
both on the lignocellulose surface and inside the pores. In this way, the growth of
microbes remains in a relatively stationary state, which decreases energy consump-
tion and investment caused by microbes’ movement. Therefore, it is a type of green
conversion method that is both water saving and energy saving (He and Chen, 2013).
4.1.3.3 Comparison between liquid and solid-state bioconversion

technology
Compared with liquid bioconversion technology, solid-state bioconversion tech-
nology is a one-step conversion mode, which avoids the process of converting poly-
saccharides into monosaccharides from lignocellulose and thus it is in consonance
with the solid characteristics of lignocellulose. The main advantages of solid-state
bioconversion technology are demonstrated in the following aspects: (1) reaction
conditions are closer to the natural environment and the conversion efficiency is
high; (2) the bioutilization ratio is higher, reaction equipment is smaller, investment
is lower, and the production yield is higher; (3) it is more prone to the recycling
transfer of oxygen; (4) the conversion products are diverse; (5) the conversion con-
ditions are various and the demands on the environment are low; and (6) water con-
sumption is low and it produces no waste water (Chen, 2013; Chen and He, 2012).
A comparison between liquid and solid-state bioconversion technology is shown in
Figure 4.1.
Liquid bioconversion Acid

Monosaccharides Fermentation Products
Biomass hydrolysis
technology
Enzymatic
hydrolysis
Solid state bioconversion
technology Biomass Fermentation Products
Figure 4.1 Routes of lignocellulose bioconversion technologies.
4.1.4 Equipment for lignocellulose bioconversion

4.1.4.1 Gas double-dynamic solid-state fermentation bioreactor
Gas double-dynamic refers to the periodic changes of air pressure inside the bioreactor
and the internal air circulation. The air pulse is realized by passing and injecting sterile
air periodically. The pressure pulse can displace traditional mechanical stirring not only
because of its improvement of water evaporation to strengthen evaporative cooling, but
also because of its obedience to the periodic stimulation principle. The pressure range
and pulse period of the cellulase solid-state fermentation process have been studied in
our previous work. Results indicated that the pressure ranges of the air pulse and the
pulse period were important factors for solid-state fermentation. While internal air cir-
culation was another dynamic condition of gas double dynamic, its main aim was to
strengthen heat transfer inside the bioreactor. In addition, the rate of air circulation could
change with different rates of metabolic heat in various fermentative phases.
Prof. Chen proposed new design principles for a bioreactor that uses normal pres-
sure as the source of outside cycle pulsation power to stimulate the fermentation pro-
cess. Based on the characteristics of raw materials and the biological characteristics of
microbes, Prof. Chen designed a pressure pulsation solid-state fermentation technol-
ogy that had completely independent intellectual property rights. On this basis, the gas
double-dynamic solid-state fermentation technology has gradually developed into one
of the modern solid-state fermentation technologies. The gas double-dynamic solid-
state fermentation bioreactor consists of a horizontal solid-state fermentation cylinder,
built-in circular duct, cooling pipes, blowing devices, and an air circulation system.
There are two types of solid-state fermentation cylinder: a binocular body type and
a monocular body type. Pressure pulsation in the gas double-dynamic fermentation
process is accomplished by supercharging and decompressing sterile air. One cycle
of pressure pulsation consists of the stamping stage, decompression stage, maintaining
stage, and the valley stage. The time of the supercharging stage is long and the corre-
sponding curve rises gently. The time of decompression should be as short as possible,
generally from a few seconds to one minute. The solid substrate could suddenly
expand. The time of the high-pressure stage and the atmospheric stage can be set
freely according to different fermentation processes. Usually, the circulation is fre-
quent in the microbial logarithmic growth period. However, in the lag phase and stable
period, the cycle is infrequent. The cycle time ranges from 15 min to 150 min. The wet
solid particles are rapidly loosened by the rapid expansion of gas, which enhances heat
and mass transfer.
The intensification effects of the gas double-dynamic on solid-state fermentation

show up in the following aspects: decreasing the temperature and moisture gradients
of the substrate; loosening the substrate particles and hence providing sufficient space
for microbes’ growth; accelerating the heat transfer rate between the substrate and the
bioreactor; and providing a stimulation effect to the growth of microbes. Success for
the solid-state pure fermentation technology via gas double-dynamic will mark the
maturity of modern solid-state fermentation technology, and this can be summarized
in the following three goals:
(1) To break the monopoly of liquid submerged fermentation technology in the traditional fer-
mentation industry. Many current liquid fermentation technologies can be replaced by mod-
ern solid-state fermentation, for example Bacillus thuringiensis fermentation, azotobacter
fermentation, cellulase fermentation, pectinase fermentation, gibberellin fermentation, and
riboflavin fermentation. In addition, it is possible for solid-state fermentation to take a place
in the antibiotic and organic acid industries.
(2) To open up a new biotech industry. For example, Beauveria bassiana and Metarrhizium ani-
sopliae do not produce conidium when they are cultivated via liquid fermentation, so it is
essential to adopt modern solid-state fermentation in these processes. More importantly, bio-
conversion and the full-use of lignocellulose is a significant task for humans, and modern
solid-state fermentation technology will be the breakthrough of solving this problem. With-
out this full conversion of lignocellulose it is impossible to start many new industries such as
the clean liquid fuel industry (whose typical representative is ethanol), an effective organic
biofertilizer industry, the bacteria feed protein industry, and the feed additive industry.
(3) To improve the traditional fermentation industry. Pressure pulse can shorten the fermenta-
tion period by one-third and the anisothermal operation could improve cell activity. In addi-
tion, solid-state fermentation plays an important role in the combinatorial optimization of
composite flora. In this way, solid-state fermentation can provide new paths to improve
production technologies in traditional winemaking and food flavor making, even creating
new kinds of fermentative food flavors and health foods such as monscuspurpureus from
monascus solid-state fermentation (Thomas et al., 2013).
4.1.4.2 Solid phase enzymolysis coupled with liquid fermentation

In a SSF process, temperatures in the cellulose pretreatment period and the sacchar-
ification and fermentation period are the optimal temperatures for cellulase and yeasts,
respectively. Therefore, it is not truly isothermal SSF. Next, the solid-to-liquid ratio is
a key factor for cellulose enzymolysis. High solid-to-liquid ratio can help improve
ethanol yield and reduce the amount of cellulase, but it will impact the enzymolysis
process due to a high viscosity. In addition, the ethanol concentration inside the reac-
tor should be controlled within 3% because ethanol fermentation is a typical end-
product feedback inhibition process. The fact is that 6–10% ethanol concentration will
inhibit the growth of yeasts.
Based on the problems of solid-to-liquid ratio, and nonisothermal and ethanol feed-
back inhibition of the SSF process, Prof. Chen developed a novel device for coupled
solid phase enzymolysis with liquid fermentation and gas stripping ethanol (shown in
Figure 4.2). This new technology aims to conduct an integrated study of solid enzy-
molysis, partition nonisothermal SSF, and ethanol gas stripping-activated carbon
A
C K
D
H
F F
J
G
B
I
Figure 4.2 Schematic diagram of the nonisothermal simultaneous solid-state saccharification,
fermentation and separation (NSSSFS) system. (A): Condensing water circulation device; (B):
Filter plate; (C): Outer cylinder with heating jacket; (D): Thermal insulation inner column; (E):
Ethanol fermentation zone; (F): Enzymatic saccharification zone; (G): Float valve; (H): CO2
circulation pump; (I): Hydrolyzate circulation pump; (J): Valve; (K): Adsorption column of
activated carbon (Chen and Li, 2013).
adsorption and desorption technology. Research using a 300-L solid enzymolysis-

liquid fermentation and ethanol gas stripping device provided the following results.
The solid-to-liquid ratio of the steam-exploded straw enzymolysis process could reach
1:3. Temperatures of enzymolysis and fermentation were 50 C and 35 C, respec-
tively. Glucose produced in the process could be used by yeasts in the fermentation
area and the ethanol in the fermentation area could be separated on line. Different
kinds of cellulose materials were appropriate for the device and the ethanol concen-
tration could reach 18.96% and 30.29%, for enzymolysis and fermentation, respec-
tively. A high ethanol yield was obtained from steam-exploded corn stalk. Prof.
Chen tested a 110 m3 device on the basis of lab research. In this test, steam-exploded
corn stalk was used as the raw material with a charge amount of 5.4 t, cellulase powder
(2 105 IU/kg) 540 kg, and water 35 t. Thirteen kilograms of yeast extract powder
were added into the system after fermentation for 36 h. Then, after fermentation
for 108 h, ethanol yield reached 15–16% and cellulose conversion ratio reached
71.2%, which indicated that this novel technology had superior industrial application
prospects (Chen and Li, 2013). To alleviate the problems of low substrate loading,
nonisothermality, and end-product inhibition of ethanol during the SSF, a NSSSFS

process was investigated; one novel pilot scale NSSSFS coupled with CO2 gas strip-
ping loop system was developed and tested. The optimal pretreatment condition of
steam explosion was 1.5 MPa for 5 min at an industrial level. In the NSSSFS, enzy-
matic saccharification and fermentation proceeded simultaneously at their own opti-
mal temperatures and were coupled together by the hydrolyzate loop; glucose from
enzymatic saccharification was consumed by yeasts in a timely manner, and the gen-
erated ethanol was separated online by CO2 gas stripping coupled with adsorption of
activated carbon; the solid substrate loading reached 25%; and ethanol yields of
18.96% to 30.29% were obtained in fermentation depending on the materials tested.
Based on the pilot-scale level of the 300-L fermenter and a novel industrial level of
110 m3, a solid-state enzymatic saccharification, fermentation, and ethanol separation
plant had been successfully established and operated. The NSSSFS was a novel and
feasible engineering solution to the inherent problems of SSF, which could be used on
a large scale in the industrial production of ethanol.
4.1.5 Products of lignocellulose bioconversion technologies

4.1.5.1 Solid phase enzymolysis in liquid fermentation
The clavulanic acid molecule has a fused bicyclic b-lactam structure. Clavulanic acid
is a powerful and broad-spectrum b-lactamase inhibitor, which can act on the
b-lactamase produced by Gram-positive bacterium and Gram-negative bacteria to
inhibit drug-resistant bacteria. Clavulanic acid can enhance b-lactam antibiotics
and recover the potency of penicillin on bacteria like Staphylococcus aureus and
Klebsiella pneumonia.
In a traditional clavulanic acid production process via submerged liquid fermenta-
tion, continuous agitation and oxygen feeding are necessary, which increases energy
consumption and the hyphae are affected by shearing force. In addition, clavulanic
acid is prone to decompose, leading to a low concentration of clavulanic acid in
the fermentation liquor and a high separation cost.
Based on the polyurethane foam synthesized by liquefied wheat straw, Prof. Chen
established a new technology for clavulanic acid production via an adsorption carrier
solid-state fermentation method. Results indicated that a certain amount of fermenta-
tion liquor had a great effect on the yield of clavulanic acid due to the restriction of
adsorption ability of the inert carrier. And the fermentation performance was affected
by excess or insufficient fermentation liquor. The inoculum size was closely related to
the porosity of the carrier substrate. For example, when the inoculum size was larger
than the microbe capacity of the carrier substrate, microbes would die due to over-
crowded and insufficient nutrients. Glycerinum was the carbon source for clavulanic
acid production via bioconversion and, therefore, the yield of clavulanic acid would
increase with an increase in the amount of glycerinum additive. Meanwhile, strepto-
mycete itself had a tolerance dose for glycerinum and growth inhibition occurred
when the glycerinum concentration exceeded the limit. In the synthesis of clavulanic
acid, glutamic acid and ornithine converted from a-glutaric acid, which was the
intermediate of the TCA process, so the addition of ornithine could improve the yield
of clavulanic acid. Because LiCl could prevent clavulanic acid from decomposing,
appropriately adding LiCl was conducive to increasing the yield of clavulanic acid
when the whole fermentation period was over (Chen, 2013).
4.1.5.2 Bacterial cellulose production from straw lignocellulose via

solid-state fermentation
Cellulose is a homopolysaccharide composed of b-D-glucopyranose units linked
together by 1, 4-glycosidic bonds. Cellulose, a linear homopolymer of anhydroglucose
units, is composed of crystalline and amorphous regions. In the crystalline regions,
there is a strong interchain hydrogen bonding among adjacent chains of a cellulose
sheet and weak hydrophobic interactions between cellulose sheets. Compared to
the amorphous regions, the crystalline regions are more recalcitrant to attack by
enzymes, playing a major role in determining the rate of enzymatic hydrolysis. Cel-
lulose has a net structure formed by glucose molecular chains via b-1, 4-glucosidic
bonds and the hydrogen bonds both within and between molecules. Researchers first
observed bacterial cellulose through electron microscopy in 1940. Bacterial cellulose
is composed of bunchy fibers with 100 nm width, 3–8 nm thickness, and 0.01–0.1 mm
diameter and each bunch is formed by many microfibers. Bacterial cellulose has
excellent properties like high purity, high degree of polymerization, high degree of
crystallinity, high hydrophily, high Young’s modulus, and high strength and nano
fineness. Bacterial cellulose also has higher biological fitness and better biodegrad-
ability and can be produced from a wide variety of substrates. Due to such properties,
bacterial cellulose has been a potential biomaterial in the food, biomedical material,
composite material, and papermaking industries (Weng and Chen, 2010).
Prof. Chen used Acetobacter xylinum to produce bacterial cellulose via solid-state
fermentation. The results showed that the product yield and productivity were both
higher than that of liquid fermentation. The product yield reached 4.86 g/L on the third
day of fermentation and then it began to decline gradually; the yield was increased at
least five-fold compared with static liquid fermentation. In addition, the volume fer-
mentation productivity reached 1.62 g/L.
4.1.5.3 Xanthan production via solid state fermentation

Xanthan has superior rheological properties, stability, increased viscosity, suspension
properties, and emulsibility, so it can be used as a thickener for the food industry and
an oil-displacing agent for the oil recovery industry. All these applications have made
xanthan one of the most important and highest output bacterial polysaccharides. Prof.
Chen proposed a method for xanthan production via solid-state fermentation based on
the problems of gas-liquid transfer difficulty during xanthan production via liquid
fermentation. In the solid-state fermentation technology, xanthan is produced by
Xanthomonas campeseris fermentation from glucose derived from straw hydrolysis.
Under optimal conditions, the solid-state fermentation system with inert carrier
could adapt to the xanthan fermentation with high carbon source concentration.
Results showed that the concentration of xanthan was first increased and then
decreased with the increase of inoculum size. The maximal concentration was
16.1 g/L, which was obtained with 15% inoculum. Also, solid-to-liquid ratio had a
great influence on the yield of xanthan and the maximal value (15.9 g/L) was obtained
with a 1:15 ratio. The oxygen transfer processes both inside and outside of the carrier
were limited when the liquid substrate exceeded the adsorption ability of polyurethane
resin. Therefore, xanthan yield would decrease when further increasing the liquid sub-
strate concentration. The optimal stacking height of the substrate was 4.5 cm during
fermentation and the corresponding xanthan yield was 17.3 g/L. Oxygen transfer to
the inner layer of substrate was hindered when further increasing the substrate stack-
ing height, which affected the fermentation process. Xanthan yields reached 30.73 and
38.65 g/L with carbon source concentrations of 60 and 80 g/L, respectively, which
were both higher than that via liquid fermentation (22.81 and 21.39 g/L, respectively)
(Zhang and Chen, 2010).
4.1.5.4 Enzyme production by solid-state fermentation

Bioconversion enzymes refer to the enzymes that can hydrolyze or use microbial
lignocellulose in the solid-state fermentation process. Fermentation microbes use
lignocellulose as a substrate and an inducer to produce the enzymes related to metab-
olism. Common invertases include cellulase, lignin enzyme, xylanase, pectinase, lac-
case, peroxidase, and so forth. Prof. Chen successfully achieved the industrialized
production of cellulase using a 100 m3 gas double-dynamic solid-state fermentation
apparatus, which was totally self-developed and designed. In the 100 m3 gas
double-dynamic solid-state fermentation production, with the aim to control the tem-
perature of the medium, the operation parameters adopted were as follows: fermen-
tation initial stage (0–6 h): pulse cycle at 1 h, air circulation speed of 1 m/s;
fermentation starting stage (6–24 h): pulse cycle for 20 min, air circulation speed
of 2.5 m/s; fermentation medium (24–72 h): pulse cycle for 30 min, air circulation
speed of 2 m/s; and end of the fermentation period (72–120 h): pulse cycle for
40 min, air circulation speed of 1.5 m/s. The pulse amplitude of the whole processes
was set at 0–0.2 MPa. Fermentation time was 120 h and the filter paper enzyme activ-
ity of the samples after fermentation was determined. The enzyme activity differed
due to different raw material compositions, which were mostly between 60 and
80 FPU/g dry yeast.
4.1.5.5 Biopesticides production by solid-state fermentation

People are showing a growing interest in the use of insect pathogens and parasitic
fungi for pest control. Producing fungal pesticides from solid-state fermentation
not only reduces the production cost efficiently, but also enhances the drug toxicity
to the pests. Those fungi with insecticidal ability, including Beauveria bassiana
and Colletotrichum truncatum, form the main routes for cultivation by solid-state
fermentation.
4.2 Lignocellulose physical conversion technologies

4.2.1 Mechanisms of lignocellulose physical conversion
technologies
Lignocellulose biomass physical conversion technology refers to the technology that
modifies lignocellulose by a physical method or process to produce high-value prod-
ucts, thereby realizing the high values of lignocellulose. Lignocellulose physical con-
version technologies are mainly applied in relation to the production of compression
molded lignocellulose fuel, artificial board, building materials, and wood plastic
materials. Physical conversion technology does not need complex biochemical con-
version processes and complicated technological process. As a result, it is easy to real-
ize industrialization in some lignocellulose resource-rich regions, such as rural areas
or mountain forest regions.
4.2.2 Products of lignocellulose physical conversion technologies

4.2.2.1 Solid fuel
Compression molding refers to compressing the loose lignocellulose raw materials
into molded materials of high density by high temperature/pressure to reduce the
transportation cost, improve the effective combustion intensity, and raise the thermal
conversion efficiency. In 1948, Japan awarded the first patent that used sawdust as a
raw material to produce rod-shaped molding fuel and successfully realized the com-
mercialization of a rod forming machine. In the 1970s, the internal pressured cylinder
particles forming machine was developed in the United States and used in large-scale
production, with an annual granular molding fuel productivity of 800,000 t. Japan,
Switzerland, Sweden, and other developed countries also carried out research and
development on fuel particle compression molding technology, which was mainly
used for household fuel and industrial power. Molding fuel production in China began
in the 1980s. Until now, the developed technology is mainly rod-like and granular
molding fuels. Rod-like carbonized charcoal molding technology is more mature, with
products exported to Japan, South Korea, and other countries. Particle technology and
equipment research and development have been increasing in recent years; however,
this technology needs to be studied further.
4.2.2.2 Man-made board

Wheat straw, rice straw, cotton stalk, and bagasse are successfully used as raw mate-
rials to produce man-made board, especially wheat straw. Both crop straw and wood
are composed of cellulose, hemicellulose, and lignin. However, they have significant
differences in terms of their structure and chemical composition. As a result, the con-
version characteristics of crop straw and wood are different and so are the reaction
features in sheet manufacturing.
In recent years, China has become the country with the fastest development in the
production of man-made board. According to statistics from the state forestry adminis-
tration, the total man-made board production reached 54.4649 million m3 in 2004. At
present, no man-made panels made from agricultural residues are sold in bulk in China.
Wheat straw particleboard can be found in the ordinary building materials market, but
the sales price is much higher than that of ordinary wood particleboard. From the per-
spective of product development, we should fully use the characteristics of wheat straw
particleboard, which does not release formaldehyde, and proactively develop high-
grade formaldehyde-free straw-based panel products. Wheat straw particleboard pro-
duction technology and processing equipment in China has developed to a relatively
mature stage, and are being constantly refined in the production process.
4.2.2.3 Building materials

Board made from lignocellulose has excellent architectural features. The advance of
modern architecture is based on light and high-strength building materials to alleviate
weight and reduce process costs. These materials must have multiple properties in terms
of fire prevention, heat preservation, heat insulation, sound insulation, antiseismic prop-
erties, prefabrication ability, and so on. In fact, man-made building materials have all the
characteristics mentioned above. In addition, man-made building materials can be used
as the internal and external walls of non-load-bearing frame buildings and ceilings,
closet boards, floors, and building template materials. This man-made architecture offers
the following features: light weight and high strength with a general bulk density of
430–1300 kg/m3; useful for walls, ceilings, built-in wardrobes or cupboards, floors,
and building templates; good energy saving, heat preservation, heat insulation and excel-
lent performance when used as partition. Man-made board has the comprehensive per-
formance needed from construction materials, such as impact resistance, water
resistance, shock resistance, fire resistance, weather resistance, surface machinability,
antimicrobial properties, and freeze-thaw resistance. In Hungary, the material life of
cement particleboard is estimated to be as long as 100 years, proving the high weather
resistance properties of the materials.
4.2.2.4 Wood–plastic composites

Although wood fiber–plastic composite material has many advantages, its biggest
drawback, higher density, restricts its application scope. Therefore, how to reduce
the density of wood–plastic composites, meet the requirements of polymer materials,
and keep the physical and mechanical properties of composite materials has become a
new research topic. Foam not only reduces the density of wood–plastic composite
material, but also improves some of the physical and mechanical properties. This
unique advantage brings it broad application prospects in many fields, such as sports
equipment with light weight and high strength, and heat preservation and heat insu-
lation materials in the packing and construction industries. In recent years the study
of microcellular foaming technology has developed from single polymer foam to
microcellular composites, but the research into wood–plastic composite foam started
relatively late. At present most wood–plastic composites are made from PVC compos-
ite material using the extrusion foaming process. According to the foaming methods
used, the wood–plastic composite foaming process can be divided into two basic cat-
egories: physical foaming and chemical foaming. There are multiple ways of introduc-
ing gas into molten polymers, such as injection of a low boiling point liquid and
conversion of the liquid into gas by raising temperature or by chemical reaction.
The success of the foaming process and foam products is restricted and influenced
by many factors, such as melt viscosity, viscoelasticity of polymer, gas permeability,
and the performance of the foaming agent (such as steam pressure, solubility and
decomposition temperature, etc.)
4.2.2.5 Ecological building boards

The existing technology used to make novel materials from straw usually does not
include any treatments to the straw except for some physical destruction. It is also nec-
essary to add some chemical thermosetting resin (such as phenolic resin) and other addi-
tives to control the dimensional stability of materials and ensure the products – including
plant fiber, plant fiber packaging materials, and disposable tableware boxes – meet the
usage requirements. Not only does the heavy use of chemical adhesives and additives
increase the cost of the whole materials, but it also generates environmental pollution.
These problems are obviously unfavorable for environmental protection, and will con-
strain the development of straw as a building material. In current reports, the methods of
transforming straw into glue-free building materials are as follows: the straw is heated
before thermocuring; in the thermocuring process, only the sugar hydrolysis solution can
be used and the adhesive effect of lignin does not play a role; the characteristics of cellu-
lose do not get improved; and all of this leads to high production costs and instability.
To date, the industrialization of ecological building boards has not been realized.
For these problems, Prof. Chen developed an effective steam explosion and solid-
state fermentation degeneration processing method, which gives high destruction effi-
ciency for cellulose, hemicellulose, and lignin of straw to form thermal curing resin
adhesive (Chen, 2008). At the same time, the straw cellulose is endowed with autohen-
sion ability, which can meet the needs of building plank formation. After steam explo-
sion pretreatment, the active groups of straw lignin increase sharply and the resulting
characteristics make it a natural adhesive agent. Hemicellulose can be degraded into
carbohydrates, furfural, soluble sugar, and dehydrated sugars, and also can undertake
cross-linking reactions with lignin instead of formaldehyde. In the process of steam
explosion, the cellulose itself does not degrade, but the degree of crystallinity improves.
This technology mainly falls into two categories. One is thermocuring technology,
which controls the thermocuring process by controlling the material moisture, leading
to molecular rearrangement; in this method the biological resin can be generated to
the highest degree with uniform distribution on the straw cellulose surface. The second
category is fiber restructuring molding technology. This means that the straw cellulose
attached with thermofixation biological resin glue bonds the straw cellulose into the
building board though a thermocuring effect in drying machinery under certain temper-
ature and pressure conditions. The board from this process has a degree of mechanical
strength as required for building materials.
We can turn an abundant “resource” into power by straw modification technology.

Building board made from lignocellulose is totally environmental friendly. The thick
filaments of straw plants treated with steam explosion can be made into green environ-
mental products by compression and processing, such as corrugated base paper, green
wall materials, green packaging materials, disposable tableware boxes, and so on.
According to expert forecasts, the building area in the next 10 years will have reached
1.5 billion m2. As 1 m2 building area needs 10 m2 of building board, about 15 billion m2
of building board are required by the market. This market capacity is very optimistic,
with the prospect of becoming a new economic growth point in the future.
4.3 Lignocellulose thermochemical conversion

technologies
4.3.1 Outlines of thermochemical conversion technologies
Compared with other conversion methods, thermochemical conversion is relatively
simple and efficient for energy utilization. Therefore, it gets more and more attention.
At present, thermochemical conversion technology mainly includes pyrolysis, gasifi-
cation, and liquefaction. The pyrolysis process refers to the process where the heated
lignocellulose is degraded under conditions supplied by no or a small amount of oxy-
gen. Gasification is the method that delivers the gas agent into the lignocellulose
directly and transforms the lignocellulose into small-molecule combustible gas under
hypoxic conditions. Liquefaction is adopted for the production of methanol, ethanol,
liquefied oil, and other chemical products (Zhang et al., 2010).
4.3.2 Mechanisms of thermochemical conversion technologies

Pyrolysis refers to the process that breaks down the chemical bonds in lignocellulose
macromolecules and converts them into low molecular substances under oxygen-free
conditions. All the carbureted hydrogen in the lignocellulose can be converted into
fuel in the pyrolysis process. The pyrolysis of lignocellulose is a complex chemical
reaction process, which includes the breaking of bonds in large molecular substances,
and reactions such as isomerization, small molecular aggregation, and the formation
of low molecular materials. Compared with the incineration process, pyrolysis has the
advantages of lower temperature and lower equipment requirements, and is easier to
build near the producing area.
4.3.3 Pyrolysis technology of lignocellulose

According to the temperature, heating rate, solid residence time, and particle size of
solid pieces, pyrolysis processes can be divided into slow pyrolysis, fast pyrolysis, and
instantaneous pyrolysis (Yang et al., 2007). Fast pyrolysis is a kind of high temper-
ature treatment process. It adopts an ultraheating rate (102–104 K/s), ultrashort resi-
dence time (0.2–3.0 s), and moderate cracking temperature, which makes the
organic polymer molecules degrade quickly into short-chain molecules. At the same
time, it minimizes the yield of coke and gas. By this thermochemical method, raw
material can be directly hydrolyzed into crude oil to obtain the maximum liquid prod-
uct (bio-oil). Bio-oil is a kind of dark brown viscous liquid, having a calorific value of
as much as 20–22 MJ/kg, and it can also be refined into a substitute for fossil oil. The
fast pyrolysis liquefaction reaction is as follows: when the heat transfers onto the sur-
face of the lignocellulose particle, part of the lignocellulose quickly decomposes into
coal and oil vapor. The vapor includes condensable gases (the condensation is bio-oil)
and noncondensable gases. Once it leaves the lignocellulose surface, oil vapor can
further degrade into stable coal, gas, and tar. The short residue time can avoid
the secondary pyrolysis of tar, so the main product of fast pyrolysis is bio-oil. The
reactions can be summarized as follows: lignocellulose can be transformed into
bio-oil, char, and gas by fast pyrolysis (CO2 þ CO þ CH4 þ CxHYOn). Compared
with traditional pyrolysis technology, fast pyrolysis has the following characteristics:
(1) very high heat and heat transfer rate, usually requiring a feed particle size that
is very fine; (2) a gas reaction temperature of about 500 C and a residue time of
less than 2 s; and (3) using the shock cooling pretreatment for pyrolysis gas
(Saxena et al., 2008).
Catalysts or other substances are also put into the reactor during the pyrolysis pro-
cess. Many kinds of catalysts can be employed in the pyrolysis process to increase the
calorific value of the gas and improve the gas components. The catalytic cracking
reaction, the most economical method at present, can be carried out at a normal pres-
sure without the addition of reducing gases. The catalyst most affects the lignin, whose
one peak on the derivative thermogravimetry (DTG) graphs changes into one high
peak and a low peak, suggesting that the pyrolysis interval moves toward the low tem-
perature zone and the conversion rate is also improved. The addition of sodium car-
bonate as a catalyst can drive the main pyrolysis interval of hemicellulose toward the
low temperature zone. Lignocellulose and coal co-firing is an important topic of cur-
rent pyrolysis studies. The co-firing of lignocellulose and coal can reduce the content
of sulfur oxide, nitric oxide, and smoke. The effect of the lignocellulose pyrolysis
locks part of carbon in the carbocoal, thus making carbocoal yield increase, and
making the surface properties of carbocoal different to pure lignite. The increase of
carbocoal particle porosity and specific surface area and the changes of the electric
polarity on the particle surface significantly increase the adsorption quantity of car-
bocoal. Experiments of co-pyrolysis of coal and lignocellulose have been carried
out to prove that the pyrolysis temperature ranges of coal and lignocellulose were
not the same. Despite lignocellulose sharing many pyrolysis characteristics
with coal, it does not promote coal pyrolysis (Saxena et al., 2008).
Pyrolysis products can be divided into pyrolysis gas, pyrolysis char, and pyrolysis
liquid (bio-oil). The framework of these products should be improved before use.
There are commonly two technical routes used to improve the calorific value of
lignocellulose pyrolysis. First, reduce the nitrogen content in the gas during the
process of gasification by physical or chemical methods. Second, transform CO
and H2 into CH4 using catalysts. Methanation technology applied in lignocellulose
gasification is an effective way to improve gas calorific value. Light aromatic
hydrocarbon has a high calorific value and is also a direction for making high-quality
fuel. However, as an intermediate product, it is not very stable, so the addition
of hydrogen and catalyst is essential. Pyrolysis liquid and pyrolysis tar (bio-oil) is
characterized by high coal and high oxygen content, so it is usually refined using
catalytic hydrogenation, heat hydrogenation, catalytic cracking, and two sections
of refined processing methods. Another method of bio-oil refining is to prepare syn-
gas from bio-oil pyrolysis gasification before transforming them into high-grade
liquid fuel.
The lignocellulose pyrolysis reactor is an important device for pyrolysis, as well as
being a research focus both at home and abroad. The countries that are carrying out
studies of lignocellulose pyrolysis reactors include the United States, Canada, Finland,
Italy, Britain, Sweden, and others. The rotating cone type reaction process developed
by the Dutch Twente University does not need the carrier gas, which not only greatly
reduces the device volume, but also reduces the condenser load; the drawback of this
reactor is that the production scale is small and the energy consumption is very high.
The Georgia Institute of Technology (Georgia Tech) developed a novel carrying bed
reactor, within which the lignocellulose is quickly pyrolyzed into combustion gas
under high temperature and 58% of the liquid products are obtained. However, it
needs a lot of high temperature combustion gases, and it also produces a large number
of noncondensable gases of low calorific value. Canadian Ensyn Engineers developed
circulating, fluidized bed equipment for lignocellulose pyrolysis processes. The
device is very small, and the gas residence time is short, which can efficiently prevent
secondary pyrolysis cracking of steam. But the main drawback is that it needs carrier
gas to fluidize the heat carrier and lignocellulose within the equipment. Other reactors
include the vortex reactor developed by the American National Renewable Energy
Laboratory (NREL) and the multilayer vacuum pyrolysis reactor developed by the
Canadian Laval University. The research into reactor structures in China mainly
includes the fluidized bed, fixed bed, circulating fluidized bed, transport bed, laminar
furnace, vacuum moving bed, and rotating cone reactor. They each have their own
advantages and disadvantages. At present, only the transport bed and circulating flu-
idized bed systems are employed for commercial purposes. Of these, the circulating
fluidized bed process is the most widely used, and it has been evaluated to be among
the best lignocellulose fast pyrolysis technology. This process has high heat and heat
transfer rate, high processing efficiency, and high liquid yield. At present, the research
on pyrolysis reactors mainly focuses on tar elimination. The quality of waste ligno-
cellulose pyrolysis oil is low, and it is easy to coke in the reactor during the traditional
hydrogenation processing. Pacific Northwest Laboratory (PNL) carried out hydro-
genation processing on waste lignocellulose pyrolysis oil with alumina as the carrier
of catalyst cobalt in a fixed bed up-flow reactor. The reactor inlet and outlet temper-
ature were controlled to within 250–280 C and 250–400 C, respectively, and the
hydrogen pressure was controlled at about 13.6 MPa. The gasoline obtained from this
process had good quality and high aromaticity.
Pyrolysis temperature, reaction time, heating rate, composition of the atmosphere,
and raw materials are the key factors that affect the yield of the gas-liquid-carbon
pyrolysis mixture products. The heating rate has many effects on the pyrolysis.
Generally, the faster the heating rate, the more serious the temperature lag, and the
lower the thermogravimetric curves, the higher the differential thermal curve resolu-
tion. For aqueous compounds, a slow heating rate can detect the water loss interme-
diately, but fast heating rate always misses this important information. Obviously,
heating rate increases will make the decomposition temperature of samples rise. When
the temperature is increased too quickly, the sample cannot reach equilibrium, and the
different stages of the reaction cannot be separated. And in the heating process,
samples often undergo endothermic or exothermic phenomena. This makes the
temperature deviate from the linear temperature programmed, which changes the
thermogravimetric curve position and affects the pyrolysis analysis result. In
addition, gas production increases with the increase in heating rate. Studies on fast
pyrolysis have shown that lignocellulose will all be converted into gas if the reaction
temperature is rapidly heated (10,000 C/s) to a high temperature (1000–2000 C),
held for a short time (<0.5 s), and then quenched quickly. Through the study of fast
pyrolysis gas products, it is found that the content of methane in the product gas will
increase when hydrogen is used, and the content of CO and CO2 will be reduced.
Pressure is one of the important factors that affects pyrolysis. Under normal pres-
sure with an increase of the heating rate, both the initial and the end pyrolysis reaction
temperatures are reduced, the reaction becomes easier and more intense, and the
reaction time is shorter. Compared with reaction rates at atmospheric pressure,
lignocellulose pyrolysis reaction rates under increasing pressure are obviously more
intense; that is, the lignocellulose hydrolyzed under pressurized conditions has better
economic efficiency. Shen et al. proved that, with the increase of pyrolysis pressure,
the initial release temperature of volatile components and DTG peak temperature
increased and the maximum weight decreased, suggesting that there was a kinetic
compensation effect between activation energy and frequency factor (Shen
et al., 2005).
The lignocellulose thermogravimetric experiment should be performed in a certain
atmosphere, mainly including static or dynamic atmosphere. Under static atmosphere,
if the reaction is a reversible decomposition process, the surrounding gas concentra-
tion can make the decomposition rate decline. In addition, the convection gas in the
furnace can cause unceasing changes in the concentration of the surrounding gas,
which will affect the test results. Therefore, the static atmosphere is not usually
adopted. In order to obtain test results with good repeatability, a dynamic atmosphere
under strictly controlled conditions is always adopted. The influence of atmosphere on
the thermogravimetric curve depends on the reaction type, the nature of the decom-
position product, and the gas type. Tar has serious corrosion effects on experimental
equipment. Due to the differences in lignocellulose structures and compositions, the
tar content in pyrolysis gas also shows significant differences. The increase of ligno-
cellulose pyrolysis temperature contributes to the secondary cracking reaction of tar,
thereby decreasing the tar content in the gas. In the process of lignocellulose
gas pyrolysis, we should try to ensure that the pyrolysis materials have long enough
residence time in the pyrolysis reactor to be fully pyrolyzed. By doing this, we can
obtain the maximum amount of gaseous products, and at the same time, reduce the
tar content in the pyrolytic gas down to a minimum level. Biochar has adsorption
ability and can be used for the removal of NOx, SOx, and other pollutants in flue gas.
Pyrolysis temperature is an important factor affecting the desulfurization performance
of lignocellulose coke.
4.3.3.1 Effects of lignocellulose on pyrolysis performance

The composition of the lignocellulose has a great influence on the composition of
pyrolysis products. This section will discuss lignocellulose pyrolytic behavior in
detail. The reaction mechanisms are complex, but can be defined in five stages for
wood (Balat, 2008): (1) the loss of water and some volatiles; (2) breakdown of hemi-
cellulose and formation of CO and CO2; (3) emission of methane and ethane caused by
the high temperature; (4) external energy is now required to continue the process;
(5) complete decomposition.
Pyrolysis mechanism of cellulose

The reaction kinetics of cellulose pyrolysis have been studied by many researchers. A
lot of mechanisms have been proposed, of which the Broid-Shafizadeh model is the
most generally accepted. Based on the Broid-Shafizadeh model, the pyrolysis mech-
anism of cellulose can be divided into three steps: (1) cellulose is activated; (2) some
of the activated cellulose is transformed into volatiles; and (3) some of the activated
cellulose is transformed into char and gas. The characteristic of the destructive reac-
tion of cellulose is a decreasing degree of polymerization, which starts at temperatures
lower than 325 K. Different thermal degradations of cellulose proceed under different
temperatures. At lower temperatures, a gradual degradation, decomposition, and char-
ring occur; and at higher temperatures, rapid volatilization occurs with the formation
of levoglucosan. First, the glucose chains in cellulose are cleaved to glucose; second,
glucosan is formed by the splitting off of one molecule of water. Fengel and Wegener
studied the isothermal pyrolysis of cellulose in air and milder conditions (623–643 K)
and the results showed that 62–72% aqueous distillate was formed and 10–18% char
residue was left (Fengel and Wegener, 1983). The pyrolysis residue consisted of some
water-soluble materials, char, and undecomposed cellulose. With the decreasing for-
mation of char, the formation of tar increased. The liquid fraction is mainly composed
of water, with small proportions of butyraldehyde, acetaldehyde, propion aldehyde,
crotonaldehyde, acrolein, furan, acetone, butanedione, and methanol. In the process
of fast pyrolysis, cellulose does not react completely at temperatures less than
400 C due to insufficient heat response; the carbonization reaction is given priority
between 400 and 450 C; after 450 C bio-oil reaction gets strengthened and the high-
est productivity is reached (78%) at about 600 C. Due to the secondary reaction of
volatile gas, the bio-oil yield is significantly decreased and light gas production is
greatly increased. With the increase of nitrogen flow, secondary reactions are partially
suppressed. At the same time, bio-oil production increases and condensate gas yield
decreases; however, their influence is much less than the temperature effect on
the pyrolysis. By GC-MS detection, the main ingredients of bio-oil are hydroxyl,
methoxy, ketone, phenol, aldehyde, alcohol compounds with a number of methyl
and ethyl functional groups, among which the left-hand glucan, ethanol, aldehyde,
and 1-hydroxy-2-acetone content accounts for nearly 80%. Ethanol, aldehyde, and 1-
hydroxy-2-acetone are directly generated as the cellulose pyrolysis products in the
process of competition with levoglucosan. To analyze the competition, Wang et al.
established a competition reaction kinetics model and simulated ethanol, aldehyde,
and 1-hydroxy-2-ketone, respectively (Wang et al., 2011). It is concluded that the pro-
duction of these two compounds has similar dynamic behavior, suggesting the same
initial reaction of these two competition compounds.
The cellulose pyrolysis mechanism and the generation of ordered cellulose can be
divided into three stages. The first stage is the preheating solution phase, in which
cellulose polymer chains break down, the degree of polymerization of the cellulose
drops, and glass transition occurs. There are also internal rearrangement reactions
in this phase. The second stage of the pyrolysis is the degradation process. Under a
temperature of 300–600 C, cellulose is depolymerized into monomers and further
forms pyrolysis products through a variety of free radicals and rearrangement reac-
tions. In this stage, the fracture and rearrangement of chemical bonds need to absorb
a lot of heat. The third stage is the coke degradation stage. In this stage, coke is further
degraded, and CdH and CdO bonds are ruptured, resulting in the formation of a
carbon-rich solid residue. The order of cellulose pyrolysis products generated is as
follows: in the 300–500 C range, mainly 2, 5-dimethylfuran, 5-methyl furfural,
1,6-dehydration-beta-pyran glucose, and 5-hydroxymethyl furfural; in the
500–500 C range, mainly benzene 2-methyl ethyl ketone, coumarone and methyl
phenol, toluene and benzene, and others; and higher than 600 C, the main pyrolysis
products are naphthol, naphthalene, fluorenone, anthracene, and fluoranthene pyrene.
With the increase of pyrolysis temperature, molecular oxygen in pyrolysis products
rapidly declines and, benzene is rapidly added to the molecular ring, whose number
significantly increases and fuses together.
The different components of lignocellulose raw materials are the main factors
influencing the composition and characteristics of bio-oil. At present, the pyrolysis
of lignocellulosic raw materials can be divided into two kinds: one is used in pyrolysis
of natural wood fiber or the residue after fermentation, including wood such as spruce,
beech, sawdust, crops such as rice, wheat and maize straw, and bagasse; the other type
of pyrolysis is used for material that contains a high percentage of fat including the
seeds of oil plants and the remaining residue after oil extraction, oil microbial bacteria,
and so on. Due to the high oil content, pyrolysis bio-oil of this kind has high paraffin
content, high calorific value, and is more suitable for biofuel production. Pyrolysis
conditions have a great influence on the composition and characteristics of bio-oil.
Pyrolysis mechanism of hemicelluloses

Hemicelluloses are complex polysaccharides consisting of branched structures. Hemi-
celluloses vary considerably among different woody and herbaceous lignocellulose
species. Hemicelluloses usually carry 50–200 monomeric units and a few simple sugar
residues, and the general formula is (C5H8O4)m. The main products from the degra-
dation of xylan are water; methanol; formic, acetic, and propionic acids; hydroxy-1-
propanone; hydroxy-1-butanone; and 2-furfuraldeyde (Balat, 2008).
During the pyrolysis reactions of hemicelluloses, water is formed by dehydration;

acetic acid comes from the elimination of acetyl groups originally linked to the xylose
unit; furfural is formed by dehydration of the xylose unit; formic acid proceeds from
carboxylic groups of uronic acid; and methanol arises from methoxyl groups of uronic
acid (Balat, 2008).
Hemicelluloses degrade at temperatures from 473 K to around 533 K. Hemicellu-
loses react more readily than cellulose during the heating process. There are several
reasons for this, as follows: (1) pentosans are most susceptible to hydrolysis and dehy-
dration reactions; (2) xylan is the most thermally unstable; (3) hemicelluloses contain
more combined moisture than lignin, so the hemicelluloses’ softening point is lower
compared to lignin; and (4) exothermic peaks of hemicelluloses appear at lower tem-
peratures than that of lignin, and their thermal decomposition occurs at a lower tem-
perature (Demirbaş, 2003).
Pyrolysis mechanism of lignin

The pyrolysis of lignin has been widely studied, and different pyrolysis products are
obtained from different lignocelluloses. Guaiacol is chiefly obtained from coniferous
wood, and guaiacol and pyrogallol dimethyl ether show the aromatic nature of lignin
from deciduous woods. Lignin from wood gives higher yields of charcoal and tar than
lignin from straw. Aromatic compounds are derived from lignin by the cracking of the
phenyl-propane units of the macromolecule lattice. Pyrolysis seems to produce the
most substituted phenols on a selective basis.
4.3.3.2 Products from lignocellulose pyrolysis technology

The differences in the raw material components is the main factor determining the
composition and characteristics of bio-oil. At present, the raw material of pyrolysis
is mainly lignocellulose or its fermentation residue, including wood such as spruce,
beech, and sawdust; and plants such as rice, wheat and maize straw, and bagasse.
The typical characteristics of pyrolysis bio-oil from lignocellulose material are
discussed below.
Water
Bio-oil after pyrolysis contains 15–30% (w/w) moisture and this makes the oil easy to
denature and the calorific value and burning temperature reduce. Meanwhile, the
water also reduces the viscosity of the bio-oil and increases its liquidity, which makes
it prone to atomization and combustion in the engine.
Oxygen content
The oxygen content of bio-oil is usually between 35 and 40%; it is distributed in more
than 300 compounds, and keeps changing according to the pyrolysis raw materials as
well as pyrolysis conditions. The existence of oxygen is the root difference between
bio-oil and hydrocarbon fuel. The energy density of high oxygen content bio-oil is
only half of that of conventional fuel. Organic acids increase the bio-oil acidity
and instability, and lead to infusibility with hydrocarbon fuels. Bio-oil contains
complicated compounds and has a wide range of boiling temperatures. In distillation,

it starts to boil at under 100 C and stops boiling at 250–280 C, and 35–50% of the oil
remains as solid residue. Because some components will polymerize or coke, it is
impossible to separate all the components by the distillation method.
Viscosity
The viscosity of bio-oil varies largely due to different substrate and pyrolysis condi-
tions. According to data from the pyrolysis of Pterocarpus indicus and Fraxinus man-
dshurica, the dynamic viscosity of bio-oil reached 70–350 mPa s and 10–70 mPa s,
respectively. Because of high water content, pyrolysis oil from straw has the lowest
dynamic viscosity, at about 5–10 mPa s. Besides water content, alcohol also influences
oil viscosity. When added with 5% methanol, there is a 35% reduction in the viscosity of
hardwood pyrolysis oil. Boucher et al. found that mixing bio-oil with methanol showed
a reduction in density and viscosity and tended to be stable when burned in the gas tur-
bine, except for a decrease in the flashing point (Boucher et al., 2000).
Acidity
Bio-oil contains stable acid components, such as acetic acid and formic acid, and the
pH stays between 2 and 3. These acids exhibit strong corrosion effects, so treatments
are necessary before utilization as transportation fuels.
Heat value
The calorific value of pyrolysis bio-oil from lignocellulosic raw materials is usually
12–19 MJ/kg.
Ash
Ash in the bio-oil can agglomerate and cause corrosion of the engine and valves, and
even damage the engine and valves directly when the content is higher than 10%. Alkali
metal plays a leading role in the erosion and deposition process. For example, high tem-
perature corrosion and deposition is usually caused by sodium, potassium, and vana-
dium. Hard sediment comes from calcium. The measurement results show that H50
bio-oil contains 2 ppm K, 6 ppm Na, and 13 ppm Ca. Hot gas filter technology, invented
by the National Renewable Energy Laboratory in the USA, is perceived to be the best
method of ash extraction, which can make the alkali metal in the bio-oil less than 2 ppm.
Composition of bio-oil
Nearly all (99.7%) of the compounds of bio-oil contain carbon, hydrogen, and oxygen
elements, including organic acid, alcohol, aldehyde, ester, ketone, sugar, guaiacol,
carophyllin, furan, and phenol produced from lignin. Wang et al. analyzed the main
composition of bio-oil from Fraxinus mandshurica pyrolysis using GC-MS methods,
and found that the components included furfural, xylene, 2-methoxy-4-methyl phenol,
eugenol, cedar alcohol, furan and so on (Wang et al., 2010). Most of the components
have the ketone and aldehyde groups, suggesting the wide presence of oxygen. The
abundant ketone and aldehyde groups contribute to the fine hydrophilous nature of
Organic compounds of pyrolysis bio-oil and their relative

Table 4.1
proportions (Chen, 2008)
Main compounds Relative amount (%)
Furfural 9.06
1-Hydroxy acetyl acetone 1.21
5-Methyl furfural 1.82
Phenol 2.55
3-Methyl-2-ring pentane-1-ketone 1.58
2-Hydroxybenzaldehyde 2.70
2-Methyl phenol 5.04
4-Methyl phenol 0.51
2-Methoxy phenol 0.27
2, 4-Dimethyl phenol 9.62
4-Ethyl phenol 2.18
2-Methoxy-5-methyl-phenol 4.15
2-Methoxy-4-methyl phenol 0.55
2, 3, 4-Trimethoxyphenol 3.80
2, 6-Dimethyl-4-propylene phenol 4.25
Diisooctyl phthalate 1.80
Furan 5.70
Levoglucosan 6.75
2, 6-Dimethoxy-4-propylene phenol 3.14
5-Methylfuran 0.49
1-(4-Hydroxy-3-methoxy)-acetophenone 2.94
Vanillin 6.35
3, 5-Dimethyl-4-hydroxybenzaldehyde 4.54
3, 5-Dimethoxy-4-styrene aldehyde 2.19
bio-oil. The close combination of water makes the following dewatering work very
tough. Table 4.1 lists some of the identified compounds and their contents in the
organic phase. Bio-oil contains almost all kinds of oxy compounds, such as esters,
ethers, aldehydes, ketones, phenols, organic acids, and alcohols.
4.3.3.3 Bio-oil modification

Bio-oil cannot be used as engine fuel directly because of its instability, corrosivity, and
high viscosity. Therefore, a modification process is necessary. The main factor leading to
this phenomenon is the high oxygen content in the bio-oil; thus removing the oxygen is
the purpose of any modification process. Modification methods include the following
aspects: hydrogenated deoxidization, catalytic cracking of pyrolysis gas, and emulsion.
Hydrogenated deoxidization
Hydrogenated deoxidization is carried out in the solvents that can provide hydrogen
and under hydrogen and/or carbon monoxide pressure conditions. The solvent is acti-
vated by catalysts with CodMo, NidMo, and their oxides or Al2O3 as the carrier.
Oxygen is removed in the form of water or carbon and oxygen, so the energy density
of bio-oil will rise after catalysis.
Zhang et al. gained liquid product that can be divided into an oil phase and a water
phase by pyrolyzing sawdust with a yield of 70% (Zhang et al., 2005). Then, the oil phase
was used for hydrotreating. The reaction was carried out in a pressure cooker, employing
vulcanizated CodModP/Al2O3 as catalyst, and 3, 4-tetrahydronaphthalene (providing
hydrogen solvent) as the reaction medium. The reaction condition was set as follows:
temperature 360 C; hydrogen pressure 2 MPa. After pretreatment, the oxygen content
decreased from 48% to 3%, calorific value rose from 21.3 kJ/kg to 41.4 kJ/kg, and oil
yield reached 48%. In order to clarify the carbonyl group deoxidization process, Şenol
et al. designed an experiment in a fluidization reactor (Şenol et al., 2005). The experi-
ments used methyl heptanoic acid and caproic acid methyl ester as model compounds,
and employed sulfided NiMo/g-Al2O3 and CoMo/g-Al2O3 as catalyst. Hydrocarbon
is generated through three steps: first, methanol is removed, dehydrated, and the
leftover parts are transformed into hydrocarbon; second, methanol and fatty acids are
formed via de-esterification; and third, hydrocarbon is formed by direct conversion
or through the intermediate of alcohols of fatty acids. Obviously, the hydrogenated
deoxidization process requires complicated equipment, skilled technology, and high
investment and often has to be stopped due to catalyst deactivation or blockages in
the reactor.
Catalytic cracking of pyrolysis gas

The use of a catalyst to improve lignocellulose pyrolysis product yield and quality is
an important topic for pyrolysis research. Catalytic cracking of pyrolysis gas refers to
the method where a catalyst is mixed with raw materials or fixed near to the raw mate-
rials during pyrolysis. Under these conditions, the produced gas contacts the catalyst
quickly before cooling, and is catalyzed into CO2 or CO. After these processes, the
oxygen is removed and high-quality bio-oil is obtained.
The main effect of the catalyst is catalyzing the transformation of oxygen in the
lignocellulose into carbon dioxide, improving the hydrogen content, decreasing water
content, and improving the calorific value and chemical stability. Analysis of
the pyrolysis oil found that the number of carbons in the catalyst product concentrated
in a smaller range (C10–C24), and the processing cost could be greatly reduced.
Nokkosmäki et al. found that ZnO was a mild catalyst and could catalyze pyrolysis
to produce bio-oil with good stability (Nokkosmäki et al., 1998). At the same time,
there was no loss of the oil yield. Though ZnO did not work on the insoluble
components mainly produced by lignin, it could decompose soluble anhydride
and polysaccharide. Being heat-preserved at 80 C for 24 h, the increase in viscosity
of bio-oil catalyzed by ZnO (55%) was obviously lower than the ones without
catalyst (129%).
Despite the catalyst passivation phenomenon, the bio-oil stability was distinctly
improved. The catalysts successfully used in pyrolysis by Ateş et al. included standard
commercial catalyst-534 (CodMo) and clinoptilolite (Ateş et al., 2005), and both of
them have been widely used in the oil chemical catalysis industry. These catalysts
removed oxygen efficiently in the form of H2O, CO2, and CO, improving the yield and
quality of pyrolysis oil to different degrees. When Euphorbiaceae sp. was pyrolyzed
in the fixed bed at 550 C, the bio-oil yield was improved from 21.6% of noncatalyzed
oil to 31%, 28.1%, and 27.5% of catalyzed oil, respectively. Pütün et al. pyrolyzed the
seed oil extraction residue with 20% (w/w) clinoptilolite as catalyst in the fixed bed at
550 C (Pütün et al., 2006). They found that the yield increased from 26.02% to
30.84% after adding catalyst and the calorific value of bio-oil increased from
30.96 MJ/kg to 33.34 MJ/kg. In the rice hull pyrolysis process, Williams and
Nurganad fixed the catalyst at the gas outlet of the reactor (avoiding the catalyst con-
tacting the substrate directly), and made the preheated nitrogen and gas from high-
temperature pyrolysis go through the catalysts at the same time (Williams and
Nugranad, 2000). The produced bio-oil and gas were collected by a condenser. Results
showed that the oxygen in the catalyzed bio-oil decreased from 41.5% (without cat-
alysts) to 8.1%.
The effect of the catalysts was removal of the oxygen in the pyrolysis bio-oil in the
form of H2O, CO, and CO2. At the same time, the long-chain hydrocarbon cracked
into short-chain compounds, resulting in a reduction of the heavy bio-oil yield. The
molecular mass became smaller and the aromatic hydrocarbon content increased.
The gas material yield was also improved, among which alkanes and olefins obviously
increased.
When summarizing the advantages and disadvantages of different catalysts for
bio-oil modification, Guo et al. concluded that there was still much work to do in
improving transfer efficiency and avoiding coking, even though the catalytic cracking
technology proved to be very efficient (Guo et al., 2009). Despite its relatively low
cost, the future of the catalytic cracking method is uncertain, for there is a lot of coke
(8–25%) produced in the catalysis process, and the liquid fuel yield is very low.
Emulsion
The simplest way to use bio-oil as a transportation fuel is by mixing it with diesel.
Although there is no solubility between bio-oil and diesel, this problem can be solved
by adding surfactants. Chiaramonti et al. mixed bio-oil with diesel at ratios of 25%,
50%, and 75%, respectively (Chiaramonti et al., 2003). They found that when 1% emul-
sifier was added, the bio-oil became more stable, the bio-oil content increased, and the
emulsified liquid viscosity became higher. Ikura et al. mixed the light components of
bio-oil from the centrifugation process with NO2 diesel at ratios of 10%, 20%, and
30%, respectively (Ikura et al., 2003). The mixture became an emulsion with the action
of a surfactant. The costs of the stable emulsion were 2.6, 3.4, and 4.1 cents/L, respec-
tively, according to the different proportions above. The viscosity of the bio-oil contain-
ing 10–20% emulsion was much lower than the pure bio-oil and the corrosivity was half
that of the pure bio-oil. Although the emulsifying technology does not need complex
chemical conversions, its high cost and energy consumption should not be ignored.
Furthermore, its corrosion of the engine and components is also very severe.
Lignocellulose pyrolysis is clean, fast, and efficient. However, the products are
often complex and difficult to separate. In particular, the water and acids within it will
reduce combustion efficiency and corrode the machines. Some low-value products are
also produced during the pyrolysis process. Therefore, up to now, the process has not
been widely promoted. Much effort has been expended on research and development
both at home and abroad. The research mainly focuses on the following four issues.
First, finding more suitable raw materials. This goal is achieved by either reducing raw
material costs or improving the production rate of the lignocellulose fuel. Second,
developing more economic and efficient conversion technologies and equipment.
Third, improving the use performance of bio-oil. And fourth, developing valuable
bio-oil by-products.
4.3.4 Gasification technology of lignocellulose

Gasification is the generation of gaseous fuel by heating the lignocellulose in a gasifi-
cation medium such as air, oxygen, or steam. The difference between gasification and
combustion is that in combustion the oxidation is substantially completed in one pro-
cess. However, gasification converts the intrinsic chemical energy of the carbon in
the lignocellulose into combustible gases through two stages. The produced gases
can be standardized in their quality and are more versatile and easier to use than the
original lignocellulose. For example, the gases can be used in gas engines and gas tur-
bines, or as chemical feedstock to produce liquid fuels. Gasification includes both bio-
chemical and thermochemical processes. The former involves microorganisms at
ambient temperature under anaerobic conditions (i.e., anaerobic digestion), while the
latter uses air, oxygen, or steam at high temperatures (>800 C). In accordance with
common practice, the term gasification here will refer only to the thermochemical con-
version of lignocellulose.
According to the relative speed and direction of flammable gas against material in
the vaporizer, lignocellulose gasification can be divided into two kinds: fixed bed gas-
ification and fluidized bed gasification (McKendry, 2002). In a fixed bed gasifier, the
gasification reaction of the material is in the relative static bed layer, where the struc-
ture is compact, easy to operate, and has high thermal efficiency. In the fluidized bed
gasifier, materials become “boiling” and the gasification rate is high. According to the
structure of the evaporator and the gasification process, fluidized bed gasifiers can be
divided into the bubbling fluidized bed and the circulating fluidized bed. Fixed bed
gasifiers and fluidized bed gasifiers have their own characteristics and ranges of appli-
cation (Table 4.2). The former are convenient to operate with a simple structure and
flexible operation mode, and are suitable for medium- and small-scale production,
while the latter are suitable for large-scale industrialization because the equipment
is relatively complex and costly (McKendry, 2002).
The lignocellulose gasification process consists of four stages: pyrolysis, oxida-
tion, reduction, and drying. The distribution of these four stages differs among differ-
ent vaporizers. In general, phase distribution in fixed-bed gasifiers is very clear, but
in fluidized bed gasifiers the situation is not so clear. The structures and reaction zones
of different gasification devices are shown in Figure 4.3. The first three stages are
explained in more detail below:
(1) Pyrolysis stage. The lignocellulose pyrolysis reaction will be initiated when the temperature
is higher than 230 C. The pyrolysis process is mainly high-temperature degradation
Table 4.2 Main types and features of biological gasifiers in China

(Chen, 2008)
Updraft Downdraft
fixed-bed fixed-bed
gasifier gasifier Fluidized bed
Material type Straw, waste Straw, waste Rice husk, sawdust, straw
wood wood
Granularity/mm 5–100 20–100 <10
Vaporization 1100 1000 650–850
temperature
( C)
Gasification 70–75 75 65–75
efficiency(%)
Gasification 200–300 200–600 1000–2000
intensity
(kg/m h)
Application Boiler heating Gas supply, Rice mill factory, lignum
fields heating boilers processing factory, power
plant
Gasified Gasified gas

Biomass Biomass
gas
Arid Arid
region region
Air Biomass
Gasified gas
Ash Air Ash Air
Upward ventilating stove Upward ventilating stove Fluidized bed and gasified boiler
Figure 4.3 Schematic diagrams of different gasification devices (Chen, 2008).
reactions of cellulose, hemicellulose, and lignin. In the process, macromolecular hydrocar-

bons degrade into low-carbon-chain organic compounds. Parts of volatiles may participate
in further decomposition reactions and transform into gas phase components at room tem-
perature, and others become empyreumatic oil through dehydration polymerization
reactions.
(2) Oxidation stage. In this stage, fixed carbon from the pyrolysis stage and ash particles are
surrounded by volatiles. The added oxygen first contacts with the volatile gas and they react
with each other; namely, “burning.” The combustion process will produce large amounts of
carbon dioxide and release a lot of heat. At this stage, the temperature is very high, and in
fixed bed gasification combustion can reach more than 1150 C. Because the reaction zone
boundaries in the fluidized bed are not obvious, there is no special high-temperature zone.
Empyreumatic oil is pyrolyzed rapidly in the combustion zone, and the degree of pyrolysis
varies with different evaporators.
(3) Reduction stage. When passing through the oxidation zone, materials enter the reduction
stage, in which large amounts of carbon dioxide and fixed carbon, which do not participate
in the reactions, will form carbon monoxide. At the same time, reactions in which water
vapor and carbon dioxide or carbon monoxide form methane also occur. This stage mainly
contains endothermic reactions, and the temperature drops to 600 C.
In short, many chemical reactions occur in the process of lignocellulose air gasifica-
tion. The chemical reaction equations can be summarized as follows:
C6 H10 O5 þ 0:5O2 ! 6CO þ 5H2 ,
C6 H10 O5 þ O2 ! 6CO þ 4H2 þ H2 O,
C6 H10 O5 þ O2 ! 5CO þ CO2 þ 5H2 ,
C6 H10 O5 þ 1:5O2 ! 6CO þ H2 O þ 3H2 ,
C6 H10 O5 þ 1:5O2 ! 4CO þ 2CO2 þ 5H2 ,
C6 H10 O5 þ 2O2 ! 3CO þ 3CO2 þ 5H2 :
Lignocellulose gasification is an important direction for the development of lignocel-

lulose energy. The major concern of research in the study of lignocellulose gasifica-
tion is gas quality; that is, how to transform the lignocellulose into gas with as high a
calorific value as possible. The measurement parameters of gas quality include gas
calorific value, tar content, and the content of alkali metal compounds. The compo-
sition of the material, the structure of the gasification device, and the running param-
eters are important factors that affect the quality of the gas produced.
For lignocellulose air gasification, the equivalence ratio is a very important param-
eter and affects gasification efficiency, gas composition, and calorific value. With an
increase in equivalence ratio, the total amount of H2, CO, CH4, and C2H2 in the gas-
ification gas is reduced and the calorific value of the product gas decreases. Con-
versely, both the yield and gasification temperatures are increased. This is because
with the increase in equivalence ratio, charging air quantity increases and more fuel
gas reacts with oxygen to produce CO2. In addition, N2 concentration in the gas
increases, resulting in a reduction in the gas calorific value and an increase in biogas
yield. The equivalence ratio of the normal lignocellulose gasification is controlled
within 0.25–0.33. The gas calorific value is related to gasification efficiency and
tar content in the gas as well. When the empyreumatic oil is within l0–15 g/Nm3,
the gas calorific value will reduce by about 10–15%.
During the entire process of incomplete combustion gasification, tar is mainly pro-
duced in the material pyrolysis stage, and the final content is directly affected by the
pyrolysis area temperature and heat transfer efficiency. Among the main factors
influencing the products of pyrolysis are pyrolysis temperature and heating rate.
The higher the pyrolysis reaction temperature and heating rate, the more efficiently
the macromolecular lignocellulose hydrocarbons are decomposed. In addition to
this, the less tar that is produced, the more pyrolysis gas is produced. The combustion
zone is the main elimination stage for tar. This is mainly caused by two factors: (1) the
temperature in the burning zone is very high, and tar will burn going through this area;
and (2) the oxidation zone contains large amounts of oxygen molecules; under the
condition of high temperature and enriched oxygen, part of the tar will burn,
generating carbon dioxide and water. Because of the different designs and structural
characteristics, reaction zones distribute differently in different equipment. Therefore
the tar content in gas varies among different gasification equipment (Table 4.3).
Alkali metal content in gas mainly depends on the content and types of alkali metal
in lignocellulosic raw materials, because different alkali metals have different melting
points and boiling points. Generally speaking, lignocellulose usually contains large
amounts of alkali metal salts, such as potassium and sodium, which are essential ele-
ments for biological growth. Especially in fast-growing organisms such as cereals and
energy crops, the potassium content is relatively high. Several compositions of ligno-
cellulose ash are shown in Table 4.4.
Using lignocellulose containing a high content of alkali metals as raw material has
a great impact on gas quality. Some of the sylvites and sodium salts can volatilize at
700 C, staying in the high-temperature gas, and then precipitating on the downstream
piping or equipment, resulting in an inconvenience when used as a transportation fuel.
Table 4.3 Tar content in the gas produced from typical gasification
equipment
Tar content in the gas product (g/m)a
Carburetor type Minimum Maximum Average range
Downdraft gasifier 0.04 6.0 0.1–0.2

Updraft gasifier 1.00 150.0 20.0–100.0
Bubbling fluidized bed gasifier <0.10 23.0 1.0–15.0
Circulating fluidized bed gasifier <1.00 30.0 1.0–15.0
a
The range of contents is only based on the common typical evaporators. They are measured on several specified types of
gasification equipment. The tar content for other types of gasification equipment should be determined by actual
measurements (Chen, 2008).
Table 4.4 The chemical composition of lignocellulose ash (wt%)

(Chen, 2008)
CaO K2O P2O5 MgO Na2O SiO2 SO3 Others
Poplar 47.2 20.0 5.0 4.4 0.2 2.6 2.7 17.9

Pine 49.2 2.6 0.3 0.4 0.4 32.5 2.5 12.1
Cereals 4.8 15.0 2.6 2.6 0.1 69.9 1.9 3.1
The evaporation of alkali metal in the ash content is a complicated process. It is gen-
erally believed that in the process of gasification, alkali metal salts experience a series
of reactions. Some transitional products such as KOH and KC1 easily form volatile
alkali metal compounds under the action of a tiny amount of S or Cl. Alkali metal
has a great influence on the gas turbine. The inlet temperature of the gas turbine is
high and after the gas expands it cools rapidly, making it easy for alkali metal to
deposit on the gas turbine blades. As gas turbine technology has not been carried
out domestically, the alkali metal in the gas has not been taken seriously.
As a result, in order to achieve good gasification effects, the points below should be
carefully considered:
(1) The factors that control gas quality include calorific value, empyreumatic oil, and alkali
metal content, and these factors interact with each other. It is necessary to take every factor
into consideration.
(2) In the air gasification process, the calorific value should be improved and the appropriation
of equivalence ratio should be ensured. At the same time, tar should be eliminated as far as
possible.
(3) To eliminate tar, the temperature in the pyrolysis stage and the heating rate should be well
controlled. In other words, the temperature should rise quickly to over 600 C and the reten-
tion time should be restricted to ensure the adequate pyrolysis of materials and the secondary
reactions of the tar. On the premise that ash is assured not to coke, the reaction temperature
should be raised as high as possible to achieve the full cracking of empyreumatic oil.
(4) The alkali metal content in the gas should be reduced to the greatest extent possible and the
temperature of the carburetor outlet gas should be strictly controlled.
4.3.5 Liquefaction technology of lignocellulose

Liquefaction technology is an important research direction for lignocellulose utiliza-
tion. Researchers, both at home and abroad, have spent lots of effort on this, with the
hope of finding novel liquid fuels and chemical materials. Lignocellulose liquefaction
is the process of chemical conversion of lignocellulose into liquid products, and can be
divided into direct liquefaction and indirect liquefaction. Indirect liquefaction refers to
the process of first gasifying the lignocellulose and then transforming it into methanol,
dimethyl ether, and other liquid products. The product produced through this method
is of high quality; however, it always suffers from a high fixed investment as well as
low overall thermal efficiency. Direct liquefaction refers to the process in which when
water or other organic solvent is employed as a medium and catalyzed by a relatively
low-temperature catalyst, lignocellulose generates a large number of liquid products
with a small amount of gas and solid residue.
Based on the temperature used and the pressure in the liquidation process, the direct
liquefaction process can be categorized as high-temperature and high-pressure direct
liquefaction or low-pressure (atmospheric pressure) direct liquefaction (also called
moderate liquefaction). Traditional direct liquefaction refers to the direct liquefaction
process with high temperature and pressure, whose product is generally used as
fuel oil, which must be modified before use, just like the bio-oil from lignocellulose
pyrolysis. In recent years, research on mild liquefaction under low pressure, even
ordinary pressure, has gained more and more attention. The product from mild lique-
faction is normally used as raw material for polymer production or as a fuel additive.
4.3.5.1 Direct liquefaction under high temperature and high

pressure
Fierz et al. started the research on wood liquefaction as early as 1925 (Fierz-David,
1925), which stimulated the coal liquefaction process and directly liquefied wood
powder into liquid fuel. The wood chips were liquefied in the H2 and/or CO medium
at 350–400 C, in which Na2CO3 was used as the catalyst and anthracene oil as the
solvent, obtaining 53% crude fuel. This research was completed in the Pittsburgh
Energy Research Center, so this method was named the PERC method. The Lawrence
Berkeley Laboratory proposed hydrolyzing for 45 min at pH 1.8 and 180 C, and then
transformed the lignocellulose into wood pulp, and adjusted the pH to 8 with Na2CO3,
and next liquefied the pulp and obtained 33% crude fuel. This method was named
“LBL.” In 1990, Goudriaan and Peferoen from the Shell Oil Company proposed
the HTU (hydrothermal upgrading) method employing water as the solvent and cat-
alyzing wood for 5–15 min at 300–350 C, then converting them into crude oil with an
oxygen content of 5–15% (Aresta et al., 2005).
The high-temperature and high-pressure liquefied solvents include water, hydro-
carbon solvent (e.g., cyclohexane), alcohols (e.g., methanol, ethanol, isopropanol,
butyl alcohol), polyols (e.g., ethylene glycol, glycerin), phenol, organic acids
(e.g., acetic acid, lactic acid), alkaline solution (e.g., monoethanolamine, triethano-
lamine), ethers and ketones (e.g., methyl glycol ether, acetone, cyclohexanone) as
well as other mixed solvents. Because it is not necessary to consider the boiling point
of these solvents in the high-temperature and high-pressure liquefaction process, it is
best to adopt the cheapest solvents with low boiling points for the subsequent sep-
aration. Heitz et al. compared the liquefaction performance of several solvents, and
found that acids and alkaline solutions were favorable for liquefaction because of
their certain catalytic effects (Heitz et al., 1994). Water, lower alcohol, multivariate
alcohol, and acetone can also liquefy lignocellulose under high temperature and
high pressure in the existence of acid or alkali as a catalyst; the role of the solvent
is to dissolve the liquefied and degraded products, and prevent them from re-
polymerizing as insoluble residue.
High-temperature and high-pressure liquid catalysts include acid catalysts (e.g.,
sulfuric acid, phosphoric acid, acetic acid), alkali and alkaline earth metal salts
(e.g., sodium hydroxide, sodium carbonate, sodium bicarbonate, sodium formate),
other Lewis acid catalysts (e.g., zinc chloride, aluminium chloride), and some hetero-
geneous metal catalysts (e.g., ruthenium (Ru), palladium (Pd), iron (Fe), nickel (Ni),
platinum (Pt), and their metal oxides). Metal catalysts are often used in catalytic deox-
idization reactions of hydrogen and carbon monoxide.
The compositions of products from high-temperature and high-pressure catalysis
are very complicated. Products of cellulose and hemicelluloses mainly include sugars
(laevo-glucose, oligosaccharides, and monosaccharides, etc.), organic acid, formic
acid, acetic acid, lactic acid, 2-hydroxy butyric acid, isobutyric acid, 2-hydroxyl-2-
hydroxyvaleric acid, levulinic acid, benzoic acid, furfural, furan derivatives, and aro-
matic compounds. The products of lignin include phenol, naphthol, wood phenol,
glycol and aromatic compounds containing oxygen (e.g., methoxyl benzene). Other
products include long-chain fatty acid, coumaric ketone (e.g., methyl ketone of cou-
maric, hydroxyl coumarone, and methylcoumaric ketone), and cyclization compounds
(e.g., methyl cyclopentanone). In general, the products under high temperature and
high pressure mainly include sugar, organic acid, ketone, phenol, and other hydrocar-
bon oxygen compounds, which are mainly comprised of small molecular weight prod-
ucts. Thermogravimetric analysis shows that as the temperature increases in the high-
temperature and high-pressure liquefaction process, lignocellulose feedstock first
decomposes into soluble products, then degrades into gas, oil and coke, then forms
small molecular products, and finally polymerizes into macromolecular products. Cel-
lulose is first degraded into oligosaccharide, then broken down into glucose, and sub-
sequently transformed into 5-hydroxy furfural though the dehydration process. And,
after that, furfural reacts with solvent (e.g., phenol) or generates autopolymerizers to
form compounds with a furan ring structure. Under the catalysis of an alkali salt (e.g.,
sodium carbonate and potassium carbonate), the macromolecular cellulose and hemi-
cellulose in the liquefication process is first hydrolyzed into small molecular com-
pounds, then micelle fragments produced from the degradation process are degraded
into smaller compounds though dehydration, dehydrogenation, deoxidization, and
decarboxylation reactions. Once produced, these compounds may form new com-
pounds by condensation, cyclization, and polymerization reactions. In the process of
cellulose decomposition, intermediates of phenoxide compounds (liquefaction in phe-
nol) and alkoxy compounds (liquefied in alcohol) are formed at 233.9 C. If heating of
the system is continued, benzene oxygen intermediates start to degrade and produce
hydroxymethyl furfural and phenol. And if a high temperature is adopted (about
302 C), hydroxymethyl furfural will aggregate into high molecular weight products.
Because the traditional liquefaction process is carried out at high temperatures and
high pressures, it consumes a large amount of energy and has a high requirement for
sustained pressure. Because of the continuous feeding under high-pressure conditions,
the equipment is very complicated and the operating conditions are very rigorous, all
of which contributes to the high cost of liquefaction. In addition, the main product of
the high-temperature and high-pressure liquefaction process is crude oil, where there
exist similar problems to those in the lignocellulose pyrolysis process. That is, both
products need refinement and modification treatments. Furthermore, some of the
chemical materials are very difficult to separate because of their complicated compo-
sition. In recent years, researchers have begun to study the direct liquidation technol-
ogy under lower temperature and pressure, and tried to replace the gas medium (e.g.,
H2 and CO) with inert gas for higher liquefaction ratios and fuel yields.
4.3.5.2 Moderate liquefaction

As a result of the problems with high-temperature and high-pressure liquefaction,
researchers proposed the low-pressure/atmospheric-pressure liquefaction (also known
as mild liquefaction) technology, which started in the 1980s. Pu and Shiraishi from
Kyoto University in Japan carried out a series of experiments aimed at wood
liquefaction (Pu and Shiraishi, 1993a; Pu and Shiraishi, 1993b). They succeeded in
liquefying the wood under normal pressure and acid catalyst conditions, which had
many advantages including being easy to control, low cost, remarkable economic ben-
efits, and minimal pollution, attracting the whole world’s attention. Thereby, they
improved the development of lignocellulose liquidation technology for chemical
materials.
Compared with the solvents used under high temperature and high pressure, moder-
ate liquefaction usually uses high boiling point solvents because the processes are car-
ried out at atmospheric pressure or in low-temperature conditions. Moderate
liquefaction solvents include water or an aqueous solution and lower-level alcohols
(e.g., ethanol, butanol, cyclohexanol), polyol and its derivatives (e.g., ethylene glycol,
polyethylene glycol (PEG), glycerin), as well as phenol. Phenols and hydroxyl alcohols
are generally believed to have better liquefaction effects at the same temperature and
pressure than simple alcohols and water, and therefore they have gained the most
research attention.
Phenol liquefaction
With phenol as a liquefaction reagent under normal pressure, and phosphoric acid and
concentrated sulphuric acid as catalysts, wood, corn bran, and all kinds of waste mate-
rials are liquefied at 120–200 C with a liquefaction residue rate of 5–50%, which is
lowest (10%) at 150 C. In the phenol liquefaction process, quite a number of phenols
will be involved in the liquefaction reaction and consumed, becoming combined phenol
in the liquefaction products at a level of 50–89% of the wood raw material. And the
phenols not involved in the reactions are regarded as free phenol. Under the action
of acid catalysts, phenol can realize a fine liquefaction effect under standard or low pres-
sure. If the catalysts are alkali, alkali salts, or phenol solution, a certain pressure and
higher temperature is needed to obtain better liquefaction results. For example, using
phenol or phenol aqueous solution as solvent, sodium hydroxide or other alkali metal
salt (such as sodium bicarbonate, sodium formate) as catalysts, wood powder can be
effectively liquefied at 250 C. The worst liquefaction effect is achieved at 170 C.
The lowest residue rate is 6% without any catalyst and 1% when sodium hydroxide
is employed to catalyze the reactions.
Polyhydric alcohols liquefaction

Polyhydric alcohol includes ethylene glycol, PEG, glycerin, or derivatives such as
esters polyols. Pu and Shiraishi reported that wood could be liquefied radically with
polyhydric alcohol as the liquefaction solvent and an acid catalyst at 150 C at normal
pressure (Pu and Shiraishi, 1993a). Under the same conditions, the liquefaction rate of
ethylene carbonate is 27.9 times faster than ethylene glycol and 10 times faster than a
mixed solvent of PEG 400 and ethylene glycol (v/v: 8:2). However, the cyclic carbon-
ate solvent is usually very expensive and degrades easily in the acid solution for a long
time, most of the solvent (for example, ethylene carbonate decomposes into ethylene
glycol and carbon dioxide) will be lost after the reactions and cannot be recovered.
Wang et al. carried out research on straw fiber liquefaction with ethylene glycol as
the liquefaction agent, and concentrated sulfuric acid and phenol as the catalysts
(Wang et al., 2004). They pointed out that liquefaction reactions destroyed the crystal
lattice of the straw fiber structure, and parts of the glucosidic bond were hydrolyzed.
Ge et al. liquefied bagasse in PEG 400 and the liquefaction ratio reached 96% (Ge
et al., 2003). Almost all of the lignin was liquefied. The liquefied products were
mainly polyurethane, whose hydroxyl value was 280–380 mg KOH/g and met the
requirements of strength in a rigid polyurethane foam. The effects of different lique-
faction conditions on corn straw were studied. It was found that the catalyst concen-
tration and the liquid-to-solid ratio affected the results more than the temperature. In
the liquefaction process, the molecular weight of polyols had no effect on liquefication
time and hydroxyl value, and viscosity was suitable for plastic foam making. The den-
sity and mechanical properties of synthesized polyurethane from lignocellulose poly-
ols instead of petrochemical polyols were the same as traditional polyurethane foam
plastics (Aresta et al., 2005).
The effect of a mixed alcohol solvent is better than a single solvent. The lowest
residue rate can be 1% when using a mixed solvent of PEG 400-glycerin (7/3,
w/w) and concentrated sulfuric acid as catalysts. Yet, the residue rate is more than
20% and 32%, respectively, when using glycerin and PEG 400-glycerin alone. This
is because the re-condensation phenomenon occurs with the extension of liquefication
time. If some glycerol is added, the phenomenon will be restricted. For soft wood with
high lignin content, the treatment effect of a mixed solvent (dimethyl carbonate and
ethylene glycol) is much better than a single solvent.
The product of high-temperature and high-pressure liquefaction, which is mainly
used as crude fuel, needs to be further refined and improved. The liquefaction products
will be different under the different conditions of moderate liquefaction versus high-
temperature and high-pressure liquefaction. Many studies have shown that lignocel-
lulose will become liquid material with high reactivity under certain liquefaction
conditions, and this can be used for synthesis of various high molecular weight mate-
rials. This will open a new area for the high-efficiency usage of lignocellulose.
At present, the moderate liquefaction products are most widely used as materials
for high molecular weight products. Phenolic resins are prepared by polymerization of
formaldehyde and liquid products, which result from the liquefaction of wood powder,
starch, corn bran, or waste paper in phenol solvents. All the free phenol can be con-
verted into resin when the liquefied products, together with the unreacted phenol, react
with methanol. The high liquefaction residue rate can also be accepted in the actual
application as the residue can be used as resin packing. The phenol content signifi-
cantly affects the liquid properties of materials and their polymerides. The flowing
temperature, action energy, and shear viscosity increase with increasing phenol con-
tent. The wood is first liquefied with concentrated sulfuric acid or sodium hydroxide
as catalysts, PEG 400-glycerin liquid mixed solvent as the medium, under normal
pressure (150–250 C). Then the liquefied products react with polymethylene diphe-
nylened isocyanate and transform into biodegradable polyurethane coating or poly-
urethane foam plastics. The liquefied products with phenol, bisphenol A, and
polyols as solvent can be used to prepare adhesives. If reacting with certain solvents
such as cross-linking agents and curing agents, the liquefied products can be used for
the production of phenolic resin, polyurethane resin, epoxy resin, and others.
Prof. Chen liquefied wheat straw with hydroxy alcohol and phenol, and used the prod-
ucts to synthesize polyurethane polymer materials and phenolic resin. Furthermore,
the mechanical properties, biodegradability, and the applications as an inert absorbent
material in stable fermentation were also investigated.
Steam explosion pretreatment can significantly improve the effect of straw lique-
faction. The residue rate can be decreased to less than 10% with the liquefaction tem-
perature at 140 C, liquid-to-solid ratio at 6:1, the addition volume of sulfuric acid and
glycerin at 5% and 20%, respectively, and straw has a 100% water content. Infrared
spectroscopic analysis of the liquefied products showed that most of the lignin and
cellulose is degraded and part of the hemicellulose is broken down in the liquefaction
process. Polyurethane foam made from the liquefaction products of steam-exploded
straw not only has good mechanical properties, but also has higher water-absorbing
qualities and biodegradability. Analysis of the physical and chemical characteristics
of liquefied products has found that the viscosity and the hydroxyl value of the prod-
ucts decrease and the weight-average molecular weight stays stable (800 or so). The
phenolic resin directly synthesized from liquefaction products has similar mechanical
properties and higher biodegradability, but the capability to absorb water is not
increased significantly. Despite its mechanical properties, the phenol resin is still
not suitable for use as a carrier in the solid-state fermentation because of its compact
structure, high density, and low water-absorbing quality. The polyurethane foam plas-
tic acquired from steam-exploded and liquefied wheat grass is ideal for use as a carrier
in solid-state fermentation. This kind of carrier not only improves the quality of fer-
mentation products but also simplifies the purification process and solves the tradi-
tional problems in the production and separation processes.
Lignocellulose liquefaction can be used in three ways: as fuel or additives; as car-
bohydrate liquefied products for fermentation; and for the preparation of polymer
materials. But there are some problems at present. The different compositions of lig-
nocellulose affect the stability of final product quality and there are gaps between
some characteristics of lignocellulose products and traditional products. Even today,
the mechanisms of moderate liquefaction and the components of liquid products are
still not clear. As the research on this aspect increases, the application prospects for
this technology will become more numerous.
4.3.6 Combustion technology of lignocellulose

Lignocellulose burning is the oldest and the most widely used method of lignocellu-
lose conversion. Even now it is still the main lignocellulose conversion method in
many rural areas in China. Lignocellulose contains high water and oxygen contents,
which determines that the calorific value of lignocellulose is much lower than that of
fossil fuels. The combustion process can be divided into three stages: the water vapor
evaporation and preheating stage, the volatile combustion stage, and the fixed carbon
combustion stage. To improve the calorific value, we can carry out pretreatment pro-
cesses as follows: in the water vapor evaporation and preheat phase, we can add fuel
initiator, supply oxygen, or enhance the ventilation rate to decrease the igniting point.
Adding catalysts such as a barium agent and manganese to the dense solid fuel can
decrease the surface activation energy of lignocellulose. What is more, after compres-
sing the loose lignocellulosic raw materials, the combustion efficiency can be
improved and the storage space can be saved (Baulch et al., 2005).
Power generation from lignocellulose combustion technology is an important
research direction for lignocellulose burning conversion. In the basic process, ligno-
cellulose is burned directly in the boiler and then the high-temperature and high-
pressure gas produced pushes a steam turbine, which finally drives a generator to pro-
duce clean and efficient power. In 1988, BWE Corporation from Denmark took the
lead in research and built the world’s first straw lignocellulose burning power plant
(Haslev, 5 MW). Later, BWE built the UK Elyan power plant, which was the largest
in the world at that time with an installed capacity of 38 MW. In 2005, there were more
than 130 lignocellulose straw power plants throughout Denmark, and the installed
gross capacity reached 7000 MW (Zhang et al., 2010). Finland and Sweden also
widely use lignocellulose combustion for power generation, and lignocellulose pro-
vides a quarter of the total electricity generated in Finland. As of 2011, America
had set up more than 350 lignocellulose power plants and the installed gross capacity
surpassed 10 GW.
While power generation from lignocellulose direct combustion has been heavily
researched, there are still some problems restricting its development.
(1) The collection radius. The lignocellulose resource is abundant, widespread, and the reserve
is large. However, collection is very difficult and seasonal, and the supply reliability is
very poor.
(2) Raw material storage. Lignocellulose density is low and it requires a large storage area. In
addition, it also requires the construction of waterproof, fireproof, and moisture-resistant
facilities.
(3) High combustion equipment requirements. Lignocellulose comes from diverse species, and
the components vary with the species types, producing area, and growth periods. So it calls
for high requirements in terms of boiler types and performance. When the material is
uploaded, it is easy for blockages to occur, leading to boiler combustion instability.
(4) High requirements for the uploading and downloading systems. Because the lignocellulose
is usually soft, and the density and calorific value of lignocellulose are low, the consump-
tion volume of lignocellulose fuel is much larger than that of coal-fired power plants of a
similar scale.
(5) The combustion of lignocellulose is not very stable; the optimal operation level needs to be
improved; the content of water and oxygen in the lignocellulose is too high; the calorific
value is low; under the same boiler steam rate condition, smoke volume is larger, the com-
bustion is not stable, and the ash carbon content is high, resulting in auxiliary equipment
failure and high energy consumption, as well as low combustion efficiency.
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Lignocellulose biorefinery product
engineering 5
5.1 Overview
Petroleum refining is a technology that uses fossil fuels as raw materials and chemical
catalysts as a means to achieve conversion of petroleum through once, twice, and deep
processing to get a series of chemical products, which are further used as the basic raw
materials for synthetic fibers, synthetic rubber, plastics, chemical fertilizers and pes-
ticides production. With the gradual depletion of oil resources, the fossil economy is
facing serious challenges. Biorefining has gradually become a new method used to
produce energy and chemical products, which parallels petroleum refining. Biomass
is used as a raw material to produce some middle platform compounds by thermo-
chemical, chemical, or biological methods, which are then processed into bio-fuels
or chemicals. Biorefining offers the possibility of achieving sustainable production
of bioenergy and biomaterials. Biorefining is a new concept in industrial manufactur-
ing, which will become a new manufacturing technology paradigm, becoming more
and more important because of its use of alternative resources and its environmental
benefits (Demirbaş, 2001).
Biorefinery products consist of: heat; electricity; various solid, liquid, and gaseous
energy products; as well as bio-based materials and chemicals. The distinctive char-
acteristics and functions of biomass allows for its use in products that will most likely
replace oil, coal, and natural gas, opening up a future nonfossil fuel energy era. Bio-
mass can produce liquid fuels to replace oil, solid fuels to replace coal, as well as gas-
eous fuel to replace natural gas.
Compared with petroleum refining, biorefining is unique for the following reasons:
(1) Biorefinery feedstock is carbohydrates while petroleum refining involves hydro-
carbons without oxygen molecules and lacking functional groups, thus biorefining
is more economical from the point of view of atom utilization. Therefore, it is
cost-effective due to the avoidance of the high-cost oxidation process. (2) Compared
with the petroleum fuels, biodiesel obtained from biorefining has better oxidation sta-
bility and higher energy density, which can reduce carbon deposits on the engine, so
that operating costs are only half those of the conventional diesel apparatus. (3) In the
petroleum refining process, the resource-rich region is separated from the end market,
which means long-distance transport is required, while biomass resources are usually
found near to the market.
Biorefinery techniques are far from mature. However, with the advances of techno-
logy, a number of bio-based products that are able to replace or partially replace
petroleum-based products – such as fuel ethanol, lactic acid, citric acid, biodiesel
and 1, 3-propanediol – have sprung up. These products can be divided into many groups
according to carbohydrates platform, oil platform, and thermochemical platform.
Crude oil
Pretreatment Biomass
Hydro-
Oil cracking
Gasification/ Other
refining Pretreatment
pyrolysis processing
Farm produce
Gas Enzymatic
Hydrogen
separation hydrolysis
Fuel/ Biochemical
chemicals Synthesis Fermentation
reactions
Energy
Post- Biochemical
Steam and processing products
power
generation Residue
Biofuel
Figure 5.1 Schematic diagram of biorefining and petroleum refining.
Although there are a variety of products from biorefining, many of them are not needed
in large quantities. Therefore, it would be not be economical to prepare all of these
products directly from the basic raw materials. Hence, it is necessary to develop many
platform products, such as succinic acid, fumaric acid, or malic acid, which can then be
economically converted into various chemicals (Wang et al., 2007; Figure 5.1).
5.2 Bioenergy
Solar energy is the source of almost all energy on earth. Biomass is a resource pro-
duced from the conversion of solar energy. The energy basis for modern industrial
development (i.e. coal, oil, and natural gas), evolved from the ancient biomass buried
under the ground through the joint action of microbes and geological chemistry.
Trends in the utilization of energy are biomass ! coal ! oil ! coal ! biomass.
Humans have improved the utilization efficiency of energy by changing their utiliza-
tion methods. Conversion of biomass to bioenergy alternatives of coal, oil, and natural
gas or other fossil fuels is in line with the balance: CO2 þ sunshine ! crops ! bio-
based energy ! CO2, and finally forms a mass cycle with a theoretically zero net
CO2 emission (Figure 5.2).
If biomass completely replaced fossil fuels, CO2 emissions during the production
and transfer of biomass energy such as bioethanol would be equal to those during the
exploitation and transfer of fossil fuels. However, alternative energy can reduce CO2
Product engineering 127
CO2+H2O Solar energy
Photosynthesis
Carbohydrates
Physical transformation Biotransformation Thermochemical conversion
Ethanol
Butanediol Gasification gas
Biomass briquette
Biogas Pyrolysis oil
Hydrogen
Combustion
CO2+H2O
Figure 5.2 Ecological carbon balance of biomass energy.
emission through improving the energy utilization methods and the utilization ratio. In
addition, in the process of biofuels production, N, S, and other impurities are removed
to a great extent. Therefore, it is a type of green energy. It meets the demand for
decreasing CO2 emissions, and creates a low-carbon economy to replace fossil fuels
with biomass energy. Moreover, it can reduce the concentration of pollutants in the
atmosphere, which helps to protect the environment.
The BP Statistical Review of World Energy Report 2011 showed that as of the end
of 2010, oil, natural gas, and coal can only be used for another 46.2, 58.6, and
118 years, respectively, according to the world’s proven reserves and production
(‘BP statistical review of world energy June 2011’, 2011, Available from: www.
bp.com/statisticalreview). China is short of fossil energy resources, especially oil
and natural gas. However, due to the rapid development of the Chinese economy,
energy consumption is increasing sharply, and accounted for 20.3% of total global
energy consumption in 2010; Chinese coal consumption accounted for 48.3% of total
global coal consumption (‘BP statistical review of world energy June 2011’, 2011,
Available from: www.bp.com/statisticalreview). China has surpassed the USA to
become the largest energy consumer in the world. Although the use of new forms
of energy is growing rapidly, coal is still the primary energy form in China, and this
is unlikely to change in the short term, resulting in the situation where China’s emis-
sions of SO2 and CO2 rank first and second in the world, respectively. Therefore, look-
ing for environmentally friendly clean energy to gradually replace oil and coal and
meet the large demand for liquid energy is an irreversible quest. We should develop
new kinds of available energy before running out of oil. The ultimate aim of bioenergy
research is to reduce our dependence on oil; thus, our current challenge is to search for
large-scale, economically feasible bioenergy technologies. As is shown by the con-
stant consumption and shrinkage of fossil fuels and their increasing price, we have
to accelerate the pace of study and production of bioenergy. In order to realize the
industrialization of bioenergy, two key factors are essential: first is the determination
and planning of government, favorable legal policy, guaranteed huge investment, and
market demand from consumers; and second is making constant progress in biorefin-
ery technologies and breakthroughs in key technology.
Biomass can be used with oil as a raw material to produce chemical products and
other substances, while other sources of energy cannot. The composition of biomass
from different materials varies widely. For example, the main components of straw
are cellulose, hemicellulose, and lignin; potatoes are mainly composed of starch;
while oil-bearing crops contain fat. However, all in all, the main components of plant
materials contain the following basic substances: carbohydrates (including sugar), starch,
cellulose, hemicellulose, lignin, fat, and protein. Biomass materials contain various sub-
stances, and many oxygen-containing groups like hydroxy, carbonyl, and benzene rings.
Compared with the linear aggregation structure of oil materials with only d(CH2)nd,
biomass is more suitable for chemical modification and producing various chemical prod-
ucts as well as providing more chances for development of new products in addition to the
conversion to bioenergy, such as biofuels (Chen and Wang, 2008).
Using different techniques, biomass can be converted into different products. Bio-
mass can be burned directly or used to generate electricity by gasification; provide gas
resources; be converted into biogas (biogas, biohydrogen), biofuels (bioethanol, bio-
diesel, biobutanol, bio-oil, solid fuel), and also into biological materials and chemicals
(acid, polylactic acid); and so on. The choice of the best pathway depends on the spe-
cific issues of each situation. Oil is processed via heated distillation, catalytic crack-
ing, hydrocracking, and other technologies to produce fuels like gasoline and
ethylene, and chemicals like propylene, based on different market needs. Therefore,
with the development of raw material resources and the utilization of advances in tech-
nology, biomass energy will play an important and indispensable role in human life.
5.2.1 Ethanol
5.2.1.1 Applications and market for fuel ethanol
The most direct and important application for the bioenergy system is to produce eth-
anol through biomass fermentation technology. With the gradual depletion of fossil
resources, more and more countries have regarded the energy supply diversification
strategy that ethanol and other alternative energy sources supply as one of the main
directions for their energy policies. The rise in oil prices, constant progress of fuel
ethanol manufacturing technology, the wide application of flexible fuel vehicles
(FFV), the widespread use of renewable fuel ethanol, and expanded sources of raw
materials have brought about reliable technology and economic viability for the fuel
ethanol industry. In addition, the application of fuel ethanol in diesel engines can fur-
ther expand the application range of fuel ethanol, which will provide a broader utili-
zation base for fuel ethanol.
Ethanol is a new kind of green energy as well as a basic chemical raw material that
is widely used in the chemical engineering, food, beverage, military, household che-
micals, pharmaceuticals, and health fields. Moreover, as an excellent fuel (combustion
value reaching 26,900 kJ/kg), ethanol can improve fuel quality. The advantages of
using ethanol fuel include the following: (1) ethanol can replace or partially replace
gasoline as a motor fuel, reduce gasoline consumption, and ease the demand for fossil
fuels, thereby reducing dependence on oil imports and improving national energy
security; (2) as a high-octane gasoline component, the octane number of ethanol is
generally above 120, it can improve the anti-knock properties of spark-ignition inter-
nal combustion engines and make the engine run more smoothly; (3) due to the fact
that ethanol is an aerobic fuel, it can replace methyl tert-butyl ether (MTBE), which is
a pollutant to water, making combustion more complete and decreasing the emission
of air pollutants such as particulate matter and CO by at least one-third, which reduces
energy consumption; (4) it can effectively eliminate carbon deposits on spark plugs,
valves, piston tops, and the exhaust muffler, thereby extending the service life of the
main parts of automobiles. The entire production and consumption of ethanol can
form a clean and nonpolluting closed cycle, which is permanent and endless
(Cardona and Sánchez Toro, 2006).
More than 90% of the ethanol in the world is produced by fermentation of biomass,
so ethanol is a renewable energy source. The exploitation of ethanol fuels has become
more and more important with intensive need for liquid fuels and the huge pressure
this puts on the environment. Attention is paid to ethanol production due to its poten-
tial to decrease oil consumption and reduce environmental pollution, especially after
the introduction of the Kyoto Protocol; the application of ethanol is regarded as an
effective measure to make use of biomass and reduce CO2 emission.
5.2.1.2 The development of ethanol production

and associated problems
The main materials used to obtain fuel ethanol by fermentation processes are raw
sugars, starch, and lignocelluloses, while cassava, sweet sorghum, and corn stalks
are the focus for the development of fuel ethanol production in China. Sweet sorghum
is a saccharine material whose syrup after pressing is mainly used for fermentation;
and cassava is a kind of starch feedstock whose glucose component from starch hydro-
lysis is used for fermentation. Both of these processes produce ethanol from parts of
the biomass materials. However, because sugar and starch are edible, the production
of ethanol from these materials faces the problem of competing for a resource that is a
source of food for humans, and what’s more, the cost of raw materials makes up more
than 40% of the total cost (Li et al., 2011). Therefore, the production of fuel ethanol
faces dual pressures on moral and cost grounds, and this has led to high hopes for
cellulose ethanol production. Corn stalks are cellulose materials, and the glucose pro-
duced via hydrolysis of cellulose is used for fermentation. Despite the fact that ligno-
cellulosic raw materials like straw are abundant, their complex structure requires
complicated technology routes, and results in low utilization rates and high energy
consumption for separation, which leads to a higher production cost than sugar and
starchy materials. To fully use lignocellulosic raw materials, the following challenges
must be overcome: technology must be simplified, production costs reduced and
wastewater emissions reduced. At present, many factories produce bioethanol from
straw, cassava, and sorghum. It is necessary to search for new technologies to produce
ethanol from agricultural and forestry wastes instead of corn and thereby improve the
multipurpose utilization, reduce the production cost of bioethanol and enhance com-
petitiveness (Figure 5.3).
In August 2006, the first fuel ethanol production demonstration project from straw
enzymolysis and fermentation with an annual yield of 3000 t was established, based on
the patents of low pressure and nonpollution steam-explosion pretreatment for straws
and cellulase production via solid-state fermentation that was proposed by Prof. Chen.
The technology could produce high-value-added xylo-oligosaccharide besides ethanol,
which conquers the problem of ethanol conversion from xylose and also improves eco-
nomic returns. Such technologies possess proprietary intellectual property rights and
complete technical parameters, which will provide a rich experience for the industrial-
ization of cellulose ethanol production at a level level of 10,000 tons (Chen and Qiu,
2007).
The cost of raw materials, which accounts for 65% of the total cost, is a key
factor for the economic feasibility of the technology. The cost of cellulase and corn
Cellulase storage tank
Dilute sulphuric acid
Seeding tank
Raw material storage
Disintegrator SSCF reactor
Pretreatment reactor
Solid liquid separator

Molecular sieve
Lignin
Rectification
Distillation
Fuel oil
Ethanol
Stillage
Figure 5.3 Process flowchart of fuel ethanol production from corn stalk.
stalks severely affects the production cost, which is also one of the key factors that
affect the ethanol cost.
However, there are still many problems to overcome to realize the industrialization
of such a process; among which are how to realize the effective saccharification of
straw cellulose and avoid the mutual inhibition effects between raw materials and
products.
5.2.2 Butanol
5.2.2.1 Applications and market for butanol
Biobutanol or bio-based butanol fuel is a second-generation alcoholic fuel with a
higher energy density and lower volatility compared to ethanol. Butanol’s application
as a replacement for gasoline will outpace ethanol, biodiesel, and hydrogen when its
safety and simplicity of use are seen. Butanol is an important chemical raw material
and organic solvent, which is widely used in industry, medicine, and food. As a better
prospective new biofuel than ethanol, butanol has broad application prospects due to
its good water-insolubility, low vapor pressure, high calorific value, and other char-
acteristics. Butanol can reach a higher mixing rate with gasoline compared to ethanol
fuel and its energy density is closer to gasoline, which is more suitable for the existing
fuel supply and distribution systems. At the same time, butanol is more environmen-
tally friendly when compared to fuels from oil refining and hence decreases the emis-
sion of greenhouse gases during the gasoline refining process.
The butanol fermentation industry began in the early 20th century, and was applied
on a large-scale in World War I. Butanol fermentation has become the second largest
fermentation industry next to ethanol fermentation (Durre, 2011). Because the
fermentation products are a mix of acetone, butanol, and ethanol (acetone–butanol–
ethanol, ABE), the solvent production fermentation is also known as ABE fermenta-
tion. With the development of the petrochemical industry, the chemical method to
produce butanol from petrochemical feedstock has shown more advantages over
the fermentation method based on both cost and productivity. Therefore, butanol
production from the synthesis method had gradually replaced the fermentation method
by the 1960s. However, people paid attention to butanol production via fermentation
again due to the outbreak of the oil crisis in the late 1970s. And in the 1980s, the study of
the genetic system of clostridium-producing solvents made great progress, which played
an important role in improving the grains’ fermentation properties. The most widely
researched subjects were the construction of excellent strains and the improvement
of fermentation and separation technologies.
5.2.2.2 The development of butanol production

Raw material cost accounts for 60–70% of the total cost of butanol, which is an impor-
tant limitation of the industrial development of butanol fermentation. Corn, wheat, and
molasses have been the primary materials for acetone–butanol fermentation for a long
time. However, with the constant rise in food and molasses prices and the potential
demand for grains by the increasing world population, choosing cheaper lignocellu-
losic feedstocks like straw has become an effective route for reducing fermentation
cost (Chen et al., 2010). The cellulose and hemicellulose produced after lignocellu-
losic feedstock hydrolysis or acid hydrolysis may be converted into sugars by micro-
bial fermentation. But due to the fact that the composition of lignocellulosic feedstock
materials is more complex than food and the conversion efficiency is relatively low,
lignocellulosic raw materials should be pretreated before fermentation. Researchers
began to study the use of lignocelluloses for acetone–butanol fermentation in
the 1980s.
In addition, for butanol production, the bottleneck lies in the low butanol concen-
tration caused by the inhibition of butanol fermentation products. Therefore, it is nec-
essary to adopt a strategy of continuous fermentation to achieve efficient production
of butanol and the aim of coupling fermentation with separation technologies. In this
way, we may realize the goals of removing the inhibition of butanol fermentation
products and saving separation and energy costs. Our group (Wang and Chen,
2011) constructed a fermentation device coupled with enzymolysis and membrane
recycling, and used steam-exploded wheat straw to produce acetone–butanol, which
realized of a maximum yield of butanol of 0.31 g/(L h), a cellulose and hemicellulose
conversion rate of 72% and 80% respectively, and achieved continuous enzymatic
hydrolysis and fermentation. This illustrates that the use of lignocellulosic raw mate-
rials to produce acetone–butanol by fermentation is feasible. Concerning the problems of
low enzymolysis efficiency and difficulty in degrading cellulose, Prof. Chen used the
hydrolysate of hemicellulose to produce acetone–butanol via fermentation, and the
cellulose was used for butanol fermentation after grading to obtain short fibers.
Meanwhile, the long fibers and lignin within the straw were used for the production of
high-value products. They accomplished an increase in butanol production with an
annual yield of 50,000 tons together with cogeneration of acetone, ethanol, furfural,
polyether polyol, and phenolic resin (Kamm and Kamm, 2007) (Figure 5.4).
Figures 5.5–5.7 show the industrial-scale application of this polygeneration technology.
A straw refinery production line established by the Institute of Process Engineering
and Songyuanlaihe Chemical Co. Ltd started to run in August 2010 with an annual
processing capacity of 300,000 tons. The line is a high value-added way to utilize
straw in which the five-carbon sugars are used to produce butanol, acetone, and eth-
anol; long-cellulose fiber is used to make paper; and short-cellulose fiber and lignin
are used to produce polyether and phenolic resins as well as other products. Using the
lignin and cellulose produced by this production line, another two production lines
with polyether polyol yields of 50,000 tons per year and phenolic resin glue yield
of 20,000 tons per year are going to start operation. After the 300,000 t/y straw refin-
ery line production was put into operation, the total sales reached 1.2 billion yuan
(US$ 192 million) with about 100 million yuan (US$ 16 million) profit.
Although lignocellulose is considered to be the best prospective fermentation sub-
strate, there are many problems in the process of converting lignocellulosic feedstock
into butanol. The current situation is that the major industrial strain of Clostridium still
cannot effectively hydrolyze lignocellulose. Therefore, lignocellulosic feedstock
Product engineering
Acid hydrolysis residue
Steam
explosion
Cornstalk vessel
Screw press dewaterer
Hydrolysis tank
Pulverizer
Furfural
P-40
Condenser Short-fiber
Vacuum distillation tank Extraction residue
P-21
Alkali
treated
materials Long-fiber
Vacuum distillation tank
Carding machine
Screw extractor P-22 NaOH solution

Alkali extract pot
P-10 Extraction liquor
Electrodialysis
Agitation tank NaOH Ultra filtration membrane
solution
Activated carbon
treatment
Furfural
Lignin
Butyl alcohol fermentation

tank Rectifier
Agitation tank
P-43
Drying machine Centrifuge
Ethanol tower Sewage

Acetone tower Waste liquor
Butanol, acetone and plant
ethanol
Solvents
Butanol tower
Vacuum distillation tank
Figure 5.4 Flowchart of converting hemicellulose into butanol and the comprehensive utilization of corn stover.
133
Figure 5.5 An 80 m3
hydrolysis tank.
Figure 5.6 A 400 m3 fermentation

tank.
Figure 5.7 Butanol–acetone distillation tower.
must be pretreated to effectively hydrolyze cellulose and hemicellulose into monosac-

charide, which is suitable for Clostridium to convert to butanol. Meanwhile, many
complex products during the pretreatment period of lignocellulose could inhibit the
fermentation of butanol. More importantly, during the utilization process of lignocel-
lulose, people often use a single technology and use only one component while ignor-
ing the use of other components, resulting in materials waste and environmental
pollution, which is the main reason that the whole biomass industry can not compete
with the petrochemical industry.
5.2.3 Biogas
5.2.3.1 Applications and market for biogas
Energy is the foundation for the progress of human civilization as well as an indispens-
able requirement for the progress of modern society (Demirbaş, 2001). For a long
time, fossil fuels have played the dominant role in the energy structure of China.
Therefore, using cleaner energy utilization technologies is essential in order to protect
the environment and tackle climate changes. Marsh gas is one kind of renewable
resource and using wastes from marsh gas production by anaerobic digestion is a
favorable avenue of exploration toward solving the energy crisis. Therefore, both
Western countries and China have attached importance to marsh gas production
(Chen et al, 2010).
China’s energy consumption increased by 11.9% in 2010, which made China the
world’s largest energy consumer, surpassing the USA. China can be described as
being rich in coal, having less oil and a shortage of gas. Of the fossil fuel reserves
in China, oil and gas account for 5.4 % and 0.6 %, respectively. China’s natural
gas resources and productivity are severely insufficient compared with the rapidly
increasing demand. For example, the natural gas yield was 103.06 billion m3 and
the consumption was 117.38 billion m3, with a 14.32 billion m3 gap between supply
and demand (‘BP statistical review of world energy June 2011’, 2011, Available from:
www.bp.com/statisticalreview). With the rapid development of its domestic econ-

omy, the gaps between supply and demand for oil and natural gas will increase and
will influence the sustainable development of China, which could also cause potential
safety hazards for the energy supply of China. Due to the huge gap, energy alternatives
are essential to release the import pressure on oil and natural gas. The effective com-
ponent of marsh gas and natural gas is methane, and the content of methane in purified
marsh gas could reach 95%. Therefore, marsh gas is almost the same as natural gas and
will be an optimal choice to displace natural gas. That is also the reason that both
medium and large marsh gas project construction has been paid much attention by
society. Moreover, construction of marsh gas projects requires a lot of money, which
encourages the government to pursue the application of agricultural waste technolo-
gies (Jiang et al, 2011).
As a molecular functional structure assembly consisting of cellulose, hemicellu-
lose, and lignin, straw has a complex chemical structure and composition, which
results in the mutual disturbance of various components and a low conversion ratio
during plant usage, and hence causes difficulties in high-value utilization. If we could
separate the components effectively and then convert them separately, we could
improve the conversion efficiency of straw by reducing the mutual disturbance, but
also make full use of the different components and increase the comprehensive utili-
zation value (Jin and Chen, 2007). Compared with the usual raw materials like live-
stock manure, straw is widely distributed and abundant and could completely solve
the problems of insufficient raw materials for marsh production. Due to its low water
content, the biogas residue is solid, which could be used as organic manure directly.
Meanwhile, biogas slurry could be used for water content adjustment for the next fer-
mentation, which meets the demand of a circular economy during a cleaner production
process. While the livestock manure has high water content, the biogas residue and
slurry are hard to use and dispose of. Moreover, some biogas residue and slurry are
discharged without treatment, which causes secondary pollution to the environment
and would not solve the environmental pollution problem. Straw can be preserved
for a long time and transferred conveniently, and has a relatively low cost. Biogas pro-
duction from straw refining is an environmentally friendly, clean process that could
realize the complete conversion of straw and the high-value utilization of resources
(Kaparaju et al., 2009a, 2009b).
5.2.3.2 The development of biogas and associated problems

Biogas can decrease energy consumption, reduce pollution, and construct a platform
of rural energy conservation and emission reduction, as well as improving rural health,
solving the problem of household energy consumption of farmers, and protecting the
environment. Thus, biogas project construction has become an essential link that
promotes construction in the countryside and develops a sustainable agricultural cycle.
The existing ecological agricultural modes “Four in One” (a typical one is pig-biogas-
vegetable-heliogreenhouse) and “Three in One” (a typical one is pig-biogas-fruit) are
choices based on the raw materials of human and animal manures. These development
modes cannot satisfy the demand of large-scale and intensive breeding, agricultural
modernization, rural urbanization, and city and countryside integration. Producing
biogas from straw has the advantages of abundant materials and wide distribution
without limitations of time and space, which can achieve a complete ecological cycle
and effective utilization of straw. Straw is rich in cellulose, hemicellulose, and lignin
that contain plentiful energy. Therefore, straw can be used as a potential energy
supplier to solve the current security issues related to the energy supply. Through
appropriate pretreatment, bioenergy in the form of biogas could partly satisfy the need
for renewable green energy (Zeng et al., 2007). In this way, biogas not only solves the
problems of agricultural waste pollution of the environment and disposal difficulties,
but also produces biological natural gas that partly displaces fossil resources. And
at last, the aims of low carbon, circular economy development, and clean energy
replacement will be achieved.
The effective constituent of biogas and natural gas is methane. Therefore, biogas is
the optimal choice to displace natural gas. For a long time, agricultural wastes such as
straw have been used as auxiliary ingredients for anaerobic digestion to adjust C/N and
not as the main materials to produce biogas via anaerobic digestion. The reasons are
the following: straw contains a high proportion of lignocellulose, which is hard to
digest using anaerobic bacteria, leading to a low digestion rate, low yield of biogas,
and poor input and output efficiency; straw cannot be digested continuously due to its
nonflowing character; straw materials cannot achieve a high production efficiency due
to their low density, large volume, and difficulties in feeding and ejecting the mate-
rials; and the existing devices are designed for the digestion of wastewater and live-
stock excrement, which are not suitable for straw materials. However, compared with
the usual digestion raw materials such as livestock excrement, straw has the charac-
teristics of being widely available, having convenient collection and storage, and
being cheap in price. Therefore, straw could be a prospective resource for a significant
bioenergy industry if all these problems are solved.
At present, the use of biogas as an alternative to coal and natural gas to generate
electricity and heat or serve as bionatural gas for automobiles has been industrialized
in EU countries (Li et al., 2011). Moreover, biogas utilization has turned into a
win–win situation of energy generation and environmental protection rather than just
simply a service for environmental protection. Despite the current situation, we think
that the economic value of biogas still remains to be exploited. Especially in China, it
is hard to realize the dual benefits of economy and environmental protection without
special project funding and fiscal subsidies from the government. Based on these
problems, we believe that biogas production via the straw refining process should start
from raw materials, the production process, and the products. After that, the issues
involving extracting xylose from straw hemicellulose hydrolyzate, and obtaining
acetic acid and bioethanol from the biogas production process should be studied.
5.2.4 Hydrogen
5.2.4.1 Applications and market for hydrogen
Fossil fuels will be used up in the near future, while hydrogen gas is one of the most
ideal alternative energy sources at present. Due to the fact that hydrogen itself is
renewable and does not generate any kind of pollutants (even CO2 during
combustion), using hydrogen gas could realize zero release. Hydrogen has a series of
advantages over other energy-containing substances. The energy density of hydrogen
is 2.68 times higher than that of gasoline; its electricity-storing properties could be
superior to any other method in terms of economic efficiency of technology; its ther-
mal efficiency is 30–60% higher than that of other fossil fuels when converted into
power; for example, hydrogen could be used as the fuel of fuel cells and combined
with fuel cells to provide an effective, clean, non-drive disk assembly and non-noise
technology, whose efficiency would be improved by 100%; hydrogen is fit for pipe-
line transportation and can share the same delivery system as natural gas; and the
delivery cost of hydrogen is the lowest and the loss is the smallest of all the energy
forms. Pint-sized, low-temperature, solid-ion exchange membrane fuel cells could be
used in automobiles and trains. In addition, hydrogen can serve as fuel for engines
directly. At present, hydrogen is used as an alternative to fossil fuels in hydrogen fuel
automobiles and hydrogen fuel cells. Powerful market demand from the oil, chemical
engineering, electricity, and chemical fiber industries should promote the develop-
ment of hydrogen industrialization. We believe that hydrogen will be one of the main
sources of energy in the post-fossil fuel era.
5.2.4.2 The development of hydrogen production

Due to its clean combustion products, high energy density, high thermal conversion
rate, and low transportation cost, hydrogen is regarded as an ideal source of clean
energy and is essential for the modern economy and sustainable development. At pre-
sent, hydrogen production from fossil fuels like coal, oil, and natural gas has begun to
take shape. However, it will not meet the need for sustainable development over the
long haul. High cost is the main problem restricting the industrialization of hydrogen
production. China has abundant materials for hydrogen production. The cost would be
decreased dramatically if industrial wastes, municipal sewage, household refuse, ani-
mal waste, and lignocellulose biomass were used to produce hydrogen after fermen-
tation. Dark fermentation coupled with biohydrogen production technology could
integrate effluent treatment, solar energy utilization, and clean energy production
organically and form a new kind of environmentally friendly industry. Therefore,
hydrogen via fermentation has huge potential either from the aspect of protecting
the environment or exploiting new energy sources and sustainable development
(Kumar et al., 2009). Research on hydrogen is relatively small compared with meth-
ane production via biomass fermentation. Studies by Chen showed that the maximal
hydrogen yield reached 68 ml/g of steam-exploded straw using Clostridium butyricum
to produce hydrogen via simultaneous saccharification and solid-state fermentation
with straws as substrate (Corredor et al., 2008).
How to reduce the hydrogen production cost is a question that perplexes hydrogen
applications, especially biohydrogen production via fermentation; this is also the
problem to solve to make hydrogen more competitive compared with other bioenergy
sources such as biogas and cellulose ethanol (De Vries et al., 2010). Additional prob-
lems include how to improve the conversion rate of hydrogen from glucose and how to
produce hydrogen effectively at the bioreactor level.
As two kinds of energy carriers, hydrogen and methane are both important raw mate-
rials for energy production and chemical engineering. More research concerns the pro-
cesses of how to produce hydrogen during methane fermentation and how the
fermentation residue of hydrogen production could be used as a substrate for methane
fermentation. In this way, the benefit of co-production would be much larger than that
of sole production. Furthermore, cheap development and utilization of substrates is
important for reducing the cost of biohydrogen production. Research is needed on both
dark fermentation and light fermentation for hydrogen production from industrial and
agricultural wastewater, municipal sewage, livestock wastewater, and lignocellulose bio-
mass materials, which could decrease production costs and help protect the environment
at the same time.
5.2.5 Biomass briquettes

5.2.5.1 Applications and market for biomass briquettes
Biomass briquette fuel technology is one of the main directions of biomass conversion
and application technologies. Studies showed that the combustion properties were
increased by 20% after the biomass was molded into solid briquettes. Moreover,
the emissions of greenhouse gas, NOx, and SO2 were only one-ninth, one-fifth,
and one-tenth that of coal, respectively. Biomass briquettes have the advantages of
an abundant supply of raw materials, simple technology, convenient operation and
low cost. Due to high thermal efficiency, excellent combustion properties, convenient
delivery properties, and ease of industrialization of biomass briquettes production,
they are fit for utilization on a large scale. Biomass briquettes are also suitable sub-
stitutes for coal in the fields of rural cooking, heating, providing clean fuels for cities,
providing energy for greenhouses, and providing fuels for industrial boilers and power
stations. The productivity and demand for biomass briquettes have recently increased
rapidly. For example, the total production of biomass briquettes was 766,000 tons in
2009, in China alone, which will have reached 20 million tons by 2015. China is a vast
agricultural country whose biomass resources are very rich, which provides a guaran-
tee for the development of biomass briquettes.
Biomass briquettes are molded materials with a certain degree of density, and are
produced as follows. Lignocellulosic raw materials are crushed into particles of appro-
priate size, and then the particles are compressed to rod-like, nubbly, or granulous
materials without either heating or adhesive under the conditions of 50–200 MPa
and 150–300 C (Jin et al., 2013). In recent years, biomass briquettes have developed
rapidly as competitive fuels (Yu et al., 2009) (Figure 5.8).
5.2.5.2 The development of biomass briquette production

The final forms of biomass utilization are gas, liquid, and solid. Conversion of bio-
mass to liquid and gaseous products must go through a chemical reaction process, dur-
ing which a certain amount of energy is lost. Therefore, compared with other
utilization technologies of biomass, biomass briquettes are easier to produce on a large
Figure 5.8 Biomass briquettes – pelleted fuel.
scale due to the simple production process and the ease of use of the end-products.
Hence, China has included the research and industrialization of biomass briquettes
in its renewable resources project.
Biomass briquettes are produced through dehydration of collected loose straw, then
grinding and extruding the straws into rod-like, nubbly, globular or granular solid
fuels, especially rod-like and granular ones. The physical and chemical properties
of briquette fuels are different from straws. Biomass briquettes solve the problems
of low bulk density, low energy density, and difficulty of storage and transfer.
The combustion properties of biomass briquettes have greatly improved, increas-
ing from 10–15% of direct burning to 30–40%. Meanwhile, biomass briquettes have
the advantages of high volatility, ease of burning, and low ash content compared with
coal. The combustion gases of biomass briquettes contain only a trace of SO2. There-
fore, biomass briquettes can realize the aim of zero CO2 emission and little pollution
of the environment as a kind of renewable resource.
However, the main problems of biomass briquettes utilization are hearth corrosion
and slag bonding (Zhang, 2007). The most significant characteristic of biomass bri-
quettes is a high Cl content (0.2–3.0%) compared to fossil fuels. The high Cl content
leads to the severe corrosion of hearth and the combustion residues tend to appear as
slagging phenomena similar to that of coal. The mechanism of deposition and corrosion
may be that the volatile alkali metal salts enter the gas phase of the hearth under 700 C
during combustion, and the volatile ash and other fine particles coagulate on the con-
densing surface to form the initial settled layer. With the increase of temperature, a melt-
ing bonding surface appears and a new settled layer is formed on the initial layer when
larger particles fall on the initial settled layer. If the hearth temperature exceeds 780 C,
these deposits form glassy slags (a complex mixture), which could take the boiler out of
operation. Usually, large-scale biomass boilers need to shut down every 10–12 months
for cleaning, and this can take about one week.
5.2.6 Bio-oil
5.2.6.1 Applications and market for bio-oil
Bio-oil is a complex mixture of organic fuel containing 25–30% water and a small
amount of fine carbon, whose calorific value is 15.0 16.0 MJ/kg and is more difficult
to ignite and burn out. Bio-oil has the advantages of abundant resources, renewability,
convenient to deliver, and high energy density, which gives it potential as a liquid fuel
and chemical raw material (Wang et al., 2010).
Depending on the sources of bio-oil, it can be divided into three categories. The first
is the liquid products derived from the destructive distillation of biomass, which is
called wood tar. Wood tar is similar to coal tar, and consists of polycyclic aromatic hydro-
carbon and asphaltene. The second category is bio-oil derived from rapid pyrolysis or
liquidation whose major component is liquid fuel. Compared with conventional crude
oil, this kind of bio-oil has some disadvantages, such as unsteady physical and chemical
properties, component changes with time and temperature, high viscosity, and high
oxygen and water content. The third category is the tar produced from the biomass
gasification process, which is an inevitable by-product that will affect the operation
of systems once condensed and coked. Therefore, corresponding measures should be
taken to control the tar yield in order to get syngas with high quality. Table 5.1 shows
the component analysis of bio-oil from straw pyrolysis (Jung et al., 2008).
5.2.6.2 The development of bio-oil production

(1) Commercial value of bio-oil (Zeng et al., 2011).
First, bio-oil can completely dissolve in alcohol. By adding a small amount of alcohol, the
fuel properties could be highly improved, the viscosity decreased, and the stability
enhanced. Compared with ethanol on a commercial level, these blended products are more
environmentally friendly due to the lower price.
Second, bio-oil is insoluble in diesel oil, although it could be emulsified by diesel oil.
Scientists from Canada and Italy have tried to make bio-oil emulsify with diesel oil using
surfactants. The stability, corrosion-preventing ability, viscosity, and quantity of diesel oil
are improved when adding 10–30% bio-oil, and diesel oil of this kind is similar to pure
diesel oil.
Third, the quality of bio-oil can be improved through catalytic reforming, which is sim-
ilar to that of petroleum. Bio-oil can be gasified or converted into manufactured gas, bio-
diesel, or biomethane. Biogas could be used in SO or PEM fuels directly and biodiesel could
be used in petrol engines.
(2) Problems in the application of bio-oil.
The composition and physical and chemical properties of bio-oil are affected by many fac-
tors, such as the raw material sources, water content, reactor types, reaction parameters, and
the production collection methods. But bio-oils derived from different routes still have
commonalities, such as high oxygen content (35–40%), high corrosive ability (pH 2–3),
poor thermal stability (polymerization over 80 C), high viscosity, and low calorific value
(the calorific value of crude bio-oil is 16-20 MJ/Kg and that of engine oil is 42 MJ/Kg).
Such properties restrict the application of bio-oil as an engine fuel. Moreover, due to
Table 5.1 Composition of bio-oil from straw pyrolysis

Substance Content (%)a
Levoglucosan 19.30
Furfural 9.29
p-Vinylguaiacol 6.59
Pyrocatechol 6.26
Acetic acid 5.73
Cresol 4.32
4-Methyl-benzaldehyde 4.17
Syringol 4.03
4-Ethyl-phenol 3.89
Guaiacol 3.81
2(5H)-Furanone 3.80
2-Hydroxy-2-cyclopenten-1-one 3.39
Phenol 2.70
3-Methyl-pyrocatechol 2.67
4-Methyl-catechol 2.54
3-Methyl-2-cyclopenten-1-one 1.82
p-Ethylguaiacol 1.72
Vanillin 1.64
Eugenol 1.59
3-Methoxy-pyrocatechol 1.37
Xylenol 0.94
4-Hydroxy-benzaldehyde 0.70
a
Analyzed by the GC–MS of bio-oils from rice straw.
(Jung et al., 2008)
the high oxygen content, bio-oil is easily hardened on contact with air. Therefore, only
after refining could bio-oil have the potential to partially displace fossil fuels and be
used in existing thermal equipment, especially internal combustion engines (Zhang
et al., 2006).
Bio-oil refining technology has been a research hotspot worldwide, and various technol-
ogies have their own drawbacks as well as advantages. Catalytic cracking has the advan-
tages of simple equipment and low cost, but the catalysts are easily coked and deactivated;
emulsification technology is simple, but its cost and energy consumption are high; catalytic
esterification is a useful method for modification, but it results in poor quality bio-oil. The
yield of bio-oil from catalytic hydrogenation and catalytic pyrolysis technologies is low,
with the deactivation of catalysts restricting the development of bio-oil refining technology.
Therefore, the key problems for bio-oil refining technology to resolve are how to develop a
catalyst with high catalytic activity and high stability and now to create a new technique to
improve the yield of bio-oil.
5.2.7 Conclusions
In order to satisfy the need for rapid economic and green development in China, the
key problem is to vigorously develop clean energy resources such as biomass to
displace fossil fuels and thereby improve the structure of the energy industry.
Emissions of CO2 and air pollutants would be decreased dramatically by displacing
coal with cleaner fossil fuels such as natural gas. This could also lay the foundation
for low-carbon development in China and provide more buffer time before fossil
fuels diminish. The low-carbon transition of the energy system is a huge opportunity
for China.
5.3 Bio-based chemicals

Biorefining, the conversion of biomass to renewable chemicals and fuels, is important
under the current situation of rising costs and decreasing oil supply. In particular, plant-
derived biomass is a reproducible and low environmental-loading resource, produced
from CO2 and water via photosynthesis using sunlight. Among various biomass resources,
lignocellulose biomass is the most abundant and is nonedible, which makes it a promi-
sing candidate for the sustainable production of chemicals. Figure 5.9 demonstrates the
path for the production of various organic acids from cellulose (Deng et al, 2014).
5.3.1 Oxalic acid

5.3.1.1 Applications and market for oxalic acid
(1) Recovery of noble metals under the action of metals, preparing materials with special
properties.
Oxalic acid can react with many metal ions and generate corresponding oxalate, which
could be dissolved and also generated in water. For example, potassium oxalate is obtained
OH
OH
O HO O
O
HO O
OH
OH n
Cellulose 2
Hydrolysis
OH OH
HO O Ana
ero OH
bic
OH O2 HO
OH
HO O OH OH O
Lactic acid
bic
OH
HO Gluconic acid
a ero OH O2
O An Glucose
O2 O2
OH HO O
O O
O OH
Levulinic acid Glycolic acid
OH OH
Formic acid Acetic acid
Figure 5.9 Organic acids produced from cellulose.
(Deng et al, 2014).
only by dissolving oxalic acid and KOH in water and neutralizing while stirring. During the
process of nuclear fuel recycling, transuranic elements can be recycled using oxalic acid as
a precipitator. Therefore, oxalic acid plays an important role in material production, leather
preparation, and tombarthite recovery. Moreover, due to the fact that China is the main pro-
ducing area of tombarthite, the interaction between tombarthite and oxalic acid is a key
aspect of domestic research.
(2) Preparation and application of glyoxylic acid.
Glyoxylic acid is obtained by reducing one carboxyl of oxalic acid into an aldehyde group
through electrochemical catalytic action. Recently, many reports have described glyoxylic
acid synthesis via electrolytic reduction from oxalic acid, but the yields in different reports
are different due to the effects of the shape, structure, and operational mode of the electro-
lytic cells. Many countries have built industrial devices to synthesize glyoxylic acid via
oxalic acid electrochemical reduction. Glyoxylic acid can be used to synthesize cosmetics
and spices, such as allantoin and vanillic aldehyde; in the pharmaceuticals industry,
glyoxylic acid is applied in the production of antihypertension, antiulcer, and tumor inhi-
bition medicines; and in agriculture, glyoxylic acid is mainly used for the synthesis of insec-
ticides, herbicides, fungicides, and plant growth regulators.
(3) Ester compounds of oxalic acid and their applications.
Oxalic acid can react with methyl alcohol, ethyl alcohol, and butanol to generate dimethyl
oxalate, diethyl oxalate, and dibutyl oxalate, respectively. Such esters are usually used as
solvents and raw materials for the production of antibacterial agents, antipyretic com-
pounds, and anticancer intermediates in the pharmaceuticals industry; they play a protective
role in the preparation of superconducting oxides; and they are also used to produce liquid
crystal materials, photosensitive materials, adhesives used during surgical procedures,
herbicides, and so on.
5.3.1.2 The development of oxalic acid production and associated

problems
Traditional preparation technologies for oxalic acid mainly consist of the carbohy-
drate oxidation method, the carbon monoxide coupling method, and the sodium for-
mate method. The carbohydrate oxidation method has the advantages of being a
simple technique and requiring moderate reaction conditions, but the yield is low
and many kinds of NOx substances exist in the tail gas. Moreover, grains are usually
used as the raw materials in the carbohydrate oxidation method, which increases the
production cost and restricts its application. The carbon monoxide coupling method
has the advantages of being a relatively simple catalytic system and having high cat-
alytic activity, which results in products with higher purity. However, the carbon mon-
oxide coupling method requires, and consumes a large amount of, high-purity carbon
monoxide, leading to high investment costs. The sodium formate method is a mature
technology, has a short production period, and high product yields, but its lead ions
would pollute the environment during production. There are also other preparation
methods including nitric acid oxidation of ethylene glycol, propylene oxidation,
glyoxal oxidation, and so on.
A novel technology to produce oxalic acid through the alkali fusion and oxidation
of steam-exploded straw in the alkali fusion system was proposed by Prof. Chen
(Figure 5.10). The basic technology is as follows: 40–60% alkali solution (KOH,
Alkali
Materials Steam
fusion and Filter
crushing explosion
oxidation
CaO
Filter precipitate
liquor
refluence
Filter
Precipitation
and
acidification
Figure 5.10 Preparation process of oxalic acid by steam-explosion pretreatment from

lignocellulosic biomass.
NaOH) is added to steam-exploded straws and the mixture is reacted for a period to
form an alkaline steam-exploded straw solution. The solution is filtered and the filter
liquor is collected. Then a certain concentration of CaO solution is added to the liquid
to generate CaC2O4 and CaOH. Then a certain amount of 20–30% H2SO4 is added to
the calcium oxalate and reacted for a certain period under a temperature of 200 C.
After acidification the solution is condensed and crystallized to obtain oxalate crystal
(Chen et al., 2000).
After the steam-exploded straw is washed by water, the hemicellulose exists in the
form of xylose or xylo-oligosaccharide in the hydrolysate. Therefore, the steam-
exploded straw hydrolysate could be used to produce oxalic acid by brown rot fungi
fermentation. Brown rot is a kind of wood rot fungi that is the collection of filamen-
tous fungi leading to the brownness and rot of wood. Brown rot fungi mainly degrade
the cellulose and hemicellulose (and not lignin) within wood. The wood is then
cracked into small pieces and becomes brown and fragile. Therefore, brown rot fungi
play the role of degradation and reduction in the forest ecosystem, which is also an
inevitable part of mass and energy recycling in the forest ecosystem. Research has
found that oxalic acid plays the role of proton donor during the enzymatic or non-
enzymatic hydrolysis process of hydrate. Oxalic acid is the primary metabolite of
brown rot fungi, whose biosynthetic pathway consists of a “short circuit” TCA route,
glyoxysome, and acetic acid recycling route. Brown rot fungi could use the sugars
inside the steam-exploded straw hydrolysate to produce oxalic acid, which then
achieves the resource utilization of biomass wastes.
5.3.2 Levulinic acid

5.3.2.1 Applications and market for levulinic acid
One of the key sugar-based building blocks that can be obtained from lignocellulose
biomass is levulinic acid (LA), which has been identified by the US Department of
Energy as a top-platform chemical. Levulinic acid is a five-carbon molecule with car-
boxylic acid and ketone functionalities, and the existence of these two functional
groups provides this compound with interesting reactivity pathways.
As a top-platform chemical, levulinic acid is the building block used to produce a
great number of biochemicals such as succinic acid, resins, polymers, herbicides,
pharmaceuticals, flavoring agents, solvents, plasticizers, and antifreeze agents. In par-
ticular, some levulinic acid derivatives can be used for fuels and oxygenated fuel addi-
tives. For example, esterification of levulinic acid with C1-C2 alcohols produces
levulinic esters that can be used as diesel additives. Elliott and Frye (1999) have also
shown that levulinic acid can be hydrogenated in the presence of a bifunctional
catalyst to produce methyl-tetrahydrofuran (MTHF), which can directly serve as a
gasoline blend stock. Levulinic acid can also undergo hydrogenation to produce valer-
olactone, which has been shown to be a sustainable liquid transportation fuel suitable
for replacing ethanol in gasoline–ethanol blends.
5.3.2.2 The development of levulinic acid production

A substantial amount of attention has been paid to the preparations of bulk chemicals
from renewable biomass resources as substitutes for traditional fossil resources. One
attractive option is the conversion of lignocellulose to levulinic acid (LA), which is
regarded as a promising platform chemical. LA contains two important functional
groups, a ketone group and a carboxylic acid group, which make LA a versatile build-
ing block for various bulk chemicals such as fuel additives, polymer precursors, and
resin precursors.
LA can be produced from glucose, fructose, starch, and lignocellulosic raw materials.
Due to a simplified and low-cost process, the direct conversion of lignocellulosic raw
materials to LA has gained considerable interest around the world. For a long time,
homogeneous acids (HCl, H2SO4, H3PO4, etc.) were the most popular catalysts for
the conversion of lignocellulosic raw materials to LA (Mosier et al., 1999), which
resulted in many problems such as difficult recovery of acid, complicated separation
of products, and serious environmental pollution. Solid superacid, stronger than 100%
H2SO4, is a kind of acid with many advantages over liquid acid; for example, it is easy
to separate from the reaction mixture and easy to regenerate and reutilize (Olah et al.,
2009). Because of these advantages, a number of research studies have appeared on solid
acid-catalyzed production of LA from hexose, obtained from lignocelluloses. However,
the solid superacid catalyzed decomposition of lignocellulose to prepare LA is still little
reported.
Microwave
Steam- Washing, Steam- Sieving catalysis
Mechanical Ultrafine
exploded press exploded using 60
pulverization grinding
cornstalk filter cornstalk mesh
High
temperature
catalysis
Levunilic acid
Air Short
production with
classification fiber
polymerization inhibitor
Figure 5.11 Levulinic acid preparation via steam explosion.
Prof. Chen established a process for LA preparation from fractionated straw com-
ponents based on the characteristics of straw (Figure 5.11). LA is prepared from
steam-exploded straw hydrolysate and short-fibers via the catalysis of solid acid
(Chen et al., 2011).
Rice straw was steam exploded at 200 C (1.5 MPa) for 6 minutes by saturated
steam in a 4.5 L reactor. Steam-exploded rice straw was dried at 105 C under vac-
uum, followed by mechanical grinding with a vegetation disintegrator to 60 mesh
(0.25 mm). Solid superacid catalyzed production of LA was conducted in the autoclave.
The solid–liquid ratio of pretreated rice straw to deionized water was 1:15 (w/v). After
being sealed, the reactor was heated to the desired temperature of 150–240 C within
30 minutes and maintained for different times of 0–15 minutes under stirring
(180 rpm). When the reaction ended, the reactor was immediately put into an ice water
bath to decrease the temperature. Then the reaction mixture was filtered and washed
with deionized water, followed by centrifugation (8000 rpm, 20 min). The centrifugate
was collected for the determination of LA.
Solid superacid, S2O82-/ZrO2–SiO2–Sm2O3, could be used as a potential catalyst
for the preparation of LA from rice straw. But the method was highly reliant on
the concentration of solid superacid and the substrate pretreatment method. Steam
explosion combined with superfine grinding could be used as an effective approach
to improve LA yield due to the increase of cellulose accessibility. Under optimum
conditions, LA yield could reach 22.8%, accounting for 70% of the theoretical value.
5.3.3 Furfural
5.3.3.1 Applications and market for furfural
Lignocellulose biomass is an abundant and renewable resource, and the conversion of
the highly functionalized carbohydrates of biomass into valuable chemicals that could
eventually replace those derived from petrochemical resources is very significant
to improve the structure of the energy industry and reduce environmental pollution.
Biomass mainly consists of cellulose, hemicellulose, and lignin. In particular, the
conversion of the hemicellulose fraction by chemical catalytic processes or other

physicochemical or thermochemical strategies is of great importance due to the fact
that the biological conversion of hemicellulose is inefficient.
Furfural, derived from hemicelluloses, is used for the production of a wide range of
important non-petroleum-derived chemicals such as furan, tetrahydrofuran, and fur-
furyl alcohol. It is also used to produce fungicide, nematicide and other products in the
plastics, food, pharmaceutical, and agricultural industries. There is no synthetic route
available for furfural production in the chemical industry. Furfural is exclusively
produced from hemicelluloses of lignocellulose biomass. About 250,000 tons of
furfural—probably the only unsaturated, large volume, organic chemical—are pre-
pared from carbohydrate sources annually.
Furfural is an important chemical that possesses a unique advantage because it is
produced from renewable biomass, such as agricultural wastes or forest residues, that
is rich in pentosan polymers. Furfural and its derivatives are considered in many
instances to be strategic chemicals based on their various applications and use. As
a non-petroleum-derived product, furfural has been broadly used as the feedstock
in the manufacturing of furfuryl alcohol, 2-methylfuran, tetrahydrofuran (THF),
2-methyltetrahydrofuran (MeTHF), plastics, pharmaceutics, and agrochemicals.
Resins with excellent thermosetting properties and extreme physical strength can also
be produced by condensation of furfural with formaldehyde, phenol, acetone, or urea.
What is more, furfural and its derivatives have the potential to serve as gasoline blend
stock (López et al., 2014).
5.3.3.2 The development of furfural production

Lignocellulose biomass is a plentiful and renewable resource for chemicals. Despite
this potential, nearly all renewable fuels and chemicals are now produced from edible
resources, such as starch, sugars, and oils. The challenges imposed by notoriously
recalcitrant and heterogeneous lignocellulosic feedstocks have made their production
from non-food biomass inefficient and uneconomical. The commercial furfural pro-
duction process employing mineral acid as a catalyst is inefficient, and suffers from
disadvantages such as furfural loss, equipment corrosion, and high energy consump-
tion. In addition, the high level of pollution caused by the acidic effluent is another key
challenge for the industrial production of furfural.
Furfural is generated by the dehydrogenation and cyclization of pentose, which
is generated from pentosan hydrolysis. The catalysts usually used in furfural pro-
duction are sulfuric acid, hydrochloric acid, phosphoric acid, and others. In the furfu-
ral production process, steam stripping and solvent extraction are simultaneously
adopted to remove furfural from the system over time. At present, the preparation
technologies of furfural include one-stage and two-stage methods. The one-stage
method is the one used by most factories in which the pentosan hydrolysis and dehy-
drogenation and cyclization of pentose are conducted in one hydrolysis kettle. Furfu-
ral technologies have improved greatly over the past few decades from the initial
single-pot cooking technology to many pots in series and continuous production.
The widely used technologies include Quaker Oats, Agrifuran, Petrole-chimie, Escher
Wyss, Rosenlew and RRL-J technologies whereby furfural is removed via steam
extraction. The steam consumption of the one-stage method is huge. For example, pro-
ducing 1 ton of furfural requires 18–25 tons of steam. The furfural yield is low in the
one-stage method, reaching 60% at most. Moreover, the one-stage method generates a
large amount of waste residues composed of cellulose, lignin, unreacted hemicellu-
lose, and residual catalysts. The present method of disposing of waste residues is
adopting mixed burning of coal cinder technology to utilize furfural waste residues
as fuels for steam generation. In the two-stage method technology, pentosan hydro-
lysis and the dehydration and cyclization of pentose are separated (Li, 2006).
The combination of steam explosion pretreatment and rinsing proposed by Prof.
Chen could separate rice straw and cornstalk into hydrolysate and steam-exploded
straw or cornstalk, which uses the hydrolysis and primary separation of pentosan.
Then the separated pentose is dehydrated and cyclized to produce furfural in a
two-stage method. The specific process is as follows: raw materials are delivered
to the processing workshop from bunkers and cut into 5 cm lengths; then steam is
passed into the vessel until the pressure is 0.1–0.3 MPa higher than the work pressure
(1.5 MPa) and the pressure is maintained for a certain time; then the bleeder valve is
opened to pop up the materials instantly. The water content of steam-exploded mate-
rials is about 50%. Hydrolysate is prepared with the addition of water (1:3), and the
hydrolysate is rich in hemicellulose degradation sugars. Then the hydrolysate is fil-
tered and condensed to produce concentrated solution that is suitable for furfural pro-
duction. Multiple-effect evaporation is adopted to produce furfural from the
hydrolysate, which helps to condense the hydrolysate rich in hemicellulose degrada-
tion sugars to 13–18% sugar concentration. The concentrated sugar solution is added
into the distilling kettle with the addition of 98% sulfuric acid (at 5%) to produce fur-
fural. Then furfural is recycled by condensation and the same amount of water is added
to achieve a 6% furfural solution. Next the furfural is transferred into the negative
pressure distillation tower to evaporate wastewater, and then crude furfural is obtained
through washing the organic acids (Chen, 2013).
5.4 Bio-based materials

About 80% of chemical products are still based on crude oil. However, bio-based
materials will increasingly gain importance. Bio-based plastics have a history of over
150 years. Key milestones include the invention of cellulose nitrate (celluloid) in the
1860s, man-made cellulose (1890s), cellulose-hydrate films (cellophane) in 1912,
casein protein (milk fiber) in the 1930s, and soy-based plastics in the 1930s. These
materials lost their importance with the rise of the petrochemical industry in the
1950s. Since the 1980s there has been increasing interest in the development of bio-
degradable plastics such as polylactic acid (PLA), polyhydroxyalkanoates (PHAs),
and various types of thermoplastic starch made from bio-based feedstock. The renais-
sance of bio-based plastics and bio-based materials in general has been fueled by
progress in biotechnology, high fossil fuel prices, as well as environmental concerns.

Bio-based materials have the potential to reduce nonrenewable energy use as com-
pared to conventional materials, but may come at the cost of additional land use
and related environmental impacts.
5.4.1 Cellulose acetate

5.4.1.1 Applications and market for cellulose acetate
Cellulose acetate is one of the most commercially important cellulose derivatives, and
is widely used as fiber, film, paint, filters, and dialyzers. A major application is in cig-
arette filters to remove particulates during smoking. As fiber, cellulose acetate is used
in textiles because of its relatively low cost, draping quality, softness, comfort, luster,
and natural feel. The material is also used as a substrate for motion picture camera
film. It also finds applications as an ingredient in sheet and molded objects and as
an additive in surface coatings and inks. Its price is around $1.80 per lb.
It is estimated that 1.5 billion pounds of cellulose acetates are manufactured glob-
ally every year. Generally, wood and cotton are the major resources for industrial
acetylation. In recent years, low-cost lignocellulose biomass has become attractive
as a renewable resource, because it is available in large quantities and is routinely cul-
tivated in the world (Cheng et al., 2010).
5.4.1.2 The development of cellulose acetate production

Cellulose acetate is typically made from wood pulp through reactions with acetic acid
and acetic anhydride in the presence of sulfuric acid to form cellulose triacetate. The
triacetate is then partially hydrolyzed to the desired degree of substitution. Recently,
several other synthetic methods have been developed for polysaccharide esterifica-
tion, including the use of ionic liquids. Another recent development is the use of iodine
as a catalyst for the esterification of cellulose and starch in the presence of acetic
anhydride.
People are always concerned about how to get products of a certain degree of sub-
stitution and uniform substitution, therefore the study of cellulose acetate preparation
and the technological difficulties involved is a key topic of current research.
Prof. Chen used waste straw as the crude material, with the straw undergoing acety-
lation reaction after pretreatment by steam-explosion, and then cellulose acetate was
separated from the acetylation products of straw according to their different properties
(Zhang & Chen, 2007). The technological route is shown in Figure 5.12.
The technology used to produce cellulose acetate from acetylation reactions of
straw has the advantages of low cost and simplicity, which is conducive to establish
an ecological industry model in which cellulose acetate is regarded as a flagship prod-
uct (Zhang & Chen, 2007).
Steam Glacial Acetic Distilled

explosion acetic acid anhydride Sulfuric acid water
Straw Activation Esterification Precipitation Rinsing Grinding Poaching
Cellulose biodegradable
Acetylized hemicellulose, film
Acetone lignin and some cellulose
extraction
diacetate Separation
Washing Drying
CH2Cl2 Hydrolysis
extraction Cellulose triacetate Cellulose diacetate
Analysis and
purification
Figure 5.12 Preparation of cellulose acetate from straw.
5.4.2 Sodium carboxymethyl cellulose

5.4.2.1 Applications and market for sodium carboxymethyl
cellulose
Sodium carboxymethyl cellulose (CMC) is one of the most important products of cel-
lulose ethers, which are formed by natural cellulose modification as a kind of cellulose
derivate with an ether structure. Due to the fact that the acid form of CMC has poor
water solubility, it is usually preserved as sodium carboxymethylcellulose, which is
widely used in many industries and regarded as monosodium glutamate in industry.
CMC could be used as flocculating agent, chelating agent, emulsifier, thickening
agent, water-retaining agent, sizing agent, and film-forming material, and so on.
CMC is also widely applied in fields such as electronics, pesticides, leather, plastics,
printing, ceramics, and the daily-use chemical industry. Moreover, due to its excellent
properties, wide application, and the developing potential fields, CMC has broad appli-
cation prospects.
5.4.2.2 The development of CMC production

With the development of domestic technology, we have made great progress in the
research and application of cellulose and its derivatives. Due to the fact that the posi-
tion of cellulose as an important source of synthetic organic materials has become
more and more prominent, people have already realized that cellulose has a superior
advantage over limited coal, oil, and natural gas. Cellulose is not only a type of renew-
able resource; it can also be turned into many kinds of functional products. What’s
more, cellulose will have more broad sources once agricultural and forest wastes
are more intensively exploited and utilized, which will promote the development
of the cellulose industry.
Despite the improvement from the water-borne method to the solvent-borne
method, the cellulose materials for CMC production are still concentrated in the linter
and wood pulp, which have a relatively high a-cellulose content and degree of
polymerization. Such materials are not abundant and have a high cost; in addition, the
pretreatment processes are also complex and will damage the environment. Therefore,
it is very important to search for cheaper raw materials, to simplify pretreatment tech-
nologies, and to decrease the pretreatment cost. Previous research has indicated that
straw, sugar cane, bamboo, beet, waste velveteen, tobacco, orange peel, paper mill
sludge, and sago could be the raw materials of industrial CMC preparation. These
materials are acid-boiled or alkali-boiled to extract cellulose and then the cellulose
is etherified. The cost of such technology has decreased, but the route is complex
and the pretreatment technology conditions are rigorous.
Prof. Chen’s group adopted a pollution-free steam explosion technology to activate
the straw materials and then introduced a carboxymethylation reaction to the system.
The different components of straw are separated according to the different physical-
chemical properties of the products and the high-value CMC is then produced (Smith
and Klosek, 2001) (Figure 5.13). In this process, the raw materials are cheap and the
technology route is relatively simple, which is of great importance in the respect of
realizing the component separation of straw, saving resources, and making the produc-
tion technology become environmental friendly.
5.4.3 Bio-based desert soil amendment materials

5.4.3.1 Applications and market for bio-based desert soil
amendment materials
Desertification is one of the most severe ecological problems in China. Although the
government has reinforced the management of deserts, desertification is still a big
problem in the country. China started the desert land governance in the 1990s and
Filter
Straw residue Cellulose and
Comb grading
lignin mixture
Filtra-
Steam tion
explosion
Filter
liquor Hemicellulose Parenchyma
macrofiber Staple fiber
hydrolysate cells
Non-acid Alkali Thermochemical

Fermentation treatment
autocatalysis treatment
Crude furfural Fermentation

Etherification SiO2 etc.
products
Refining CMC
Etherification
Carboxymethyl
products
Furfural lignin
Figure 5.13 Preparation of CMC from straw.

the preliminary stage was similar to other countries, in which straw was used to pre-
pare sand-protecting barriers. However, it could not solve the problem fundamentally;
actually, it could only supplement desert soil governance. Drought, vegetation dete-
rioration, and poor soil texture are the main driving forces of soil desertification.
Therefore, researchers around the world have realized that the fundamental actions
needed to prevent soil desertification are to improve the soil texture, improve the
water conservation force, and strengthen the vegetation construction. Plenty of studies
have been carried out around these measures and chemical materials were once one of
the research focuses. However, the cost of chemical materials is high and the absorp-
tivity of plants for massive chemical amendments is limited; moreover, a lengthy
period of chemical amendments usage would pollute the underground water, make
the soil harden, and destroy the environment. Under such conditions, there is an urgent
need to find a biodegradable material that could solve the problems effectively and
enhance soil fertility.
At present, most of the domestic practice of treating straw to be used as desert soil
amendment materials is simple mechanical pulverization. Straws, after such simple
pretreatment, are of poor quality, the stacking and retting period is long, and the
fertilizer efficiency is low when returning to the field. Existing research indicates
that the results of using straws as desert soil amendment materials are no less favorable
than those of chemical materials, and straws have advantages like easy acquisition of
materials, being low cost and long lasting, and having multiple functions.
5.4.3.2 Bio-based desert soil amendment materials

China is one of the countries most severely affected by desertification, and the rapid
development of desertification and the significant influence on the social economy
and the environment have attracted much attention. The desert land is mainly distrib-
uted in the arid and semiarid regions and some semihumid regions in north China
including Inner Mongolia, Ningxia, Gansu, Xinjiang, Qinghai, Tibet, Shannxi, Shanxi,
Hebei, Jilin, Liaoning, and Heilongjiang, especially centered on the semiarid region to
the east of Helan Mountain. Desertification is a kind of land deterioration that causes a
decrease in land output and the loss of land resources, presenting a desert landscape due
to the combined effects of human economic activity and the fragile environment in
these areas. At present, the desert area in China is vast and, what’s worse, the rate of
development of desertification is still increasing. The ever-expanding area of desert
land has severely affected our domestic ecological environment and social and eco-
nomic development. It has also caused huge harm in China, by destroying the ecological
balance, decreasing the land productivity, endangering the survival and development of
citizens, and accelerating the degree of poverty. Hence, it is essential to develop
bio-based desert soil amendment materials in order to promote the processes of com-
bating desertification, redeeming the economic loss, and repairing the environment.
Present pretreatment methods to prepare desert soil amendment materials from
straws have disadvantages like unsatisfactory technology, environmental pollution,
and high cost due to additional demand for inorganic fertilizer, humic acid, and nutri-
ents. Based on these facts, the author’s group developed a method to prepare desert
soil amendment materials from the fermentation of steam-exploded straws, in which

the steam-exploded straws under pretreatment were solid fermented with wheat bran
to prepare functional materials including biofertilizer and prophylaxis treatment of
plant disease, and then the functional materials were compounded with biodegradable
bacterial cellulose with high water-absorbing qualities. These products not only can
improve the soil microstructure and decrease the amount of active water-retaining
agent required, but also gather plenty of beneficial microorganisms that have func-
tions like water preservation and sustained release of nutritients. Therefore, such
bio-based desert soil amendment materials are propitious to the large-scale applica-
tion of desert land control (Kaparaju et al., 2009a, 2009b).
The technology route for production of desert soil amendment materials is shown
in Figure 5.14. Compared to pulverizing straw via machines, the water absorption and
water-retention rates of steam-exploded straw are increased by 32–40% and
80–100%, respectively. Moreover, after solid-state fermentation the materials func-
tion as a biofertilizer and prophylaxis treatment for plant disease. The organic content
of desert soil amendment materials after solid-state fermentation exceeds 60%, humic
acid content is 15%, the total number of active bacteria is 300 million/g, and the N, P,
and K contents are all higher than 5%.
5.4.4 Lignocellulose board

5.4.4.1 Applications and market for lignocellulose board
With the development of China’s domestic economy, the market for building mate-
rials has turned to quality from an initial emphasis on quantity, and one of the most
active fields in the building materials market has become the production of boards for
construction and structural shapes from lignocellulose.
Due to the low cost of both straw raw material and materials used in its processing,
the cost of lignocellulose board is lower than any other boards of the same type. The
preparation of straw boards has successfully relieved the situation of undersupply of
domestic wood raw materials, which also opens up a new route of straw substitution
for wood materials. Experimental results indicate that producing slabs only from
straws or mixing the straws with composite wood are both available options. More-
over, the success of straw boards could increase farmers’ incomes and broaden income
sources through developing the artificial straw boards. Besides, straw boards also
solve the straws collection problem to some extent, remit the atmospheric pollution
Straw
Filter liquor
Bacterial
Steam fermentation
explosion Appropriate mixture
Filter Complex microbial for bio-based
residue solid fermentation desert soil
amendment materials
Figure 5.14 Preparation of desert soil amendment materials from straw (Chen, 2009).
due to straws combustion, and at the same time, decrease the consumption of a forest
resource, thus protecting the environment.
5.4.4.2 The development of lignocellulose board production

The TianBao Project (the natural forest protection project) avoids mass deforestation
and also provides a chance for the application of lignocellusic boards. Producing
boards and building materials from lignocellulose biomass is an effective route for
the high-value utilization of biomass, which could help to maintain the ecological bal-
ance and satisfy the requirements for planks. The structure and properties of straws are
changed by physical, chemical, and biological methods. The degradation could con-
vert hemicellulose and lignin directly and rearrange the hydrogen bonds within the
cellulose to prepare straw materials with new properties and make it easy to produce
a variety of products. The application of modified straws currently focuses on wall
materials in the building industry, e.g., artificial beaverboard; inner packing materials
in the packing industry; and disposable tableware and seeding devices in agriculture.
Straw building material is a kind of “green building material” that has a low weight.
Therefore, it could save forest resources and avoid the severe air pollution caused by
straw combustion if wood was replaced by straw materials. Besides, great contribu-
tions have been made to the ecological environment by replacing packing plastics and
plastic disposable tableware. However, a certain amount of thermosetting resin and
formaldehyde should be added during the production of wall materials, green beaver-
board, inner packing materials, disposable tableware, and seeding devices from
straws, which could not compete cost-wise with other kinds of decorative materials
and plastics, and also causes environmental pollution. Hence, it is attractive to produce
materials without sizing materials economically and environmentally, which could
not only decrease production cost, but also avoid environmental pollution.
There are problems of tackifier contamination, non-uniform gluing, and unsteady
properties during the production of new materials from straws, so it is essential to
improve from the very beginning in order to develop green tackifiers or new technol-
ogies of lignocellulose board production to satisfy the need for industrialization.
Cheng and Logan proposed a new concept for modified straw and developed a set
of methods for straw modification via steam explosion based on straw modification
methods and thermocuring, and then put forward new methods for the clean produc-
tion of ecological materials from modified straws (Cheng and Logan, 2007). The route
is shown in Figure 5.15
Modified straws refer to straws that have changed their structure and properties
through physical, chemical, or biological methods. The degradation of cellulose, hemi-
cellulose, and lignin in the straws helps the formation of thermocuring resin adhesive,
which gives the fiber the characteristic of autohension to satisfy the demand for molding
of the building boards. The modification of straws by steam explosion makes the lignin
active groups increase rapidly, which has similar properties to those of polyphenols
and could be used as a natural adhesive. During this process, hemicellulose is degraded
into soluble sugar, dehydrated sugar, and furfural, and could be reacted with lignin
instead of formaldehyde. During steam explosion, cellulose is not degraded, while
Straw
Air-dried
Filter liquor
straws
Steam
explosion
Phanerochaete
Filter residue chrysosporium Modified straws
fermentation Thermocuring
Figure 5.15 Technology route of xylose extraction via steam explosion.
the crystallinity of cellulose is increased. The modification technology mainly consists

of two molding technologies. One is thermocuring, in which the thermofixation process
is directly controlled by controlling the water content to rearrange the cellulose hydro-
gen bond and form the thermoset biological resin adhesive. The other modification
technology is cellulose recombination and molding technology, in which the straw
fibers pass through molding devices and then bond together under certain temperature
and pressure conditions to form boards that can meet the mechanical strength require-
ments for building material. Ecologically friendly materials without synthetic adhesive
are attractive to both the economy and the environment. The route simplifies the pro-
duction process and decreases the cost through reducing the procedure of glue mixing
and the corresponding devices. Moreover, the produced materials can be degraded
completely in nature and they can also be used as feedstuff or manure that has no envi-
ronmental pollution effects. In addition, the strength of the ecological materials is
increased greatly due to the effective modification.
The abundant straw resources can be turned from waste into wealth via straw mod-
ification technology. The thick filamentary products derived from steam explosion
can be used to produce fluting mediums, wall materials, fiber slabs, packing materials,
disposable tableware, and seeding devices through compression and processing.
Experts predict that the annual construction area in China could reach 1.5 billion
m2. If the demand for building boards for a 1 m2 area is 10 m2, the quantity of building
boards required is 15 billion m2; therefore, the market capacity for building boards is
considerable and represents a promising source of future economic growth.
5.5 Food and animal feed

5.5.1 Food
5.5.5.1 Xylose and xylitol
Applications and market for xylose and xylitol
Xylose (C5H10O5) is a type of pentose that is soluble in water and some organic sol-
vents like hot ethanol, while insoluble in diethyl ether. Xylose often exists as a
colorless or white crystal or powder that tastes sweet and refreshing. It exists in the
form of a polysaccharide (melting point is 145 C) in plants, especially in product

wastes like straws and ears of rice. Xylitol is produced by catalytic hydrogenation
from xylose. Xylitol is widely used for food additives due to its outstanding features
like anticaries properties and because it can be used by diabetics.
Xylo-oligosaccharide is a kind of oligosaccharide linked by b-1, 4-glycosidic bonds
from 2 to 7 xylose molecules. The main composition of xylooligosaccharide is xylo-
biose and xylotriose; some of them contain side chains like D-arabino-2-hexulosonic
acid or glucuronic acid. The solid form of xylo-oligosaccharide is a milk white or faint
yellow powder with good processing characteristics and storage stability.
Xylitol is a type of sugar alcohol (C5H12O5, white powder or crystal) with five-
carbon molecules and exists widely in vegetables and fruits in nature, while the con-
tent is usually less than 900 mg/g. Xylitol is also an intermediate metabolite of mam-
mals. For example, 5–15 grams of xylitol is produced by a person every day. The
sweetness of xylitol is very close to saccharose, and has the specific property of cool
sensations. Among its many excellent properties, the edible-medicinal one is the most
important. Xylitol has sweetness that is close to saccharose and the sugar cannot be
used by caries bacteria, so xylitol can protect teeth from corrosion. Because xylitol can
absorb lots of heat under dissolution and thus decrease the temperature of the medium,
xylitol crystal tastes cool and, like mint, it can improve food flavor. Xylitol has a spe-
cific metabolic pathway in which insulin is not needed. Therefore, xylitol passes
through the glucuronic acid xylulose pathway and the phosphopentose pathway
and generates ribose phosphate. The key product of this metabolism is glucose-6-
phosphate, and then glycogen is produced to generate energy by oxidative metabo-
lism. Therefore, xylitol can regulate the disturbance of carbohydrate metabolism in
humans. When a lack of insulin occurs, xylitol can pass through the cytomembrane
as usual and provide nutrients and energy for cells. Xylitol can slow the production
of fatty acid in plasma, and does not result in a rise in blood sugar, so xylitol is a ther-
apeutic agent and nutrient for diabetics and also a liver-protecting medicine for liver
infections. Xylitol has good thermal stability and will not react when heated with
amino acids, so it can be mixed with amino acids to produce medicinal nutrients.
Xylitol can also promote the secretion of gastric juice, promote the activity of the
pancreas and the gallbladder, and accelerating corticotrophin releasing hormone, so
it is suitable for the old and the weak.
Prof. Chen and his team have established a new technology to extract xylose via a
steam-explosion method, which is described as follows: the appropriately crushed bio-
mass materials are steam exploded to get steam-exploded straws; then xylitol is
recycled by counter-current extraction and detoxified to eliminate the inhibitors like
formic acid, acetic acid, and furfural; and xylitol is hydrolyzed into xylose by micro-
organisms. In this process, the concentration of xylose can reach 30.12 g/L, and the
extraction rate is more than 80% (Xu & Luo, 2011) (Figure 5.15).
The development of xylose and xylitol production

As is widely known, xylitol is a kind of functional sweetening agent produced via tra-
ditional catalytic hydrogenation. In fact, this technology has the problems of complex
processing, poor security and high cost because of the pure xylose required. Due to the
problems existing with the chemical methods, the main technology for xylitol produc-
tion is microbial conversion, in which microorganisms convert xylose into xylitol by
xylose reductase within microbial cells. The advantages of the microbial conversion
technology are as follows. First, it has a high utilization ratio of raw materials. The
chemical method uses only pure xylose as raw materials, thus the xylose (30%) in corn
stover hydrolysate cannot be used. However, the bioconversion method can use the
xylose in corn stover hydrolysate, improving the utilization ratio of raw materials. Sec-
ond, the bioconversion process can reduce the environmental pollution because in this
process raw materials are directly used without pretreatment. Third, bioconversion
consumes less energy. In a traditional chemical process, corncob hydrolysate is con-
centrated and crystallized to obtain xylose and then xylose is redissolved and diluted
before being hydrogenated, re-enriched, and crystallized, which uses a lot of energy. In
the bioconversion process, xylitol is produced through one-stage concentration and
crystallization, thereby decreasing energy consumption. Fourth, the bioconversion pro-
cess needs simpler devices. Xylitol production via the chemical method requires hydro-
gen and this process has to be conducted under high temperature and pressure, placing
high demands on the devices. In the bioconversion process, the main devices are simple
reaction tanks and a few fermentation cylinders. Fifth, the process is safe and easy to
operate. Bioconversion is processed under normal temperature and pressure without
asepsis operation. Sixth, the process can provide better products. The products are more
suitable for food processing because the whole process avoids contact with metal pow-
der catalysts. As mentioned previously, the screening and optimization of new strains
and the foundation of new routes are the key problems for xylitol production in the
future (Fang et al., 2013).
5.5.1.2 Vanillin
Applications and market for vanillin
Vanillin is also called vanillin or 3-methoxy-4-hydroxybenzaldehyde; it is a white to
faint yellow crystalline powder or acicular crystal. The melting point of vanillin is
80–81 C and the boiling point is 285 C. Vanillin is slightly soluble in cold water,
but dissolves well in ethyl alcohol, diethyl, chloroform, glacial acetic acid, and pyr-
idine. Vanillin usually exists in vanilla, clove oil, benzoin extract, and caryophyllus.
Pure vanillin has the rich aroma of butter with no peculiar smell. Pure natural vanillin
is mainly extracted from the pods of vanilla, and the yield is too low to satisfy market
demand (Chen and Wang, 2008). “Biovanillin,” produced from the natural precursors
of vanillin by microorganisms, could displace natural vanillin.
Vanillin is widely applied in industrial production. For example, it is used as a per-
fume or perfume fixing agent in food, toothpaste, fancy soap, and tobacco. Vanillin is
also an important intermediate material in pharmaceutical chemicals. Specifically, it
can be used to produce drugs for hypertension, cardiopathy, dermatosis, ozostomia
and hydragogue. Additionally, vanillin can be an auxiliary material in chemical engi-
neering, an antihardening agent for plastics, and an electroplating brightening agent
for Ni, Cr, and Cd. In agriculture, vanillin can be used as a yield-increasing agent or
ripening agent for sugarcane, as well as a material for the preparation of herbicides and
insect attractants.
Vanillin is the main component extracted from the pods of vanilla and is also one of
the most widely used spices. A large demand for vanillin has arisen due to the high
value that many countries put on food security. As an important high-ranking spice,
vanillin is closely related to humans’ daily life and the demand for it has been enlarged
gradually. As a rough estimate, the yield of vanillin worldwide is around 5000–8000
tons and the demand exceeds supply by 3000–4000 tons. Therefore, vanillin produc-
tion has been an attractive proposition. The most frequently used method to prepare
vanillin is to take advantage of lignin and guaiacol, which have the advantages of
being cheap and easily procured materials and use a mature technology.
Development of vanillin production and associated problems

Vanillin production via the bioconversion method has been developed for more than
10 years, and this technology makes use of multiple biological materials including
fungi, genetically engineered bacterium, and extracted enzymes. It is known from
the literature that at the beginning of such research, most studies were biased toward
a theory including various microorganisms and the metabolism routes of vanillin syn-
thesis and degradation in plant cells. Of course, extensive research was conducted at
the cell, enzymology, and gene level and lots of excellent results were obtained. With
the deepening of the research, many researchers turned to the study of the industrial
production of vanillin and the technical routes described were also diverse. However,
there has been no report on the multiple industrialization of vanillin until now. Such
researche in China is still at the initial stages and relative developments have not yet
been reported (Chen, 2013).
The most studied bioconversion method is a two-stage technology where vanillic
acid is produced from ferulic acid and then vanillin is further prepared from vanillic
acid (Prifert et al., 2001) (Figure 5.16).
5.5.2 Animal feed

5.5.2.1 Applications and market for animal feed
With the rapid increase of the population and individual incomes, the composition of
food consumed by Chinese residents has improved greatly, which calls for more edi-
ble animal by-products. Therefore, the demand for animal feed is increasing as a result
O
HO O O
OH
OCH3 OCH3 OCH3

OH OH OH
Ferulic acid Vanillic acid Vanillin
Figure 5.16 Conversion route of vanillin from ferulic acid.
of rapid increase in demand for animal foods like meat, eggs, and milk. Meanwhile,
the cultivated land resource in China is decreasing and the natural grassland keeps
vanishing. Under these conditions, it becomes especially important to use existing pre-
cious resources more reasonably and effectively.
Using straw as a feedstuff has a long history in China, and the main crop straws
used are wheat straw, rice straw, corn stalk, sorghum straw, and beanstalk. The nutri-
tional components of the different kinds of straw vary, but all kinds of straw have the
following things in common: the crude protein content is as low as 2–5%; the crude
fiber content is as high as 20–45%; the content of minerals such as Ca and P is low and
unbalanced; and the palatability is poor, leading to a low feed intake by animals. It is
worth noting that after processing treatments such as ensiling, microbiological fer-
mentation, and ammoniating, the feed intake, nutritive value, and digestibility
increases. Hence, the improvement of feedstuff has rewards and economic benefits
beyond adding weight to grass-eating animals.
In the international market, Japan, South Korea, Taiwan, and some Southeast Asian
countries need to import a large amount of forage grass due their lack of biomass
resources. For example, Japan has to import millions of tons of bulk forage grass from
Canada; but in order to decrease the cost of transportation and animal feeding, Japan
has explored opportunities to imported processed feed products derived from crop
straw like cornstalk, rice straw, and beanstalk from China. In the Chinese domestic
market, grass yield has decreases dramatically due to the severe degradation of grass-
land; in order to recover vegetation and protect the ecology, measures such as grazing
prohibition, returning grain acreage to forestry and grassland, and rearing livestock in
pens have been conducted in many places in China, which again leads to the demand
for storing plenty of forage grass. In China alone, the number of cows was 0.14 billion
and sheep 0.27 billion in 2010. Calculated by the ratio of 20% of the animals being
reared in pens, the annual demand for various forage grasses was as much as 0.16 mil-
lion tons. Statistics show that the crude demand per cow for feedstuff is 10 kg/d and
3.3 kg/d for sheep, and the total crude feedstuff demand in China is 0.8 billion tons
per year.
Therefore, feedstuffs made from straw will enjoy a broad development space and
huge market potential if product quality is improved, products are easy to transport
and wrap, and the price is reasonable.
5.5.2.2 The development of animal feed production

The degeneration and desertification of grassland lead to the shortage of animal feed
of high quality, while the development of large-scale farming practices calls for a
large amount of animal feed. There are many reports on feedstuffs made from straw
via microorganisms’ fermentation, but due to the single metabolism of microorgan-
isms and difficulties in degrading the stable macromolecular compound formed by
cellulose, hemicellulose, and lignin within straw, the opportunity for improvement
of nutrients inside the feedstuff is very limited. At present, research is centered on
the methods of microbiological fermentation, ensiling, and ammoniating to treat

straw, and these measures cannot realize the efficient conversion of crop straw to
feedstuff of high quality and high nutritive value. In addition, the focus of the indus-
trialization of feedstuff production from straw by steam explosion is only on cornstalk,
and no reports on wheat straw have currently been seen.
Cornstalk is the main source of traditional feedstuffs, but its application is limited
due to its high C/N ratio. Prof. Chen established an ammonium salt presoaking
coupled with steam explosion method to increase the nitrogen content in straw
(Chen & Liu, 2007). Results show that except for urea, the addition of other nitrogen
sources is conducive to the degradation of hemicellulose, producing a large amount of
soluble sugar (Figures 5.17–5.19). The degradation ratio of hemicellulose can reach
over 58% when adding 5% of (NH4)2SO3. The addition of ammonium salts can help
increase the nitrogen content of straw compared to steam explosion without ammo-
nium salts, and the highest nitrogen content can reach 2.3%. The addition of
(NH4)2SO3 is the most efficient way to improve nitrogen content in straw, and the
nitrogen source conversion ratio can be up to 84%. After steam explosion, the biode-
gradability of straw is dramatically improved and the maximum value is 71%. This
novel method has obvious advantages compared to traditional methods aimed at
increasing nitrogen content. Liquid ammonia presoaking can increase nitrogen con-
tent, but the reaction time is long and the ammonia is easily volatilized, leading to
inconvenience for operations. Steam explosion coupled with ammonia presoaking
can significantly increase the nitrogen content of straw, and the recycle cost is high
even though the ammonia can be reused (Chen et al., 2005).
CHC
CC
CL
35
30
25
CHC, CC, CL (%)
20
15
10
0
Water (NH2)2CO (NH4)2SO3 NH4HCO3 NH3.H2O
Additive
Figure 5.17 Hemicellulose, cellulose, and lignin content (% DW) of cornstalk after amination
by steam explosion. Note: water control; CHC, the content of hemicellulose; CC, the content of
cellulose; CL, the content of lignin.
16
14
12
Soluble sugars (%)
10
0
Additive
Figure 5.18 Soluble sugars content (% DW) of cornstalk after amination by steam explosion.
Note: water control.
Predicted in vivo digestibility (%)
70
60
50
40
Additive
Figure 5.19 Speculated in vivo digestibility of treated cornstalk by amination coupled with
steam explosion.
Note: water control (Chen & Liu, 2007).
Research into silage feed started years ago. Ensiling is a process coupling anaerobic
fermentation and acidifying, during which the soluble sugar and protein contents are
low, which is unfavorable for animal consumption. Adding cellulase during the ensiling
process can increase the soluble sugar and organic acid contents during fermentation. In
this way, lactic acid fermentation and saccharification processes are synchronized by
adding lactic acid bacteria and hydrolase. The soluble sugar produced from enzymolysis
can be used by lactic acid bacteria, and the growth of lactic acid bacteria can inhibit the
growth of other microorganisms. However, the enzyme cost is high in this process. To
solve the problems, Prof. Chen put forward the method of in situ fermentation coupled
with ensiling. Results of this study showed that both cellulase and hemicellulase were
produced during fermentation; nitrogen content was increased from 6.7% to 14.7%
after fermentation; and the cellulose was degraded by 38% and hemicellulose by
21%. Ensiling proceeded, followed by solid-state fermentation. During this process,
lactic acid content increased dramatically, and the pH value decreased rapidly, which
was conducive to the subsequent ensiling of feedstuff (Chen et al., 2005).
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Lignocellulose biorefinery process
engineering 6
6.1 Introduction
Lignocellulosic feedstocks are inhomogeneous, and the chemical compositions are
complex. At the micro level, the structure – composed of cellulose, hemicellulose,
and lignin – determines that the degradation of any ingredients will be subject to
the constraints of other ingredients. That is to say, there are both active ingredients
and inert ingredients in the material systems of the biorefining process. Thus, in
the transfer process, the basic assumption of a proposed homogeneous model is not
valid. At the macro level, due to the heterogeneity of lignocellulosic feedstock, there
are a lot of pores in the raw material system. These pores are not only gas transmission
channels, but also the interface of gases, liquids, and solids.
Due to the complexity of lignocellulosic feedstock components, a homogeneous
model is no longer applicable for a mass and heat transfer study in the biorefinery
process. Meanwhile, the lignocellulosic feedstock system itself is a typical porous
media system consisting of gas, liquid, and solids. Therefore, the author proposes
to use porous media theory to study the transfer principles in the biorefinery process.
The porous medium is a subject involving both theory and applications that are widely
applicable in geology, and in the petroleum and chemical industries. Combining bio-
logical reaction characteristics with porous media theory, this chapter aims to explore
the transfer principles in the lignocellulose biorefinery process, while guiding
lignocellulose biorefinery engineering practices.
Process engineering is a new discipline that has developed when basic theory and
methods of chemical engineering processes are applied in the materials, metallurgy,
biology, environment, and energy industries. Process engineering includes the study
of process engineering principles, systemic measurement of data and information
(databases), as well as process integration, as shown in Figure 6.1. Process
engineering focuses on the study of physical, chemical, and biological conversion pro-
cesses (including material movement, transfer, reactions, and their relationship), aim-
ing to solve the bottleneck in the transfer of laboratory results to industrial processes,
and create clean and efficient technology, processes, and equipment, with the goal of
solving the common problems of different areas in the process (Gutierrez-Rojas
et al., 1996).
This chapter begins with the special heat and mass transfer laws that apply in ligno-
cellulose biorefinery process engineering, using porous media theory to explain the
specific transfer laws for heat, water, and gas in the lignocellulose biorefinery process.
Then typical process units and equipment, as well as the rapidly developing online
monitoring technology and automatic control technology and its application in the

Market demand
Laboratory Industry
Process innovation Process engineering Engineering practice
Biochemistry
Material Process
Process Integrated
Data engineering Industry
Energy theory system
company
Resource/
environment
Figure 6.1 Diagram of process engineering.

(Gutierrez-Rojas et al., 1996)
lignocellulose biorefinery process, are introduced in detail. Finally, examples of the

integration of various unit processes in the lignocellulose biorefinery process are
demonstrated.
6.2 Transfer principles of typical lignocellulose

biorefinery process engineering
The porous medium (mainly the pore structure and physical and chemical properties
of the porous medium), the fluid (mainly the components of fluid and its physical
and chemical characteristics), and the flow status (mainly the environment and
conditions of flow, and the interaction between the fluid and solid) determine the
regulation of fluid flow through porous media. The material system in the lignocel-
lulose biorefinery process is a three-phase system consisting of porous media, which
can be seen as a typical porous media system, and thus could be analyzed by corre-
sponding theory on porous media. Studies on the transfer process of lignocellulose
biorefining can refer to the porous media process, which involves multidisciplinary
theory of the flow porous medium theory, capillary theory, diffusion theory, fluid
mechanics, heat and mass transfer, thermodynamics, and so on. Solid-state fermen-
tation and steam explosion are two key units in the lignocellulose biorefinery pro-
cess, and both have been studied by the current author for about 20 years. This
section focuses on solid-state fermentation and steam explosion, which are two
representive units that can be used to explore the heat and mass transfer laws in
the main lignocellulose biorefinery processes.
Process engineering 169
6.2.1 Heat and mass transfer in porous media

6.2.1.1 Heat transfer process in porous media
Analysis of the heat transfer process in porous media shows that the process includes:
the heat conduction process of contact of a solid body with fluid in the gaps between
particles; convective heat transfer of the fluid in the gap (it could be forced convection,
or natural convection, or mixed convection of both, and also comprises the liquid boil-
ing, evaporation, and condensation of steam); and the radiation heat transfer between
the solid body and the gases. A large number of experimental studies and results
of theoretical analysis show that, for a particle that is not more than 4–6 mm in diam-
eter, the contribution of convective heat transfer within the fluid is negligible, and the
radiation heat transfer contribution is obvious only when there is a great temperature
difference between solid particles and the pores are in a vacuum or are occupied by
the gas. Thus, for a solid-state fermentation system, evaporative cooling and convec-
tion is a more important method of heat exchange (Gutierrez-Rojas et al., 1996).
6.2.1.2 Mass transfer processes in porous media

The mass transfer process in porous media includes the following two aspects (Shao
et al., 2006): molecular diffusion and convective mass transfer. Molecular diffusion is
caused by the random motion of the fluid molecules or solid microscopic particles. It
corresponds to the heat conduction mechanism in the heat transfer process. Convec-
tive mass transfer is caused by the macroscopic motion of fluid; and corresponds to
convective heat transfer. Briefly, Convective mass transfer includes both the mass
transfer between the fluid and the solid body wall and the convective mass transfer
between two immiscible fluids (including a gas-liquid phase). Single-phase fluid con-
vective mass transfer is divided into laminar and turbulent flow according to different
fluid states. The gas-liquid two-phase flow (i.e., nonsaturated flow in porous media)
has more and different forms of convective mass transfer. Obviously, the macroscopic
motion of the fluid in the gap is caused by the capillary force, pressure, gravity, and so
on. It should be pointed out that there is mutual influence and a coupling effect among
the transfer processes of momentum, energy, and mass in porous media.
In recent years, some scholars have summarized their research work in porous
media and suggested that studies on heat and mass transfer in a porous medium should
focus on the following aspects:
1. Combine the macro and micro aspects of research, taking theoretical analysis, experimental
research, and numerical simulation as a means to establish and improve the micro- and
macromodel of the porous medium.
2. Develop measurement principles and methods, especially measurement technologies for
heat and moisture transfer characteristics in porous media; enrich and improve the basic
database of porous media; and explore methods for measurement of the permeability,
porosity, capillary force, surface tension, and contact angle.
3. Strengthen basic research into heat and mass transfer in porous media that is at the back-
ground of engineering applications, which also becomes the main research directions of heat
and mass transfer in porous media.
6.2.2 Theoretical basis of heat, moisture, and solute

transfer in solid-state fermentation
The solid-state fermentation system is one of the most typical porous media systems.
It contains the solid body, aqueous solution, and gas phase, and involves moisture
and heat transfer. Heat and mass transfer properties of the medium have a great deal
to do with the moisture content of the medium and energy types of water in the solid-
state fermentation system. When studying heat and mass transfer in the matrix, the
substrate is divided into three categories based on the amount of moisture in the sub-
strate: water content of 100%, i.e., the pore space is filled with the liquid water
(water saturated); moisture in the presence of liquid and gases form in the nonsatu-
rated matrix; only moisture vapor appears in the pore space of the dry saturated
matrix (this state is clearly not suitable for the growth of microorganisms, and is
excluded in the subsequent discussion of this case). In most cases, the substrate is
an unsaturated multiphase system containing solid particles, water, steam, and air.
In this section, we will analyze the transfer processes of heat, moisture, and solute,
and the factors that influence them.
6.2.2.1 Transfer mechanism of heat and water in solid-state

fermentation
Water vapor transfer mechanism
1. Transfer mechanism of water
In the solid-state fermentation (SSF) process, water presents in the form of water vapor in the
gas phase, liquid free water (water film or droplets on the surface of the material particles,
capillary water, water in the gaps between the particles), and bound water of materials. The
water vapor in the gas phase includes water vapor in the air phase of the headspace layer and
gaps between particles.
Most of the moisture in the material is presented in the form of bound water. The solid
matrix is often porous in nature; these pores can be regarded as capillary tubes. The different
curvatures of the liquid level in and out of the pores lead to different vapor pressures. In the
case of a concave liquid surface, the equilibrium vapor pressure is lower than the normal
vapor pressure of the liquid. Therefore, water condensation can occur in the capillary
(capillary condensation) when the vapor pressure of the system is lower than the normal
saturated vapor pressure. This explains the capability of normal growth of microorganisms
in a solid matrix of low moisture content, and there is still some residual moisture in the
capillary, so the water activity is still relatively high.
Free water can be used by microbes; however, bound water cannot. The combined water
can be divided into (a) chemically combined water, that is, crystallization water of the com-
pound as well as moisture linked by hydrogen of certain compounds; (b) physically bound
water, that is, the moisture absorbed on the outer layer of material particles; and (c) solution
moisture, which comprises the water solvent of the liquid phase, the solution in the biolog-
ical cells, and solution discharged after cell rupture.
The bound water is closely combined with the dissolved macromolecules to form a
hydrate. The bound water includes all of the water molecules near the hydrated layer, as well
as water molecules close to the outside of the hydration layer. The hygroscopic water is a
monomolecular layer covering the nonwater component, and it is combined close together
with some specific hydrophilic group of the nonaqueous components. The membrane water
is the hydrogen bonding water combined with the solute, whose water activity is greatly
reduced. The combined water is closely combined with the objects mentioned above; there-
fore, there is a great difference in their natural properties. Bound water does not have the
characteristics of the solvent. It is difficult to boil, evaporate and to crystallize. Bound water
does not freeze, even at 40 C. The binding force between the water and the object is very
strong; the water integrated with the macromolecules relies on the ionic bonding and hydro-
philic polar group. This combination reduces the vapor pressure and chemical potential
of water.
There is also another type of bound water combined with biological macromolecules,
which is the nonwater component. The content of this type of water is low and it is present
deep inside the folded macromolecules, it does not substantially participate in chemical
reactions.
From the perspective of water used by microorganisms, the moisture includes intracel-
lular water and extracellular water (i.e., water outside all of the mycelium, including the
moisture in the material).
Figure 6.2 shows a diagram of the vertical distribution of the substrate water. From the
above analysis, the film water, capillary water, and gravity water show migration character-
istics (Chen, 2013). The moisture movement is driven not only by capillary forces, but
also by a variety of other forces, such as Darcy resistance of solid particles to liquid, the
interaction between the gas and the liquid, inertial force of liquid film movement, the liquid
gravity, and so on. Figure 6.2 provides the status and characteristics of the fermentation
substrate and the water in a SSF system.
There are a variety of ways of moisture transfer in solid materials including molecular
diffusion and convection. In the pretreatment of raw materials (such as soaking and cook-
ing), materials will absorb enough water. From the macroscopic viewpoint, the partial mate-
rial moisture content decreases and forms a moisture concentration gradient in different parts
of the material. From the microscopic viewpoint, moisture transfer exists in internal and
external particles as well as inside and outside of microbial cells.
Moisture transfer occurs inside the material particles; the moisture content of the surface
and the interior of the material particles is different; and the diffusion of water occurs auto-
matically in the material particles due to the presence of a moisture concentration gradient.
Limited by the oxygen supply, aerobic microorganisms mainly grow on the outer surface of
the material particles. Evaporation of moisture and water intake of new cells also takes place
Substrate
Free water
water zone
Transit- Water vapor; absorption water; Hanging water

ional zone gravity water
Capillary
Capillary water
zone
Saturation
Hygroscopic water; film water Saturation water
zone
Figure 6.2 Vertical distribution maps for matrix water in solid-state fermentation.
(Chen, 2013)
on the surface of the particles, so the moisture content of the surface of the particles is rel-
atively low, and the water could reach the surface of the material from internal particles by
diffusion. In addition, microbial hyphae always utilize the sugar nearby, which will cause a
solute concentration gradient in different parts of the material particles (Nagel et al., 2002).
The moisture concentration gradient caused by the solute concentration gradient further gen-
erates the diffusion of water.
The flowing water between the material particles is mainly free water. Assuming that the
moisture absorbed on particles would not be transferred to the other adjacent particles, the
transfer of moisture between particles is limited to the free water on the surface of the particles.
To model the water distribution of the sprayed water throughout the mixed substrate bed, Schu-
tyser et al. distinguished three different processes (Schutyser et al., 2003): (1) external addition
of water to the particles; (2) absorption of water by individual particles; and (3) transfer of
water between neighboring particles (Figure 6.3).
Schutyser et al. thought that the transfer of water between particles can only take place
via the fraction of water that is freely present on the surface of particles, called “free surface
water volume” (Schutyser et al., 2003). The precise location of the water on the surface is not
considered, but it may be envisaged as a film on the surface of the particles. Experimental
data indicated that the absorption process could be divided into two cases (a and b). If the
amount of total water was below a critical value, the water present at the surface was
absorbed instantaneously into the particle (case a). If this critical volume was exceeded,
absorption took place at a constant rate (case b).
Particle i (see Fig. 6.3) is located on the surface of the bed. Two varying water fractions
are distinguished: the absorbed water and the free surface water. The different water trans-
port processes are depicted as open arrows: (1) the addition of water; (2) the absorption of
water by the grains; and (3) the transfer of water between two grains (Schutyser et al., 2003).
2. Diffusion mechanism of vapor
Diffusion of vapor in the matrix has a very close relationship with the internal structure of
the matrix. The shape, size, and gas density of the internal pores determine the diffusion
mechanism. When denser gas gets through the matrix pores, the vapor molecules collide
with the pore wall with fewer opportunities; this diffusion still follows Fick’s law, which
is the Fick-type molecular diffusion. When the diameter of pores road is small, collision
occurs mainly between the gas molecules and the pore wall surfaces when the less dense
gas gets through the pore, and collision between the molecules is relegated to a secondary
position. The diffusion resistance is mainly caused by collision between the gas molecule
3 3
Free surface water Free surface water
Particle i Particle j
1 Absorbed water Absorbed water
2 2
Figure 6.3 Scheme of the moisture distribution model for two particles (i and j).
(Schutyser et al., 2003)
and the pore wall, and this diffusion does not follow Fick’s law, but is called Knudsen dif-
fusion. When the diameter of the pores equals the mean free path of the gas molecules, the
collision between the molecules and collision between the molecules and the pore wall are
both important; that is, both Fick diffusion and Knudsen diffusion exist, which is called tran-
sition zone diffusion. The structure of the matrix particles determine the form of the vapor
diffusion, typically Fick diffusion, Knudsen diffusion, or both. Due to the large capillary
channels in general research, Fick diffusion predominates.
3. Movement mechanism of gas phase in substrate
In the nonsaturated matrix, gas is mainly composed of air and water vapor, and air and
water vapor fill the pore space. The migration of the gas in the matrix is of four types; that
is, Knudsen diffusion, viscous flow, continuous diffusion, and surface diffusion.
Heat transfer mechanism

Generally speaking, to study the heat migration of internal particulates, three common
forms are mainly considered as follows:
1. Heat conduction. When there is a temperature gradient in the substrate, heat is transferred by
heat conduction in solid matrix, liquid water, vapor, and air.
2. Convection. Convective heat transfer is caused by flow of liquid water, vapor, and air within
the pore channel of the matrix.
3. Phase change. Liquid vaporization and vapor condensation may occur on the liquid surface
within the matrix because of the temperature gradient, which produces heat by phase change.
Meanwhile, due to the humidity difference between the substrate surface and gas on the top
of the matrix, an evaporation phenomenon will be produced on the surface of materials, and
subsequently bring the phase change heat.
Theoretical model of heat and moisture transfer

Researchers have made considerable progress in theoretical studies of water movement
in unsaturated or saturated porous matrix under isothermal conditions. The early studies
have shown that under nonisothermal conditions, the distribution and changes of tem-
perature in the matrix impact the physical and chemical properties of the matrix water
and subsequently affect the matrix potential, solute potential, and hydrodynamic param-
eters. These parameters, in turn, affect the fermentation temperature. Therefore, in the
study of water and heat transfer, researchers should highlight the mutual coupling rela-
tionships between them.
In a brief introduction to the theoretical model of water and heat transfer in porous
media under nonisothermal conditions, the Philip and de Vries model, (De Vries,
1958; Philip & De Vries, 1957), Philip and de Vries presented water and heat coupling
migration as follows:
@y @K
¼ rðDT rT Þ + rðDy ryÞ (6.1)
@t @z
@T
Ch ¼ rðlrT Þ LrðDyv ryÞ (6.2)
@t
where y is the water content of materials; t is time; DT is the diffusivity of matrix water
under temperature gradient; Dy is the diffusivity of matrix water under moisture
gradient; T is temperature; K is hydraulic conductivity; Ch is heat capacity; l is ther-

mal conductivity; L is latent heat of vaporization; z is the perpendicular distance.
The above equations take into account the liquid-gas two-phase flow under the
water content and temperature gradients at the same time. It describes the two coupled
nonlinear partial differential equations to explain the relationship between heat and
water transfer. Because of the wide application of the theory of Philip and de Vries,
it promotes the combined study of water and heat transfer in the matrix.
Cassel et al. applied the above theory to predict moisture movement in a porous
medium under a temperature gradient, and they proved that the theory of Philip
and de Vries could predict soil water movement, especially in substrates with lower
water content, and that the calculated and measured values of water flux could fit well
(Cassel et al., 1969).
Heat and moisture transfer process in moisture stratification

Solid-state fermentation substrates are typical water unsaturated porous media. How-
ever, in some cases, water is seriously lost and utilized as well as strong ventilation in
the fermentation process, and the surface water will be depleted, resulting in the usage
of the water inside the pore. When the water inside the pores is also dissipated
completely, the substrate will form a dry saturated layer (moisture content about
10%). After the dry saturated layer forms, evaporation does not take place on the sur-
face of the substrate, but only inside the matrix. The moisture evaporation intensity
decreases, and the loss of matrix moisture is controlled by diffusion from vapor to
air, and it is related to the thickness of the dry saturated layer. Therefore, the study
of the actual system must also consider the impact of moisture stratification on its
internal heat and moisture migration. Figure 6.4 shows a schematic diagram of the
moisture stratification in a substrate.
z
Air above matrix
Zone II, dry saturated zone Vapor diffusion
H1
Zone I, unsaturated zone Gas transfer

Liquid transfer
The lower surface of the substrate bed
Figure 6.4 Schematic diagram of moisture stratification.

(Chen, 2013)
Effect of temperature on the heat and moisture transfer in a solid matrix

Essentially, the temperature changes affect the physical parameters of the matrix. Gardner
put forward that there was a positive correlation between the temperature and the matrix
water potential according to capillary theory (Gardner, 1959). Zhang et al. considered that
the water suction of a porous matrix decreased with the increased temperature, and thus
improved water potential and water energy (Zhang et al., 1990). Philip and de Vries
(Philip & De Vries, 1957) first quantitatively studied the effect of temperature on the soil
water potential, and pointed out that soil water suction of the wetting front lowered by
1 cm when the temperature was increased by 0.002 C.
Preliminary studies showed that with an increase in temperature, the moisture
transfer accelerated (Constantz & Murphy, 1991). The changes in temperature can
also cause differences in the density of the water vapor, and subsequently cause
the movement of water vapor. In addition, temperature variations will affect some
physicochemical properties of water, such as viscosity, density, surface tension,
and so on, which affect the water potential and water movement. Philip & De
Vries (1957) attributed the effect of temperature on the water potential to its effect
on the surface tension of water. Haridasan and Jensen’s experiments showed that
the impact of temperature on the unsaturated hydraulic conductivity of matrix at a
given water content level could be completely attributed to its influence on the vis-
cosity of water (Haridasan & Jensen, 1972).
Thermal effects on solute transport in the matrix

Temperature greatly affects moisture movement. For the water-soluble organic salts
and organic nutrients, the diffusion coefficient of the solute is also associated with
temperature. Table 6.1 gives the diffusion coefficient of NaCl in water under typical
temperature conditions. From the table, the diffusion coefficient of NaCl in water at
35 C is twice that at 5 C, indicating that temperature largely affects the diffusion of
salt. The relationship between the diffusion coefficient of NaCl in the water and the
temperature can be shown as follows:
Dw ðtÞ ¼ 0:77669 + 0:0272t + 0:00025t2 (6.3)
The fermentation substrate is a porous medium, while diffusion of salt in water is dif-
ferent to that in a matrix solution; thus, the impact of substrate water content and
matrix body tortuosity factor need to be considered.
Table 6.1 Diffusion coefficient of NaCl in water at different

temperatures
Temperature ( C)
5 15 25 35
Diffusion coefficient (109 m2/s) 0.91 1.241 1.612 2.031

6.2.3 Heat and mass transfer in the steam explosion process

and its impact on the intensity factor
6.2.3.1 Introduction
Steam explosion is considered as an effective pretreatment method of lignocellulose.
Explosion intensity is the most important parameter of steam explosion, and directly
determines the effect of lignocellulose pretreatment. Commonly, explosion intensity
is characterized by an intensity factor or modified intensity factor of the hydrothermal
pretreatment process, as shown in Table 6.2.
The effects of the steam explosion technique on lignocellulose structure are sum-
marized into two aspects: (1) In the high-temperature cooking stage, hemicellulose is
degraded, lignin is softened, and cellulose is exposed (Cantarella et al., 2004); (2) In
the instantaneous relief phase, superheated state water flashes into steam, causing an
instantaneous expansion. Then a strong impact force acts on the material, resulting in
tissue tearing and fiber loosening.
Currently, the intensity factor summarizes the influences of time, temperature, and
acid concentration. Although it is easy to compare the experimental results, and the inten-
sity factor is to be applied in process design and operation, the intensity factor does not
summarize all the factors that influence the pretreatment effects (Hosseini & Shah, 2009).
Unlike some other hydrothermal pretreatment technologies, steam explosion, as an effi-
cient component separation technique, is notable in that its physical tearing impact is not
only conducive to strengthening the lignocellulose fiber solutions, but also increasing
specific surface area. The intensity factor derived from hydrothermal treatment processes
Table 6.2 Intensity factors of hydrothermal pretreatment processes

No. Equations References
(6.4) R ¼ t exp[(Tr Tb)/14.75] (Overend

et al., 1987)
In ½Pol=½Pol0
(6.5) (Chum et al.,
∝½H + exp½ðTr Tb Þ=14:75Dt + constant
h i 1988)
Er TTisor
(6.6) RBr + ¼ Tiso
T
r
exp ETiso r T CH + t (Belkacemi
h i et al., 1991)
RBs + ¼ Tiso
T
s
exp ETEisos TTT isos CH + t
s
TTref tR g
(6.7) RO ¼ exp o g (Abatzoglou
et al., 1992)
XX TTref tR g
ROH ¼ exp lXrefref exp o g
h i tg
(6.8) R0 ¼ exp o10 1 Tref
T g (Montané
T100
et al., 1998)
(6.9) R¼ t
e 14:75 10pH (Hosseini &
rd 1:5
0:67 0:5 0:33 Shah, 2009)
fD ru m
M 112Lnf
0:48 mð1e Þ r DC
cannot characterize the physical process of tearing in the instantaneous relief stage, but
only characterizes the role of the high-temperature cooking process.
Based on the diffusion process of steam into the material, Hosseini and Shah
(Hosseini & Shah, 2009) included the material size and processing time in the inten-
sity factor formula (Equation (6.9)). Although the particle size is considered in the
steam transfer process for the first time, Equation 6.9 still represents the effect of
the high-temperature cooking process, while physical tearing in the instantaneous
decompression stage has still not been included.
Physical tearing is affected by many factors, including particle size, loading factor,
and material moisture content (Chen & Liu, 2007; Chen et al., 1999). In addition, the
design parameters of the steam explosion tank also affect the tearing effect, such as the
ratio of height to diameter, the discharge port area (Chen et al., 1999), and the buffer
tank volume. Of course, the dimensional pressure (temperature) cannot be ignored.
Based on the three transfer theories and brittle fracture theory, the physical tearing
in the instantaneous decompression phase is analyzed, and the material size, moisture
content, and material discharge port area are included in the intensity factor formula.
The consolidated intensity factor not only takes into account the vapor explosion dur-
ing high-temperature cooking but also includes the physical tearing effect in the
instantaneous relief phase. It not only helps to fully understand the mechanism of
steam explosion, but also guides equipment and process design.
6.2.3.2 Multistage model of the instantaneous relief phase in the

steam explosion process based on energy conservation
Model assumption
It is assumed that the material density does not change with vapor infiltration and the
buffer tank is large enough, which means that the pressure of the buffer tank is con-
stant. Therefore, the variable parameters are dimensional pressure, time, particle size,
and moisture content of materials and relief port area.
Efficient physical tearing occurs at the cellular level, which means each cell can be
treated as a “microgas blast pot.” A cellular-level steam explosion model is shown in
Figure 6.5.
The material cell is assumed to be a ball with a radius of d. The total wet weight of
the material is m, the initial moisture content of the material is w; P1, T1, r1, m0 are the
state parameters in the initial stage; Pa, T2, r2, m0 + mw are the state parameters in the
final stage after steam relief; and v1, v2 are the speed of the steam and material, respec-
tively. For better understanding, it is assumed that an intermediate state existed. P3, T2,
r3, m0 + mw q are steam parameters in the intermediate stage, while q is gasification
rate of too-hot steam.
Establishment of the material brittle fracture criterion

The too-hot water in the cell flashes into steam during the steam relief stage, which
means P3 > > P1. The brittle fracture process of materials is seen as a quasi-static pro-
cess, which relies on the largest pressure P3. Without external load, the pressure of the
closed elastic body is expressed as
State 1 Intermediate state State 2

v3 ms, v2
Pa, Ta
P1, T1, r1, m0 Pa, T2
P3, T2, r3, m0 + mw . q Pa, T2, r2, m0 + mw, v1
d
Flash evaporation
mw
ms
Cell model
Figure 6.5 Cellular-level steam explosion model (Zhang & Chen, 2012).
siK ¼ PdiK (6.10)
Accordingly, the elastic energy per unit of solid material before and after the brittle
fracture can be written as
P23
Us1 ¼ (6.11)
2Ks rs
P2a
Us2 ¼ (6.12)
2Ks rs
where Ks is the bulk elastic modulus of solid materials. Therefore, the dissipated
energy in the brittle fracture process of the solid material is
E ¼ ðUs1 Us2 Þms (6.13)
Reorganizing Equations (6.11), (6.12), and (6.13), we obtain Equation (6.14):
P23 P2a
E¼ ms (6.14)
2Ks rs
In the instantaneous relief stage, the too-hot water releases some energy for its own
vaporization.
mw cm ðT1 T2 Þ ¼ mw qr (6.15)
where cm is the specific heat capacity of water, kJ/kg; and r represents vaporization
heat of water under the temperature of (T1 + T2)/2.
According to the ideal gas equation,
P1 V ¼ n1 RT1 (6.16)
P3 V ¼ n2 RT2 (6.17)
Equation (6.18) is then obtained,
P3 n2 T2 m0 + mw q T2
¼ ¼ (6.18)
P1 n1 T1 m0 T1
Since,
MP1 V
m0 ¼ (6.19)
RT1

rMP1 V + mw cm ðT1 T2 ÞRT1 T2
P3 ¼ (6.20)
rMV T1
Assuming that
T2
0:8,
T1
thus,
0:2 mw cm T12
P3 ¼ P1 + (6.21)
rMV
Reorganizing Equations (6.14) and (6.21), we obtain Equation (6.22):

0:2mw cm T12 2
P1 + rMV Pa2
E¼ ms (6.22)
2Ks rs
Establishment of conservation equations

1. Energy conservation equation.
The energy in the intermediate stage contains internal energy e1 (m0 + mw q) and potential
k ðm0 + mw ÞP3
energy . The energy in the final stage contains internal energy
k1 r3
e2 (m0 + mw q), kinetic energy 12 ðm0 + mw qÞv21 + 12 ms v22 , and potential energy
k ðm0 + mw qÞPa
.
k1 r2
According to the principle of energy conservation,
k ðm0 + mw qÞP3
e1 ðm0 + mw qÞ + ¼
k1 r3
(6.23)
1 1 k ðm0 + mw qÞPa
e2 ðm0 + mw Þ + ðm0 + mw qÞv21 + ms v22 + +E
2 2 k1 r2
where e1 and e2 are the internal energy per kilogram of steam of the intermediate and final
stage, respectively, and k refers to the volatile index of steam (Ning et al., 2010).
According to the polymer state equation (Ning et al., 2010),
P ¼ Ark (6.24)
A
e¼ rk1 (6.25)
k1
where A is a constant, the value depends on the gas type. Therefore, the relation of e, P, and
r is
P
e¼ (6.26)
rðk 1Þ
Accordingly,
P3
e1 ¼ (6.27)
r3 ðk 1Þ
Pa
e2 ¼ (6.28)
r2 ðk 1Þ
P3 k ðm0 + mw qÞP3
ðm0 + mw qÞ + ¼
r3 ðk 1Þ k1 r3
(6.29)
Pa 1 1 k ðm0 + mw qÞPa
ðm0 + mw qÞ + ðm0 + mw qÞv21 + ms v22 + +E
r2 ðk 1Þ 2 2 k1 r2
P3 k ðm0 + mw qÞP3 Pa 1
ðm0 + mw qÞ + ¼ ðm0 + mw qÞ + ms v22
r3 ðk 1Þ k1 r3 r2 ðk 1Þ 2

2 2
0:2 mw cm T1 (6.30)
P1 + P2a
1 k ðm0 + mw qÞPa rMV
+ ðm0 + mw qÞv1 +2
+ ms
2 k1 r2 2Ks rs
2. Momentum conservation equation

The impulse acting on the material is equal to the momentum increase of the material during
the instantaneous relief stage. Because the material cell is assumed to be a ball, on which the
pressure is described as below:
s ¼ ðP3 Pa Þpd 2 (6.31)
ðP3 Pa Þpd 2 t ¼ ms v2 (6.32)
where t is the lasting time of the steam decompression stage.

Assuming that the steam relief speed is equal to the sound speed (Wang, 2006), the time
that needed for steam escape depends on the relief area; that is, t ¼ =A, where is a
parameter of the device, depending on the design of the relief port.
Thus,
ðP3 Pa Þpd 2
¼ ms v2 (6.33)
A
P3 k ðm0 + mw qÞP3 Pa
ðm0 + mw qÞ + ¼ ðm0 + mw qÞ
r3 ðk 1Þ k1 r3 r2 ðk 1Þ
2
0:2 mw cm T12
P1 + Pa p2 d4 2
rMV 1
+ + ðm0 + mw qÞv21 (6.34)
2A2 ms 2
2
0:2 mw cm T12
P1 + P2a
k ðm0 + mw qÞPa rMV
+ + ms
k1 r2 2Ks rs
Reorganizing Equations (6.15), (6.19), (6.21), and (6.34), we obtain Equation (6.35):

0:2 mw cm T12
P1 + MP1 Vr + 0:2 mw cm RT12 ðk + 1Þ
rMV
r3 RT1 r ðk 1Þ
2
0:2 mw cm T12
P1 + Pa p2 d 4 2
Pa MP1 Vr + 0:2 mw cm RT1 ðk + 1Þ
2
rMV (6.35)
¼ +
RT1 rr2 ðk 1Þ 2A2 ms
2
0:2 mw cm T12

P1 + P2a
1 MP1 Vr + 0:2 mw cm RT12 2 rMV
+ v1 + ms
2 RT1 r 2Ks rs
In the steam decompression stage, the steam relief speed is equal to the sound speed c
(Wang, 2006),
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
ffi sffiffiffiffiffiffiffiffi
@p1 P3
c¼ ¼ k (6.36)
@r1 s r3

0:2 mw cm T12
P1 + MP1 Vr + 0:2 mw cm RT12 ðk + 1Þ
rMV
r3 RT1 r ðk 1Þ
2
0:2 mw cm T12
P1 + Pa p2 d4 2
Pa MP1 Vr + 0:2 mw cm RT1 ðk + 1Þ
2
rMV
¼ +
RT1 rr2 ðk 1Þ 2A2 ms

0:2 mw cm T12
MP1 Vr + 0:2 mw cm RT12 P1 +
1 rMV
+
2 RT1 rr3
2
0:2 mw cm T12
P1 + P2a
rMV
+ ms (6.37)
2Ks rs
6.2.3.3 Significance of the multistage model

Optimization of the temperature and material moisture of steam explosion based
on the maximum dissipated energy E
Equation (6.22) shows that moisture and the pressure (temperature) are key factors
affecting the physical tearing in steam explosion. The Antoine equation is widely used
to calculate the saturated water vapor pressure. However, saturated water vapor pres-
sure and temperature conversion are difficult due to their complexity. Therefore, we
fit a simple quadratic equation to characterize the relationship between saturated
vapor pressure and temperature:
P ¼ 3:6 107 179876T + 224:9T 2 ðR ¼ 0:999Þ (6.38)
Thus, Equation (6.22) can be transformed as below:

2
0:2 mw cm T12
P1 +
rMV
E ms ¼
2Ks rs

2 2
(6.39)
2 0:2 mwcm T1
3:6 10 179876T1 + 224:9T1 +
7
mð1 wÞ
rMV
2Ks rs
Equation (6.39) means

2
0:2 mwcm T12
3:6 107 179876T1 + 224:9T12 + mð1 wÞ
rMV
E¼ (6.40)
2Ks rs
E ¼ ðA + BwÞ2 ð1 wÞð0 < w < 1Þ (6.41)
pffiffiffiffi
3:6 107 179876T1 + 224:9T12 m
A¼ pffiffiffiffiffiffiffiffiffiffiffiffiffi (6.42)
2Ks rs
p ffiffiffi
ffi
0:2 mcm T12 m
B¼ pffiffiffiffiffiffiffiffiffiffiffiffiffi (6.43)
rMV 2Ks rs
When the first derivative
E¢ ¼ ðA + BwÞ2 + 2Bð1 wÞðA + BwÞ ¼ 0 (6.44)

2B A
wopt ¼ (6.45)
3B
4 ð A + BÞ 3
Emax ¼ (6.46)
27B
Each temperature T (range: 160–235 C) corresponds to an optimum water content
wopt. In this case, the energy dissipation E of solid material in the process of brittle
4(A+B)3/27B
Emax
(2B − A)/3B
0 wopt w
Figure 6.6 Effect of material moisture content on energy consumption in the steam
relief phase.
fracture reaches the maximum. The relationship between T and wopt can be expressed
as wopt ¼ 2BA
3B (A and B refer to Equations (6.42) and (6.43), respectively). At this time
the tearing action on the material reaches a maximum, which is beneficial for com-
ponents separation and increases the specific surface area.
From Equation (6.39), it can be deduced that
E∝T14 (6.47)
Therefore, the energy dissipation of a solid material in the process of brittle fracture
increases with the increase of T1, illustrating that high temperature is good for tearing
and increasing specific surface area.
Optimization of the material particle size and the discharge port area of the steam
explosion tank based on the maximum dissipated energy E
Based on the above equations,

0:2 mw cm T12
2 P1 + Pa MP1 Vr + 0:2 mw cm RT12 ðk + 1Þ
rMV

0:2 mw cm T12
MP1 Vr + 0:2 mw cm RT12 P1 + ðk 1Þ
rMV

2r3 RT1 r ðk 1Þ
2 2
0:2 mw cm T12 0:2 mw cm T12
P1 + Pa p d
2 4 2
P1 + P2a
rMV rMV
¼ + ms
2A2 ms 2Ks rs
(6.48)
Because Pa < < P1, we can ignore Pa. Therefore,

MP1 Vr + 0:2 mwcm RT12 ðk + 3Þ
2r3 RT1 r ðk 1Þ

0:2 mwcm T12 0:2 mwcm T12
P1 + p d
2 4 2
P1 +
rMV rMV
¼ + mð1 wÞ
2A2 mð1 wÞ 2Ks rs
(6.49)
Reorganizing Equations (6.38) and (6.49), we obtain Equation (6.50),

M 3:6 107 179876T1 + 224:9T12 Vr + 0:2 mwcm RT12 ðk + 3Þ
2r3 RT1 r ðk 1Þ

2 0:2 mwcm T1
2
3:6 10 179876T1 + 224:9T1 +
7
p2 d4 2
rMV
(6.50)
2A2 mð1 wÞ

0:2 mwcm T12
3:6 107 179876T1 + 224:9T12 +
rMV
+ mð1 wÞ
2Ks rs
Equation (6.50) can be expressed as

d4
K1 T1 + K2 wT1 ¼ K3 T12 + K4 T12 2 + K5 T12 + wK6 TI2 ð1 wÞ (6.51)
A ð1 wÞ
MVr 224:9
K1 (6.52)
2r3 Rr ðk 1Þ
0:2 mwcm ðk + 3Þ
K2 ¼ (6.53)
2r3 r ðk 1Þ
224:9p2 2
K3 (6.54)
2m
0:2 wcm p2 2
K4 ¼ (6.55)
2rMV
224:9m
K5 (6.56)
2Ks rs
0:2 m2 wcm
K6 ¼ (6.57)
2Ks rs rMV
It can be deduced from Equation (6.51) that
ðK1 + K2 wÞA2 ð1 wÞ
T1 ¼ (6.58)
ðK3 + K4 wÞd 4 + ðK5 + wK6 Þð1 wÞ2 A2
As shown in Figure 6.6, each temperature T (range: 160–235 C) corresponds to an

optimum water content wopt. Therefore, wopt and T can be assumed to be constant.
aA21 aA21
T¼ ¼ (6.59)
bd14 + wA21 bd24 + wA22

a ¼ K1 + K2 wopt 1 wopt (6.60)
b ¼ K3 + K4 wopt (6.61)
2
w ¼ K5 + wopt K6 1 wopt (6.62)
According to Equation (6.59),

2
A1 d1
¼ (6.63)
A2 d2
That is,
A∝d 2 (6.64)
It can be seen from Equations (6.63) and (6.64) that the discharge port area A is related to
the particle size d under certain T and wopt, which can be expressed as A ∝ d2. This means
that the material in the different particle sizes require matching to different discharge port
areas, whereas a fixed discharge port area should correspond to the appropriate particle
size to achieve optimal physical tearing. Thus, material particle size for steam explosion is
not randomly selected but should be limited according to the discharge port area.
6.2.3.4 New content of steam explosion intensity factor

Based on the material particle size, discharge port area, and material moisture content,
a new steam explosion intensity factor can be calculated. If the intensity factor R was
used to describe the steam explosion process, the chemical and physical effects should
both be taken into account. Thus,
ðK1 + K2 wÞA2 ð1 wÞ

373
td1:5 ðK3 + K4 wÞd 4 + ðK5 + wK6 Þð1 wÞ2 A2
R¼ e 10pH (6.65)
K7 14:75
r
K7 ¼ !0:67 0:5 0:33 ! (6.66)
fD ru m
M 0:48 DC
1 12 Lnf mð1 eÞ r
where r represents the density of water; m represents the viscosity of water; u refers to
the steam penetration rate; e represents the porosity of the material; f represents poros-
ity in the system; D represents the effective diffusion coefficient; t refers to the dimen-
sion time; d refers to material particle radius; A refers to the relief port area; w refers to
the moisture content of materials; and K1–K6 are seen as constant. Equation (6.65) indi-
cates that the material particle size d, the discharge port area A, and the moisture content
of materials w all have a significant impact on the steam explosion intensity factor R.
According to Equation (6.64), A ∝ d2, assuming A ¼ k¢ d2 (because the R-value in this
1
case reaches maximum), R∝d 1:5 ew . The R-value increases as the values of w and d
decrease. That is, relatively small particle size d and relatively low moisture w will pro-
duce a greater R. In this condition, the physical tearing will reach the optimum level.
In addition to traditional chemical factors such as time and temperature, the
enhanced steam explosion intensity factor R also includes physical factors, providing
a theoretical basis for further research. R would provide theoretical guidance for the
steam explosion process and equipment design. At the same time, R needs to be further
simplified. The particle size and moisture content of materials also need further opti-
mization, and the relationship between A and d needs further clarification.
In summary, based on the material brittle fracture criterion E ∝ T41, it can be seen
that the physical tearing effect of a material is proportional to the fourth power of the
steam explosion temperature, indicating that high temperature is a benefit for physical
tearing. Based on the maximum energy dissipation in the steam explosion relief pro-
cess, the relationship between material moisture content and temperature T $ wopt,
and the relationship between the discharge port area and material particle size
A ∝ D2 are optimized, providing a theoretical basis for choosing the optimal temper-
ature and material particle size in steam explosion. The traditional explosion intensity
factor has been modified. The new steam explosion intensity factor R contains mate-
rial parameters, such as particle diameter d and initial material moisture content w;
operation parameters, such as temperature T and time t; and device parameters, such
as discharge port area A, which not only helps to explore the steam explosion mech-
anism, but also provides a scientific basis for steam explosion process design.
6.3 Unit process and equipment in lignocellulose

biorefining
The lignocellulose biorefinery process is a system integrating a series of unit operations,
mainly including raw material pretreatment (chopping, rehydration, steam explosion,
etc.), fractionation, fermentation, hydrolysis, drying, and online determination and auto-
matic control operation. Based on the main techniques and equipment, this section will
introduce the key unit processes in lignocellulose refinery engineering.
6.3.1 Steam explosion pretreatment and equipment

The first attempts at steam explosion for the pretreatment of lignocellulose began in
the early 1980s. Raw materials were heated to 180–235 C by steam and the pressure
was maintained for a certain time. Under high temperature and pressure, the acetyl of
the hemicellulose generates organic acids and then participates in the catalytic process
of hemicellulose and lignin depolymerization. Hemicellulose is hydrolyzed into sol-
uble polysaccharide and lignin is softened due to the breakage of the a-propylene ether
bond and parts of the b-propylene ether bond. As a physical and chemical method, the
steam explosion pretreatment method enables the three main components of lignocel-
lulose substances to be utilized respectively, because it can effectively isolate the
active fiber without the use of chemicals. Therefore, steam explosion pretreatment
technology has the advantages of no environmental pollution and low energy con-
sumption, which makes it one of the most widely used methods of lignocellulose
pretreatment.
Steam explosion adopts high-temperature and high-pressure steam to deal with the
lignocellulose, and component separation and structural change of lignocellulose are
realized through the process of instant decompression. Generally, raw materials are trea-
ted with high-pressure steam in a pressure-resistance reactor, under the conditions of
16–34 kg cm2, 200–240 C, holding for 30 s to 20 min, and then decompressed rapidly,
forcing the material to be released into the atmosphere. The earliest study by the Lotech
Company indicated that, under any given pretreatment pressures, the pretreatment time
required for obtaining the highest yields of xylose and glucose will differ. Therefore, it
recommended that the best pretreatment conditions for holocellulose (including xylose
and glucose) were 500–550 Pa for 40 s. Since then, steam explosion technology has been
widely used in the pretreatment of hardwood, softwood, agricultural waste (such as
bagasse, wheat straw, rice straw, and corn stalks), and other noncellulose materials.
Chen et al. proposed that the steam explosion process imposes two effects on
the structure of lignocellulose; namely, the high-temperature cooking effect and the
mechanical effect of instantaneous decompression (Chen & Li, 1999). First, at the
high-temperature cooking stage, hemicellulose is degraded into soluble sugar, and lignin
in the intercellular layer is solubilized and partially degraded, which is a benefit for the
mechanical separation of lignocellulose as it reduces the binding between celluloses. Sec-
ondly, under instantaneous decompression, superheated water flashes into steam and the
steam volume abruptly expands. The impact force generated by flashing and the volume
expansion destroys the cell structure. In this stage, materials are torn into small pieces;
fiber bundles are separated from each other and their structures are loosened. Therefore,
cellulose is fully exposed and lignin is redistributed. After being treated at 240–250 C for
1 min, Schultz et al. found that the enzymatic hydrolysis yields of steam-exploded wood
chips, rice husks, corn cob, bagasse, and other lignocelluloses were significantly
increased. And the enzymatic hydrolysis yields of these pretreated materials showed
almost no decrease, even after being kept for 8 months (Schultz et al., 1984). Laser et al.
gave an explanation for the results, noting that the cellulose conversion rate of steam-
exploded pretreated bagasse (216 C for 4 min) could reach 67% (Laser et al., 2002).
Under the steam explosion conditions of 230 C for 1–2 min, Martinez et al. pretreated
broad-leaved wood chips, then the steam-exploded chips were used for enzymatic hydro-
lysis; the saccharification rate reached 90%, and the enzymatic hydrolysis yields of
steam-exploded eucalyptus and bagasse and the recovery yields of xylose both increased,
generally reaching 45–65% (Martinez et al., 1990).
Steam explosion pretreatment has several advantages: (a) Pretreatment conditions
can be easily optimized to produce high yields of specific chemicals from a wide variety
of plant lignocellulose. (b) Hemicellulose, lignin, and cellulose can be separated during
three different process units, to produce water-soluble, alkali-soluble, and water- and
alkali-insoluble fractions, respectively. (c) Theoretical enzymatic hydrolysis conversion
yields of cellulose can be achieved. (d) The lignin component is still suitable for
chemicals production even after steam treatment. (e) Sugars generated from hemicellu-
lose can be fully utilized and converted into liquid fuels. (f) The release of fermentation
inhibitors can be considerably reduced under optimal pretreatment conditions. In addi-
tion, the cost of the steam explosion pretreatment process is low; generally, 1 ton of mate-
rial consumes 0.5–1.0 tons of steam. These advantages make steam explosion one of the
most widely used pretreatment technologies for lignocellulose biomass.
In the steam explosion process, some chemical reagents are usually added as cat-
alysts, such as H2SO4 (or SO2, CO2, etc.). These reagents can also be added before
steam explosion to improve the hydrolysis rate of hemicellulose and reduce the inhib-
itors for enzymatic hydrolysis. The addition of this kind of reagent can increase the
proportion of monosaccharides in the total hydrolysate and decomposition of the
acid-soluble lignin. The removal of lignin and degradation of hemicellulose increase
the pore size of cellulose, enhancing the hydrolysis efficiency of cellulose. However,
the addition of chemical reagents causes environmental pollution and the equipment
requirements also increase. The non-polluting steam explosion technology proposed
by Chen and Liu (2007) does not require the addition of any chemicals; instead, it just
controls the water content of the straw. It can isolate more than 80% of the hemicel-
lulose, and the enzymatic hydrolysis rate of straw is more than 90%.
In 1989, an intermittent steam explosion device was produced in China by the Inner
Mongolia Boiler Plant. However, problems of rapid reaction and heating up, and
uneven heating of materials of the intermittent steam explosion reaction still need
to be solved. Currently, the most successful commercial application is the SBC pro-
cess by Canada’s Staketech Company. This technology uses a continuous steam
explosion process, and the heating time and temperature are strictly controlled.
The cost of steam explosion pretreatment is low and the enzymatic hydrolysis
yields of steam-exploded lignocellulose are improved markedly. But in this process,
lignin is still not removed, and the material is extruded at the same time, resulting in a
low concentration of sugar even with high substrate concentration; for example, 10%
of the substrate concentration can only get about 5% sugar.
Currently, steam explosion devices have been successfully applied from a laboratory
scale to an industrial scale. Figure 6.7(a) shows a 5-L laboratory steam explosion device
designed by Prof. Chen’s research group, which mainly consists of a steam generator, a
pressure holding tank, and a receiver. The operating pressure is 0–2.5 MPa and the tem-
perature is 0–250 C. The feeding valve is manually controlled and can be connected
with nitrogen bottles to achieve a mixed gas steam explosion. Figures 6.7(b–d) show
the enlarged steam explosion devices covering 1 m3, 5 m3, and 50 m3 respectively.
6.3.2 Carding fractionation equipment

6.3.2.1 Hydraulic carding fractionation equipment
(Paul screening instrument)
A Paul screening instrument consists of four arranged oval cylinders as shown in
Figure 6.8. The material in the highest cylinder passes through the following three
cylinders by gravity. Each jar is equipped with a screen of a different size, on which
fibers of different lengths are retained.
Figure 6.7 Steam explosion devices. (a): 5 L; (b): 1 m3; (c): 5 m3; (d): 50 m3.
Figure 6.8 ZT10-00 Paul

screening instrument.
6.3.2.2 Air classifier

An air classifier is a commonly used separation method for material particles, driven
by centrifugal force. When the mixed particles and air enter the classifying chamber at
a constant speed, the particles are subjected to centrifugal force from the turbine blade,
the air resistance, and their gravity. By adjusting the rotational speed of the turbine,
materials of different particles can be classified. Figure 6.9 shows a schematic dia-
gram of the air classifier, which mainly consists of a feeding tube, adjusting tube,
adjusting ring, fractionation part and gear, a middle barrel, and a lower cone barrel.
To achieve multilevel product separation, several air classifiers can be connected to
form a multiproduct fractionation system.
6.3.2.3 Mechanical carding fractionation

Mechanical carding fractionation equipment mainly consists of a high-speed rotation
drum and a fixed curved concave plate, so that the materials between the drum and the
concave plate can pass through as a result of the turning teeth blowing, rubbing, and
rolling. Material is fed from one end of the drum, moves along the roller axis, and then
is thrown from the other end of the drum. During the moving process, long and short
fibers are divided by centrifugal force. The main factors influencing the fractionation
effect include the drum speed and the moisture content of raw materials. Mechanical
carding fractionation is shown in Figure 6.10.
3 4
Feedstock
1
Emissions
Product 1 Product 2 5
Product 3
6
Figure 6.9 Schematic diagram of the air classifier. (1): Feeding tube; (2, 3): fractionation part;
(4): receiver; (5): rotary ejector; (6): fan.
Figure 6.10 The mechanical carding

fractionation equipment.
6.3.3 Solid-state fermentation and gas double dynamic solid-

state fermentation bioreactor (GDSFB)
6.3.3.1 Introduction to gas double dynamic solid-state
fermentation technology
SSF plays a more important role in industrial fermentation processes compared to the
traditional submerged fermentation (SMF), because it resolves the problem of solid
waste disposal. SSF is defined as fermentation involving solids in the absence (or near
absence) of free water; however, the substrate must contain enough moisture to sup-
port the growth and metabolism of microorganisms. It offers advantages including low
energy requirement, high products concentration, and little wastewater production and
is environmentally friendly compared with SMF. However, given that the substrates
used in SSF are always agroindustrial products with low thermal conductivities, the
heat removal in the SSF process is slow. Thus, the problem of overheating in the fer-
mentation medium has become a bottleneck of SSF technology. To strengthen heat
transfer and avoid microbial mycelium damage, Prof. Chen proposed new principles
of bioreactor design using normal pressure as an outside cycle pulsation power source
to stimulate the fermentation process. Based on the characteristics of the raw materials
and the biological characteristics of the microbes, Chen designed a pressure pulsation
SSF technology that has completely independent intellectual property rights. In 1998,
a large-scale solid-state pure culture fermentation demonstration plant was built, and
the results showed that economic indicators of this technology were better than
traditional submerged fermentation. On this basis, the gas double dynamic solid-state
fermentation (GDSSF) technology has gradually developed into one of the modern
SSF technologies (Foong et al., 2009).
In the traditional SSF process, the transfer of heat and mass were usually enhanced
by mechanical agitation, in which the gas phase was fixed and the solid phase was
continuously agitated, in order to mix the solid substrate particles completely and
strengthen the contact between the particles and gas molecules. During the agitating
SSF process, the growth of microbes would be damaged by the shearing force. In addi-
tion, it is difficult to seal the equipment, and energy consumption is high. The sticky
wet materials also make direct contact with the fermentation tanks, which can easily
cause the occurrence of dead corners in the fermenter. If the agglomeration of the
medium cannot be completely avoided, the efficiency of heat and mass transfer are
adversely influenced. These shortcomings of traditional SSF can all be overcome
by gas double dynamic solid-state fermentation. The transfer of mass and heat can
be improved, and both the gradient of temperature and the O2 and CO2 concentration
can be reduced. At the same time, the activity phase of microbial metabolism can be
promoted by periodic high-pressure pulse. Table 6.3 shows the productivity of cellu-
lase in pilot- and large-scale solid-state fermenters, indicating that industrial-scale
GDSSF has clear advantages in both enzyme activities and fermentation.
6.3.3.2 Characteristics of gas double dynamic solid-state

fermentation
The GDSSF consists of a horizontal SSF cylinder, a built-in circular duct, cooling
pipes, blowing devices, and an air circulation system. GDSSF can be divided into
two types: i.e., systems using a single vessel or using double vessels as shown in
Figure 6.11 (Chen & He, 2012) and Figure 6.12 (He & Chen, 2013), respectively.
The characteristics of GDSSF can be summarized as follows: (1) No mechanical
agitation device. The transfer of mass and heat is achieved by air circulation.
(2) The bioreactor structure is simple and easy to seal. (3) The fermentation tank is
Table 6.3 Production of cellulase under solid-state fermentation

at pilot and large scale
Cellulase
activity
Mass and heat (U g1 dry
Strains Fermenter type transfer mode substrate) Reference
Trichoderma 100 m3 gas double Circulation and 60 Unpublished

viride dynamic periodic air results
fermenter pulsation pressure
Aspergillus 50 L tray Laminar air flow 35.8 (Dhillon et al.,
niger and fermenter 2011)
Trichoderma
reseei
Trichoderma 130 L packed bed Without agitation 18.26 (Roussos
harzianum fermenter et al., 1993)
T. viride SL-1 4 m3 rotary drum Forced aeration 14 (Sun et al.,
fermenter 1999)
T. harzianum 50 L rotary drum Rotating and air 10.1 (Alam et al.,
solid-state circulation 2009)
bioreactor
Thermoascus 10 L rotating drum Intermittent 5.48 (Roussos
aurantiacus type bioreactor agitation et al., 1993)
5
2 9
4
3
11
8
6 7
10
Figure 6.11 Schematic of GDSSF with a single vessel. (1): Aseptic air system; (2): Vessel of
GDSSF; (3): Quick opening mechanism; (4): Air inlet valve; (5): Electric-contact pressure
gauge; (6): Air outlet valve; (7): Medium trays; (8): Blower; (9): Controlling line;
(10): Industrial computer; (11): Air flow circulation.
(Chen & He, 2012)
5
9
2 4
6 8
11
10
Figure 6.12 Schematic of GDSSF with double vessels. (1): Aseptic air system; (2): Vessel of
GDSSF; (3): Quick opening mechanism; (4): Air inlet valve; (5): Electric-contact
pressure gauge; (6): Air outlet valve; (7): Medium trays; (8): Blower; (9): Controlling line;
(10): Industrial computer; (11): Air flow circulation.
(He & Chen, 2013)
a pressure-resistant container, which can be sterilized by steam pressure. (4) During

the fermentation process, the pressure of the fermenter is kept positive, which is easy
to keep sterile. (5) The microbial metabolism could be enhanced by cycle stimulation.
(6) The temperature and humidity of the bioreactor are easy to control. (7) The fer-
mentation process is automated (Chen et al., 2007).
6.3.3.3 Process of gas double dynamic solid-state fermentation

GDSSF technology is developed from tray solid-state fermentation. Pressure pulsation
in the gas double dynamic fermentation process is accomplished by supercharging and
decompression of sterile air. One cycle of pressure pulsation consists of four stages:
pressurization, high-pressure holding, de-pressurization and low-pressure holding,
as shown in Figure 6.13 (Xu et al., 2002). The duration of the supercharging stage
is long and the curve rises gently. The duration of decompression is as short as possible,
generally from a few seconds to one minute. The duration of the high-pressure stage
and the atmospheric stage can be set freely according to different fermentation
Air pressure
100
Air pressure relative value (%) 80
60
40
20
0 20 40 60 80 100 120
Culture time (min)
Figure 6.13 Inside air pressure pulsation curve of GDSSF.

(Chen, 2013)
processes. Usually, in the microbial logarithmic growth period, the circulation is fre-
quent. Yet, in the lag period and the stable period, the cycle is infrequent. The cycle
time ranges from 15 min to 150 min. The wet solid particles are rapidly loosened by the
rapid expansion of gas, which enhances the heat and mass transfer (He & Chen, 2013;
Selinheimo et al., 2006).
6.3.3.4 Future trends in gas double dynamic solid-state

fermentation
The gas double dynamic solid-state technology has groundbreaking significance both
in terms of theory and industry applications. Based on the results of experiments and
practice, the technology can be applied to a wide range of microorganisms, such as
bacteria, fungi, and actinomycetes.
GDSSF technology breaks the monopoly of SMF technology in the modern fer-
mentation industry. Due to the unique advantages of this fermentation, a lot of liquid
fermentation technology could be replaced by GDSSF technology, such as production
of pesticides, production of cellulase, production of pectinase, and production of ribo-
flavin. A lot of new products can be produced by GDSSF, and more importantly, the
bioconversion of lignocellulose substrate can be achieved to produce for example
cellulose ethanol and bioorganic fertilizer. Compared to traditional SSF technology,
fermentation time tends to be shortened by one-third using GDSSF technology. In
addition, it could also play an important role in mixed culture fermentation, such
as Chinese traditional liquor brewing, and flavor food production.
Based on the laboratory level GDSSF process and a combination of bionics knowl-
edge, Prof. Chen designed and established a breathing SSF bioreactor (Figure 6.14).
The whole fermentation system consists of two fermentation tanks. There is a recip-
rocating pump between the two fermentation tanks. The air passes from one fermenter
Figure 6.14 Breathing solid-state fermentation bioreactor.

(Chen, 2013)
into the other. The negative pressure tank sucks fresh air, and forms an atmospheric
pressure tank. At the same time, the high-pressure tank outlets exhaust gas, and sub-
sequently forms atmospheric pressure. The circulation of negative pressure,
atmospheric pressure, and high pressure proceed until the end of fermentation. Carbon
dioxide could be discharged and heat could be removed by repeated cycles of
“breathing” and “sucking” in the two parallel fermenters.
6.3.4 Online determination in the lignocellulose

biorefinery process
6.3.4.1 Comparison of the process parameters and parameter
determination methods
Determination of environmental parameters and process parameters is the basis for
exploring and optimizing the lignocellulose biorefinery process. Environmental
parameters – mainly pressure, temperature, and humidity – can be easily measured
by conventional sensors, and is not discussed further here. However, process param-
eters such as moisture content, fermentation biomass, and enzyme activity, need to be
measured by developing the relevant techniques.
6.3.4.2 Online determination using digital image analysis

According to the theoretical basis of fractal geometry, the author’s team studied the
morphological changes of the cell matrix in the bacterial fermentation process by
using the digital image processing method and the established kinetic model (Duan
et al., 2012). They also examined the changes of matrix morphology with cell growth
under three different phase structures, and provided a new approach for the character-
ization and optimization of the SSF process.
Materials and methods

Three milliliters of Penicillium decumbens JU-A10 spore suspension (5.2 108/ml)
were seeded in a 50 ml liquid culture medium, shaking the culture for 24 h at 30 C
and 170 rpm. The solid medium consisted of 4 g of steam-exploded wheat straw,
and 1 g of wheat bran. Then 10 ml inorganic salt solution was added with stirring. After
sterilization, the medium was inoculated with 3 ml seed liquid and cultivated at 30 C.
In the fermentation process, the medium was removed every 24 h to take pictures with a
Cannon Powershot A650 camera (50 mm lens) (Figure 6.15).
The digital image processing method is shown in Figure 6.16. First, the RGB color
image was converted into grayscale by adjusting the background. Histogram equali-
zation and low-pass filters were used to enhance the grayscale. Then, the improved
image was converted into a binary image using the Ostu threshold segmentation
Camera
Polystyrene plate
Column bottle
Culture
Polystyrene plate
R 35 mm Central hole
140 mm
R 25 mm
Bottle mouth
140 mm
Figure 6.15 Schematic diagram of image acquisition device. (a): Three-dimensional diagram
of device; (b): top view of device.
(Duan et al., 2012)
Figure 6.16 Numerical image

processing step.
Image acquisition (Duan et al., 2012)
Background correction
Histogram equalization
Low-pass filter
Threshold
segmentation (OSTU)
Erosion Binary image
Contour extraction
Candy operator
Contour image
method (Mitchell et al., 2004; Rahardjo et al., 2006). In addition, the erosion operation
was used to enhance the image quality. Finally, the outline of the image was extracted
by using the Candy operator for the subsequent calculation of fractal dimension. The
above steps were accomplished using Matlab 7.1 programming.
The samples were accurately weighed after drying at 60 C for 24 h and their water
content was obtained. The biomass in the culture medium was measured by the gluco-
samine method. Fractal dimension was calculated by the methods of Theiler et al.
(Otsu, 1975).
The calculation is as follows: the obtained image is divided into a grid side length
of 1–1024 pixels. When the images are measured with a different scale, the following
equation is obtained:
N ðsÞ ¼ csDB (6.67)
DB is fractal dimension, N(s) is the number of grids covering the test area, and c is a
constant. By taking the logarithm on both sides of the above equation, using the
regression method, and fitting the equation of log N(s) and log s, –DB is obtained, as
follows:
log N ðsÞ ¼ log c + ðDB Þ log s (6.68)

Results and discussion

1. The relationship between the fractal dimension of SSF and mycelial growth.
In order to investigate the effect of mycelium growth on the lignocellulose matrix morphol-
ogy, samples of bacteria-matrix mixtures in the fermentation process are photographed every
24 h and the images are processed to calculate fractal dimension. The results are shown in
Figure 6.17. With the growth of the mycelium, the structure of the matrix fiber is damaged,
fibers become slender, and the entire mycelium-matrix mixture structure becomes more
complicated.
According to the principle of the meter box dimension, the fractal dimension of
bacteria-matrix demonstrates that the outline of the matrix changes from complicated to
simple and then becomes complicated again; the pore structure of the matrix also experi-
ences the same changes (Figure 6.18). Combined with previous research, the changes can
(a) 24 h 48 h 72 h 96 h 120 h 144 h
(b) DBS = 1.6909 DBS = 1.6722 DBS = 1.6709 DBS = 1.6994 DBS = 1.7185 DBS = 1.7279
Figure 6.17 Morphological changes of matrix-bacterial mixtures in the solid-state

fermentation process. (a) Morphological changes of matrix-bacterial mixtures in the
fermentation process. (b) Matrix-bacterial contours after digital imaging.
(Duan et al., 2012)
0.65 1.740
Biomass
Fractal dimension
0.60 1.725
Fractal dimension
Biomass (g/g)
0.55 1.710
0.50 1.695
0.45 1.680
0.40 1.665
24 36 48 60 72 84 96 108 120 132

Time (h)
Figure 6.18 Changes of matrix fractal dimension with cell growth in the solid-state
fermentation process.
(Duan, 2012)
Figure 6.19 Physical model of the morphological evolution of the matrix-bacterial complex in
the solid-state fermentation process.
(Duan, 2012)
be explained based on the growth of the microbial cells in the porous matrix (Figure 6.19).
At the beginning of cultivation, only a small amount of bacterial cells exist in the pores of
the porous cellulose matrix, the pore morphology is intact, and the overall structure of the
matrix is not significantly affected. With the continuous growth of bacterial cells, the inter-
nal pores of the matrix are occupied by bacterial cells and that results in porosity reduction
and decreasing fractal dimension, which happens in the log phase and the earlier part of the
stable phase. When the cell growth accesses the stable phase, further utilization of the
matrix destroys the overall structure and the matrix debris increases both the porosity
and the fractal dimension. Late in the stable phase, the bacterial cells secrete large amounts
of enzymes. The matrix is further degraded into smaller fragments and that further
increases porosity and the fractal dimension.
2. Establishment of bacterial growth and fractal dynamics model of bacteria-matrix.
The fractal dynamics model of the bacteria-matrix is established based on the above results.
As a logistic equation is the best simulation model for microbial growth, the model is applied
to simulate the growth of Penicillium decumbens. The model is as follows:

dX X
¼ mM X 1 (6.69)
dt XM
where:
X is the biomass in the solid matrix, g/g;
XM is the maximum biomass, g/g;
mM is the maximum specific growth rate, 1/h.
As the temperatures of the matrix and water activity are constant in the experiments, the
effects of variation of environmental factors on microbial growth are ignored in these
models. Based on the above analysis, it is assumed that an equal fractal dimension for
the whole bacterial cell-matrix layer is reasonable. The biomass at the inflection point of
fractal dimension is named Xg. When X < Xg, the relationship of DB with biomass variation
is approximately linear and is in accordance with the logistic equation as follows:

dDB DB X
¼ aM DB 1 ¼ k1 aM X 1 (6.70)
dt DBm XM
When X > Xg, as the bacterial cells are in a balanced state between growth and apoptosis, the
growth
variation of DB is affected by the and death of bacteria and the kinetic equation con-
tains a decreasing coefficient XXg 1 :

dDB DB X X
¼ bM DB 1 ¼ k2 bM 1 1 (6.71)
dt DBM Xg XM
In the equation, aM and bM represent the maximum specific reduction rate and the maximum
specific growth rate, respectively, DBm is the minimum fractal dimension at the inflection
point, DBM is the maximum fractal dimension of the fermentation process, and k1 and k2
are the equivalence factors of aM and bM, respectively. Derived by the following formula
to obtain the equation, these two equations directly reflect the variation of fractal dimension
with bacterial growth, wherein d and represent the equivalent reduction rate and equivalent
rate of increase of DB.
8
> dDB dX k1 aM dX d
>
> ¼ ¼ , DB > DBm
>
< dt dt mM dt mM

(6.72)
>
>
>
> dDB dX 1 1 k2 bM dX 1 1
: ¼ ¼ , DBm < DB < DBM
dt dt Xg X mM dt Xg X mM
The present study uses a minimum error method to calculate the model parameters of d, ,
and mM, and the initial values of XM, X0, Xg, and DB are needed for the calculation. The cal-
culation process is accomplished by using Matlab 7.1 programming. In this algorithm, the
approximate ranges of d, , and mM are confirmed first. The optimal parameters are calcu-
lated by repeating the cycles of the known range, and under these optimal parameters the
values of X and DB show the smallest deviation compared to the experimental values.
For the steam-exploded wheat straw-bran matrix in this research, the optimal d, , and
mM are –0.006, 0.17, and 0.0333, respectively. The errors of X and DB obtained from the
optimal parameters and the experimental values are 0.776% and 0.0932%, respectively.
The relatively good fit shows that the model established in this study is suitable for the pre-
diction of microbial growth and fractal dimension variation of the bacteria-matrix in this
fermentation system for steam-exploded wheat straw-bran (Figure 6.20).
6.3.5 Automatic control in the lignocellulose

biorefinery process
With the advance of modern industrialization processes, using automatic control to
replace manual operation is the trend to improve production efficiency and reduce
labor costs; and this also applies to the lignocellulose biorefinery process. There is
a variety of automatic control software on the market currently. This section intro-
duces the self-developed monitor and the control system for GDSSF based on the
MCGS (Monitor and Control Generated System) industrial control configuration
software (Kunlun Tongtai, China).
0.60 Figure 6.20 Comparison of

real values and fitted values
of matrix fractal dimension
0.56
and biomass.
(Duan, 2012)
R2 = 0.9984 (for biomass)
Biomass (g/g)
0.52
R2 = 0.9310 (for DB)
0.48
0.44 Fitted curve

Experiment result
0.40
1.66 1.67 1.68 1.69 1.70 1.71 1.72 1.73

Fractal dimension
6.3.5.1 Introduction to MCGS

MCGS is a Windows-based platform for rapid construction and generation of a PC
monitoring system that runs on Microsoft Windows 95/98/Me/NT/2000/2003,
Win7, and other operating systems. MCGS solves practical engineering problems,
providing a complete solution and developed platform, and is able to achieve data col-
lection, real-time and historical data processing, alarm, process control, trend curves
and report output, production monitoring, and other functions. MCGS has been suc-
cessfully applied in many fields, such as petrochemicals, with the advantages of good
visibility, maintainability, high performance, and high reliability.
MCGS includes a configuration environment and a running environment. In prac-
tice, the configuration environment is a complete set of configuration tools that helps
users to design and construct their own applications, while the running environment
completes the users’ configuration objectives and functions according to the project
designed by the users.
The project established in MCGS consists of a main window, a device window,
a user window, a real-time database, and an operating strategy. Each part has dif-
ferent characteristics and is operated separately. The main window, which is the
main frame of the project, is responsible for scheduling and managing the opening
and closing of the device window and user windows. The device window connects
and drives external devices. Data acquisition, output devices control, devices
driver registration, and data variables definition are accomplished in this window.
The user window is mainly used to set the human–computer interaction interface of
the project, for example to generate a variety of animation displays, alarm outputs,
and data and curve charts. The real-time database is a data exchange and proces-
sing center for each part of the project, connecting the various parts into an organic
complete project in MCGS. The different variables are defined within this window
for data acquisition, processing, output control, and so on. The operating strategy
achieves the process control of the project operation, including the preparation of
controlling programs and the selection of a variety of functional components, such
as data extraction, historical data curves, timers, and multimedia output.
For example, a controlling program script is shown as follows, which is similar to
Visual Basic.
F1.Value ¼ 0‘Turn off F1’
F3.Value ¼ 1‘Open F3’
FL.Value ¼ 0‘Turn off the fan’
T1.Value ¼ T1.Value + 1‘Timer’
IF T1.Value > 5 THEN
IF (T1.Value-5) > (TDY.Value * 60) THEN
T1.Value ¼ 0‘Timer return to 0’
STI.Value ¼ 2‘Entering next running stage’
ELSE‘Entering low-pressure running stage’
F1.Value ¼ 0
F2.Value ¼ 1
F3.Value ¼ 0
F4.Value ¼ 0
F5.Value ¼ 1
F6.Value ¼ 0
FL.Value ¼ 1
ENDIF
ENDIF
6.3.5.2 Automatic configuration control

After successful configuration, automatic control of the fermentation can be achieved
by running the configuration program. Figure 6.21 shows the automatic control inter-
face, in which the humidity, temperature, and pressure in the reactor are monitored
and displayed. In addition to these parameters, the operation stage and the
running time of this stage are shown, which is beneficial for controlling the fermen-
tation process.
6.3.5.3 Operation records and process analysis

Operation records could be generated to report the experiment and practice data.
Furthermore, the data could be output for further analysis to guide the subsequent
processes (Figure 6.22).
Figure 6.21 Automatic control interface.
Figure 6.22 Operation report interface.
6.4 System engineering and integration of lignocellulose

biorefining
Design is the soul of engineering construction, which is the bridge from scientific
research to industrial productivity. Bioprocess design refers to using drawings, tables,
and the necessary text to describe a biotechnology project, which is then completed by
the construction team. The biotechnology industry is an integration combining several
units in a systematic and reasonable way. Process design involves selecting the appro-
priate materials, determining the most economical and safe way of production, and
producing high quality products.
6.4.1 Concept design and preliminary evaluation

Concept design is the hypothetical design of industrial-scale production facilities from
the engineering point of view, based on the obtained research results (Douglas, 1994).
The aim of concept design is to find the existing problems in the basic research and to
provide guidance to the following pilot tests and simulation tests. Concept design
mainly includes the following aspects:
1. Design scale, operation time, production methods, basis of design.
2. Raw materials, products, catalyst, by-products, and other chemicals.
3. Device descriptions.
4. Process flow diagram and a simple instruction.
5. Mass and energy balance.
6. The results of equipment calculation, equipment inventory, and equipment design instructions.
7. Production control and instrumentation.
8. Analysis of consumption and workers’ arrangement.
9. Labor protection, health and safety, and the impact on the environment.
10. Investment and cost estimates, the payback period, and the major technical and economic
indicators.
11. Potential problems in industrialization and advice to process design, basic research, and
process development.
12. Diagram of major equipment and equipment layout diagram.
In brief, concept design is a summary and identification of the basic research. Design
and research is combined early through concept design, thus the existing problems in
the basic research can be found earlier and solved in a timely manner. Concept design
is conducive to using technical and economic points of view to guide the pilot study,
providing accurate information for process development. As concept design ensures
the integrity of basic research, it is helpful to prevent errors in the pilot test.
Therefore, concept design can shorten the development cycle and improve develop-
ment quality.
After concept design, a technical and economic assessment (i.e., a preliminary eval-
uation) is needed to evaluate the technology reliability and progressiveness and the eco-
nomic rationality to decide whether to continue the development (Chen & Wang, 2008).
In a preliminary evaluation, the payback period is generally the evaluated index of
the project. According to the “economic performance and technical evaluation” pro-
mulgated by the Ministry of Chemical Industry Planning Council, China, the payback
period of chemical industry projects is 2–4 years, and fine chemicals should take the
lower value. A large foreign company prescribed that the profitability of their chem-
ical industry projects should meet the following indicators:
l
Initial evaluation a return rate 50–100%
l
Middle evaluation a return rate 30–40%
l
Final evaluation a return rate 20%
An investment estimate is one of the main elements of a preliminary evaluation.

It can be achieved by a production-scale index method and a proportion method
(Chen, 2009).
6.4.2 Pilot test

The laboratory results are scientific and theoretical achievements through the explo-
ration of the objective world. Fundamentally speaking, it is still a form of hidden
knowledge productivity, which can form a true productivity through a pilot test.
In addition, there are many technical, market, and financial risks in the realization
process of the industrialization of scientific and technological achievements. Thus,
a pilot test is helpful to solve any problems in the basic development stage, laying
a foundation for industrialization. To conclude, the pilot test is a very important part
in the development process.
The necessity of a pilot test is shown in the following four aspects:
1. The data for materials circulation, accumulation of impurities, causticity, and the operation
of key equipment can only be obtained through a pilot test.
2. Only by the use of pilot test devices can the transfer of data be obtained.
3. Only in the pilot test can a certain volume of industrial products be produced to conduct
experiments and provide to users.
4. The equivalent of the mathematical model should be tested in the pilot test.
To establish the pilot plant, the following basic principles should be applied.
1. The scale of the pilot plant. The pilot scale depends on the properties for verification of the
model and the reactor and other key equipment requirements. Specifically, the following
questions need to be considered.
(A) The special characteristics of the reaction process.
The special characteristics of the reaction process decide the reactor type and the smal-
lest size of the test reactor, some examples are given below:
(i) The particle size of the catalyst in a gas-solid phase catalytic reactor should be the
same in both the pilot plant and the industrial plant. Only when the diameter and
length of the reactor are 30 times and 100 times more than the catalyst particle size
is the transfer process within the catalyst particles and in the catalyst bed similar to
the industrial process.
(ii) For the reaction involving bubbles, droplets, and particles, the size of distri-
bution holes, mesh, and injection holes in the pilot should be similar to industrial
installations, so as to ensure the transfer consistency within bubbles, droplets,
and particles. In addition, the pilot plant size should also meet the consistency
requirement of the transfer process outside the bubbles, the droplets, and the
particles.
(iii) The size and form of blender in the reactors, the import and export positions of the
reactors, and the stirring power per unit volume should be strictly similar in pilot
plants and industrial plants.
(iv) When tubes are used in industrial reactors, the pilot plant should also use tubes of
the same size.
(B) The pilot test equipment should meet the various requirements of the production process.
The pilot test scale should adapt to products application, the installation and control of
instruments, sampling and production safety, environmental protection evaluation, and
other aspects of requirements.
(C) The essential conditions of key equipment.
The pilot plant equipment should be suitable for the internal components (such as
blenders, heat transfer equipment, spray device, large lining, etc.) processing and
installations.
(D) The market demand.
It is necessary to develop the application and market for a new product. The pilot plant
should be able to produce a certain volume of products according to the market demand.
2. The completeness of the pilot plant. A complete chemical engineering process consists of pre-
treatment of raw materials, the chemical reaction process, separation and purification, and
materials recovery and recycling. The traditional pilot plant is a small production plant with
large investment and long experimental time. According to modern theories of chemical
process development, the pilot plant is not always needed to simulate the whole process of
industrial production. Sometimes only part of a pilot test is necessary. The necessity of con-
ducting a pilot test of the whole process should be assessed according to the following
principles.
(A) A whole process pilot test is necessary in the following situations:
(i) when conducting a comprehensive study on the whole production process based on
a small trial;
(ii) when a certain amount of samples need to be produced for an application test; and
(iii) when the effect of the materials cycle on production is unpredictable.
(B) It is necessary to conduct a pilot test for the chemical reaction and fermentation pro-
cesses because the reactor is the core of chemical process development. For distillation,
absorption, extraction and heat exchange, and pumps, the processes are relatively
mature, so it is unnecessary to conduct a pilot test.
(C) It is necessary to conduct a pilot test for the separation of new contents, new separation
methods, and new equipment.
(D) It is necessary to conduct a pilot test for the recycling process. If the one-way conversion
rate is low, a considerable number of materials need to be recovered. While impurities
in the process would accumulate, probably causing poisoning of the catalyst and micro-
organisms not growing, it may even lead to serious security incidents due to the accu-
mulation of explosive components. Therefore, the effect of the recycling process on
production needs to be studied in detail and a method to remove the impurities should
be researched. In addition, the detection and control points, the detection accuracy,
and the range in the pilot test should be respectively more, higher, and larger than in
practical production to enable detailed study of the process. The design of the pilot plant
should be convenient for observation and sampling to obtain the data for analysis.
To conclude, from the beginning of basic research and development, particular atten-
tion should be paid to the transfer process and the dynamics of data. When doing
experiments, it is necessary to identify the key parameter affecting the reaction pro-
cess and use it as the basis for enlarged-scale production. The key parameter is studied
as a key criterion in the pilot plant study, which will lead to improved efficiency.
6.4.3 Basic design and final evaluation

Basic design is the final result of chemical process development, and is the foundation
for engineering design. Basic design should include detailed data about key
technologies, which is helpful for the design department as they complete an engineer-
ing design that addresses the specific conditions of factory construction. Engineering
design is focused on a specific construction project with a specific site, which is a
rational combination of many products. However, basic design has no specific site
and a single product. In basic design, systems engineering theory is used combined
with engineering experience to conduct an optimized design to reduce fixed consump-
tion (especially energy), product costs, and total project investment so that the whole
process is optimal.
1. Design principles
(i) Technical and economic indicators. The payback period should be less than 2–4 years
while the investment profit margin should be greater than 15%.
(ii) The level of production reliability. That is, the allowance should be determined.
(iii) The range of production capacity. There are fluctuations in production capacity. Gen-
erally, the lowest operating load should be larger than 50% of the normal load.
(iv) The principle of material selection. Whether to use expensive corrosion-resistant
materials or cheap corrosion-tolerant materials depends on the corrosion-resistant
hierarchy of the entire process.
(v) The level of automation.
(vi) Tank storage time.
(vii) Standby equipment principles. The principle of standby equipment is that equipment
that rotates, or that rapidly wears, corrodes or cokes should have standby equipment.
(viii) The development plan.
2. Design content
(i) Annual operation time. When deciding annual operation time, the following factors
should be taken into consideration: media corrosion, coking and polymerization,
standby equipment, management, and the maturity level of techniques. The annual
operating hours are generally from 7000 h to 8200 h.
(ii) The purity of raw material. The purity of raw material is related to the prices, which
should be chosen reasonably.
(iii) Product quality. Product quality should meet the national standards or user needs.
(iv) Product yield and consumption of raw material. Consumption of raw materials
should be provided as an indicator. If it cannot meet the requirements, the process
or process parameters should be modified to reduce the consumption, until it is
eligible.
(v) The conditions in the handover area.That is, the temperature, pressure, and phase at the
edge of the handover area of raw materials/intermediate goods transported in the
pipelines.
(vi) Public works. Public works mainly include power, water, steam, compressed air, and
waste treatment.
3. Process and instruction

A process flow diagram should be drawn and explained.
4. Equipment and instruction
(i) The equipment selection and process calculation.
(ii) Equipment material selection.
(iii) Safety factors. Due to the design errors and production fluctuations that may exist, a
safety factor should be considered for the equipment.
(iv) Design temperature. Not only the normal operating temperature but also the maximum
and minimum temperatures may appear in case production fluctuations need to be
considered.
(v) Design pressure. The greatest possible pressure in various operating conditions should
be considered. Generally, design pressure is equal to 1.1 times the operating pressure.
Vacuum equipment should support the maximum pressure difference inside and
outside.
5. The piping and instrument diagram (PID) with control points

The pipeline flow and control program are shown in the PID. The main functions of the
PID are:
(i) To determine pipeline processes. According to the PID, to learn the operations and
check the pipes and valves;
(ii) To determine the diameter of pipelines;
(iii) To determine the control program;
(iv) To analyze the security and performance according to the pipeline process and control
program.
Finally, the technical and economic evaluation of the process development project can
be conducted according to the requirement of the feasibility study, which focuses on
the forecasted economic benefits (including investment recovery and profit potential
extent) to provide a basis for investment decision making:
1. Commercial feasibility study, focused on market demand and forecast.
2. Technical feasibility study, analyzing the advancement and reliability of the project.
3. Economic feasibility study, mainly analyzing the investment, profit, and risk.
4. Financial feasibility study, focused on finance.
5. Management feasibility study, focused on staff and human resources.
A feasibility study should mainly be focused on the construction progress, environ-

mental protection, and legal issues.
6.4.4 Technology system for lignocellulose biorefinery

process engineering
The globally recognized problem of waste of lignocellulose has attracted much
attention, but has not yet been solved with a comprehensive and effective approach.
Traditional chemical methods have been proven to neither help the economy nor fit
ecological engineering principles; therefore, only the progress of modern biotechnol-
ogy can be helpful. Bioconversion is not a problem for biologists; it is an inherent
part of the natural ecological cycle. However, using or emulating the natural ecolog-
ical processes is a low-efficiency and high-cost choice. Obviously, this is not just a
biological issue, but also an engineering problem. Technical and economic issues are
not often considered by theoretical scientists. Instead, they become the responsibility
of biochemical engineering scientists. Prof. Chen has an in-depth understanding of

the complete utilization of lignocellulose. The complete utilization of lignocellulose
is not a single technology, or just a single product, and you do not achieve the eco-
nomic benefits just by building a factory. Only in accordance with the principles of
ecological engineering, will complete utilization find its rightful place by incorpo-
ration into the system of ecological agriculture (Chen & Li, 2000).
The connotation of ecoindustry is different from that of the agricultural and sideline
products processing industry. Ecoindustry is a new and high-level biotechnology
industry. This is a high-level ecological agriculture, whose scale needs to be large,
but also needs high technology and high quality, emphasizing complete utilization
and economic efficiency. New products and technology systems need to be created
to realize straw bioconversion and complete utilization, with efficient, comprehen-
sive, and universal characteristics. Further research ideas are as follows:
1. SSF should be chosen as the main bioconversion technique. The main research should focus
on the SSF reactor and its new theory, such as momentum, quality, heat, transmission of
information, and biological reaction kinetics.
2. The SSF production of cellulase enzymes and the separation of coupling technologies of
other products are key breakthroughs in technology and cost. The specific technologies
are as follows: the fermentation and separation coupling method and the mathematical
model of cellulase during SSF, cellulose simultaneous saccharification and SSF, and the eth-
anol separation coupling method and its mathematical model.
3. The utilization of lignin and hemicellulose is the key to achieving complete utilization of
lignocellulose. The research into lignocellulose conversion should be strengthened to pro-
duce high value-added products, which would enable more progress in the utilization of
lignocellulose.
4. Strain selection is the basis of complete utilization. Therefore, the gene pool of
cellulose microorganisms and hemicellulose to ethanol fermentation should be built and
applied.
5. A large-scale industrial simulation plant should be established on the basis of the above sys-
tem and previous work. An ecoindustrial park of lignocellulose would achieve the pattern of
multichannel, multiproducts, and comprehensive utilization that is helpful for an economic
feasibility analysis.
6.4.5 Integration examples of lignocellulose biorefinery

process technology
Industrial lignocellulose biorefinery processes should be integrated. In summary,
based on the author’s work of more than 20 years in researching new processes,
developing new equipment, and integrating with existing conventional equipment,
a series of achievements in the field of lignocellulose biorefining have been obtained
and carried forward to industrialization. The following two representative cases are
selected to introduce the lignocellulose biorefinery process from a practical
engineering view.
6.4.5.1 Ecological industrial chain demonstration of enzymatic

hydrolysis and fermentation fuel
The major difficulties for the production of ethanol from lignocellulosic raw materials
are primarily technical and economic issues, including the following aspects:
1. It is difficult to realize the simultaneous utilization of cellulose, hemicellulose, and lignin
components with a single technology. Emphasis only on the use of cellulose, discarding
other components, will undoubtedly cause environmental pollution and resources waste.
2. Key technology breakthroughs are needed in the lignocellulose conversion process. For
example, the application of traditional acid pretreatment results in high costs and serious
environmental pollution. On the other hand, indiscriminate application of technology and
equipment of ethanol fermentation from starch results in high cost of ethanol due to high
dosage of cellulase and low ethanol conversion efficiency.
3. There are difficulties in technology integration and technical research. The economical and
high-efficiency conversion of straw is a systematic engineering problem due to the highly
complicated structure of the raw material and the shortage of appropriate techniques.
In order to achieve an ethanol production system economically, composition classi-

fication and oriented conversion, and the concept that each composition of raw mate-
rial can be converted efficiently, were proposed to realize the simultaneous conversion
to ethanol and other high-value co-products of agricultural residues.
Based on the concept of fractional conversion, a demonstration project with annual
straw ethanol output of 3000 tons has been successfully established in Dongping,
Shandong Province, China. This demonstration achieved the high-efficiency and
environmentally friendly production of ethanol by integrating the following technol-
ogies: steam explosion technology, GDSSF of cellulase, solid-state enzymatic hydro-
lysis coupled with liquid ethanol fermentation and CO2 gas stripping, and organic
fertilizer production technology using fermentation residue.
As shown in Figure 6.23, ethanol, organic fertilizer, and xylo-oligosaccharide
would be produced simultaneously. In this process, hemicellulose is separated from
straw and converted into high-value products instead of low-value or low-yield fuel
ethanol. Meanwhile, fermented residues enriched in lignin are further used for the
bioconversion to organic fertilizer. Lignin mainly acts as the inert support with slow
release characteristics to further enhance the practical application of bioorganic
fertilizer.
The major equipment of this demonstration project includes a 5 m3 steam explo-
sion tank, two 100 m3 GDD-SSF reactors, a 110 m3 solid-state simultaneous enzy-
matic hydrolysis, ethanol fermentation, and ethanol separation plant, and four
ethanol distillation towers (Chen and Qiu, 2007). The process operating results indi-
cated that the average yield of ethanol was more than 0.15 g/g dry straw, and the final
ethanol concentration, desorbed from activated carbon, was higher than 69.8%. The
overall production cost of the demonstration project is around 5900 RMB/t ethanol,
having an annual production of 3000 tons of bioethanol and simultaneous production
of 200 tons of xylo-oligosaccharides and 3000 tons of organic fertilizers.
Strain Corn stalks
Seed tank Oligoxylose

Steam explosion
SSF Membrane
Water extraction Liquid Decolorization
filtration
Solid phase simultaneous Solid

saccharification and
fermentation Dehydration Dry Mixed Compound fertilizer
Rectification Dehydration Ion exchange Ultrafiltration
Crystal
Dehydration
Dry
Bioethanol
Xylose
Figure 6.23 Multilevel conversion to ethanol using straw as feedstock.
6.4.5.2 Fractionally converting Pennisetum hydridum into fuel

ethanol with co-production of electricity and paper pulp
Fermentation conversion utilizing lignocellulose as raw material accords with the
principle of “no competition with humans for food stuff and no competition with food
stuff for soil” and is an attractive prospect for producing fuel ethanol. The advantage
of producing fuel ethanol by fermenting the lignocellulose raw material is obvious,
and furthermore, Pennisetum hydridum has been gradually recognized due to its
advantages of high lignocellulose accumulation, high thermal value, water and soil
maintainability, and the like.
P. hydridum is a high-quality fodder grass with high output and high protein that
was introduced from Colombia into China. It is referred to as “king grass,” “emperor
bamboo,” and “giant elephant grass.” It is a monocotyledon, belonging to the Poaceae
family, and Pennisetum genus. The yield of P. hydridum is high, and high-quality Poa-
ceae fodder grass is cultivated by hybridizing elephant grass with American Pennise-
tum. The P. hydridum growing straight in a cluster form is a tall plant, has an advanced
root system, and is a perennial plant in areas with adequate temperature. The plant has a
height up to 4–5 m and a length of 9–15 cm between joints; there are 15–30 effective
sprouts; and one axillary bud is grown on each joint and is encapsulated with leaves
with a length of 60–132 cm and a width of 3–6 cm. The planting of P. hydridum in the
areas of Guangdong Province, Guangxi Province and the like in China has the
advantages of fast growth, long harvest period, as well as a stable and high output.
P. hydridum can be harvested 2–3 months after being planted in spring and will
keep growing after harvesting. It can be harvested 4–6 times a year and can
be harvested for 6–7 years from one planting. The output per year for each hectare
is up to 375 tons.
The main chemical ingredients of P. hydridum include cellulose, hemicellulose,
and lignin, and these three ingredients constitute the supporting skeleton of the plant
body; wherein, the cellulose forms microfibers that constitute the net-like skeleton of
the cell walls of the plant, while the hemicellulose and lignin are the “adhesive” and
“filler” between the fibers. In P. hydridum, the total content of cellulose is 75% or
more, the content of Klason lignin is 20% or more, and ash comprises about 3%. Addi-
tionally, P. hydridum further comprises pectin substances, lipids and waxes, lipins,
low-molecular carbohydrates, and so on.
At present, the main application of P. hydridum in industry is as a high quality fodder
grass and a new raw material for feedstuffs, papermaking, and construction materials.
As raw materials for fodder grass, P. hydridum is the best succulence for phytophagous
livestock, fowl, and fishes. It has a large harvest yield per year and can be harvested for a
long period. However, when P. hydridum is used as feedstuff directly, it has the disad-
vantages of difficult absorption, poor palatability, and low added value. Chinese Inven-
tion Patents 200410040941.4 and 200610138365.6, respectively, introduce the methods
for producing protein feedstuffs by utilizing P. hydridum. As a raw material for paper-
making, P. hydridum is a fast-growing resource with great potential and good paper-
making performance. P. hydridum has the advantages of long fiber length, high
aspect ratio, good beatability, soft fibers, and relatively high tearing strength. It is suit-
able for preparing top-grade paper pulp and dissolved pulp, and can be used as raw mate-
rials for papermaking instead of wood and therefore saves on the country’s wood
requirements. A method for preparing bleached pulp by utilizing P. hydridum as the
raw material has been introduced. As a raw material for building material, Chinese
Invention Patents 200410016746.8 and 200610011006.4 separately introduce building
material boards (e.g. fiber boards, medium-density boards, molded board) with excel-
lent quality and low price, as well as various artworks, that can be manufactured by
utilizing P. hydridum.
However, the above applications of P. hydridum only aim at the utilization of
a single component in P. hydridum or utilization with low added value. For exam-
ple, as a papermaking raw material, only the cellulose in P. hydridum is utilized
and the other components such as hemicellulose and lignin are discharged as
papermaking waste liquid; therefore, not only the resource is wasted, but also
the environment is seriously polluted. Thus, to increase the added value of
P. hydridum, and conserve the resource, it is imperative to develop a processing
route for the comprehensive utilization of P. hydridum. Planting and managing
P. hydridum as an energy source crop will provide a new route for solving China’s
energy source problems.
Additionally, in recent years, a lignocellulose electricity generation technology
has rapidly developed. In countries such as Austria, Denmark, Finland, France,
Norway, Sweden, and America, lignocellulose has drawn more and more attention
for use as a fuel for electricity generation. In China, since 1987, research work on
biomass energy miniaturized gasification electricity generation technology has been
carried out, and is regarded as a key project by the Ministry of Science and Technol-
ogy. In 2000, a demonstration project for straw gasification electricity generation
was performed in China. However, because of the low thermal value, low density,
relatively widely dispersed raw materials, etc. of lignocellulose, electricity generation
using lignocellulose cannot make a breakthrough because of economic cost. There-
fore, in order to satisfy the national energy source demand and increase the compre-
hensive utilization value of P. hydridum, further in-depth research is needed on
producing fuel ethanol with co-production of a bio-based fuel for electricity genera-
tion by fermenting P. hydridum (Chen, 2014).
Strain Grow seedlings

P. hydridum
Cultivation
Seed Steam transportation
tank explosion
Liquid Membrane Oligo

Water Decolorization
filtration xylose
Cellulase by SSF
Solid phase
simultaneous
CO2 saccharification
and Dehydr
fermentation Residues Electricity generation
ation
Distillation Ion Ultrafiltration

Dehydration Crystal
exchange
Dry
Dehydration
Xylose
Bioethanol
Figure 6.24 Fractionally converting P. hydridum into fuel ethanol with co-production of
electricity generation and paper pulp.
In summary, the invention illustrated in Figure 6.24 has advantageous effects as

follows:
1. Because of the compact structure of P. hydridum, P. hydridum is subjected to a pretreatment
of steam explosion that increases the degree of fiber dispersion of P. hydridum greatly and
benefits the growth of microorganisms and the separation of the long and short fibers.
2. To overcome the previous disadvantage of a single product for P. hydridum, a full utilization
technology for P. hydridum is emphasized, which increases the utilization ratio of P. hydri-
dum and helps conserve the resource.
3. By producing fuel ethanol through P. hydridum fermentation with co-production of
other products with high added value (e.g. lignocellulose electricity generation, xylo-
oligosaccharide, paper pulp, alcohol-soluble lignin, recovered CO2, and others), the compre-
hensive utilization route for P. hydridum is optimized.
4. By overcoming the disadvantages of the pollution of traditional methods of component sep-
aration and single component utilization, a clean full utilization of P. hydridum is realized.
To conclude, this chapter began by describing the special heat and mass transfer laws
that apply to lignocellulose biorefinery process engineering, and used porous media
theory to explain the transfer of heat, water, and gas in the lignocellulose biorefinery
process. Then typical process units and equipment, as well as the rapidly developing
online monitoring technology and automatic control technology and its application in
the lignocellulose biorefinery process were introduced in detail. Subsequently, the dif-
ferent implementation phases of refining process were described, combined with the
flow of engineering design. Finally, two integration examples of lignocellulose bior-
efinery process technology and its application prospects were demonstrated.
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Integrated industrial lignocellulose
biorefinery chains 7
7.1 Overview
To achieve efficient conversion of lignocellulosic resources is a worldwide technolog-
ical problem. The current major investment in existing technologies presents hurdles
for the large-scale industrial application of lignocellulose. Through research on the
present technical global status as well as the main reasons for economic and technical
barriers, it has been concluded that the following three common problems exist in the
conversion and utilization of lignocellulosic resources. First is single component utili-
zation. A key reason for the slow industrialization of lignocellulosic feedstock produc-
tion is the lack of efficient technologies for separating each component. The complex
composition and high strength of lignocellulose biomass makes it difficult to separate
into useful molecular components. Overemphasis on the use of single components with-
out consideration of other components will inevitably result in a severe waste of
resources and environmental pollution. Second is the simple technology of lignocellu-
lose utilization. That is to say, in the research into lignocellulose conversion, there exist
problems of one-sided efforts on biological or thermochemical technologies and a lack
of the multilevel utilization concept of natural solid phase organic materials. Third, and
finally, is the lack of studies on systematic technology integration and ecological pro-
cess engineering. Existing treatments mostly continue to use conventional starch fer-
mentation and wood processing technologies, resulting in high cost of raw material
pretreatment, low conversion efficiency, and environmental pollution.
Therefore, it is necessary to follow the principles of clean production and sustainable
development, from the perspective of green chemistry and ecological processes
engineering systems, through integrating multiple technologies to acquire the effective
separation of lignocellulose components and then undergoing multiproducts-oriented
fractionation, consequently achieving the full utilization of lignocellulose. The full uti-
lization industry of lignocellulose biomass is a component separation-centered industry
where processing products from three major components, in which raw material refining
is core, and conversion technologies are the keys, and the formation of the whole indus-
try chain is the integration of the lignocellulose biorefinery process.
In this process, because the dense spatial structures of lignocellulose biomass mate-
rials make them difficult to use directly, feedstock pretreatment is a necessary means
to achieve efficient conversion of lignocellulose. However, from the perspective of the
full utilization of lignocellulose, the existing feedstock pretreatment technologies
focus on the hydrolysis and fermentation of cellulose, and the high-value utilization
of hemicelluloses and lignin is rarely considered. Breaking through the economic and
technical barriers and establishing an effective multicomponent separation-integrated
refining industry chain is very important. The component separation of natural
lignocellulosic feedstock means that in refining natural lignocellulosic feedstock,

these materials are not only regarded as cellulose resources, but are also used as multi-
component materials. Natural lignocellulosic raw materials should be refined into sev-
eral components with a certain degree of purity, and these components should be
processed into valuable products, so as to establish the new concept of component
fractionation and comprehensive utilization.
Component fractionation and oriented conversion is the further enhancement of
raw materials pretreatment. It has not only been a pretreatment method, but is a
resource allocation process for the macromolecular components in lignocellulosic
feedstock, which helps to achieve the separate conversion of cellulose, hemicellu-
loses, and lignin. It is the most important high-value lignocellulose utilization idea
and has seen significant progress both domestically and abroad. However, simple reli-
ance on the above idea makes it still difficult to break through the economic and tech-
nical problems to large-scale, clean, and highly-efficient conversion of lignocellulose
as an industrial material. Thus, to become universal biological and chemical raw mate-
rials, lignocellulosic resources must be developed to exploit the refining process and
technology for the functional high-value utilization of lignocellulose while maintain-
ing its original structure, thereby forming a lignocellulosic resources refining industry
chain featuring lignocellulose characteristics.
Prof. Chen, based on the structural characteristics of the raw materials and the
requirements of the target products, has promoted pretreatment-component fraction-
ation to the multiproduct-oriented fractionation according to the product functional
requirements. The purpose of this process is not only to obtain several products,
but also to achieve the goals of minimized energy consumption, optimized efficiency,
maximized value, and clean conversion, for the purpose of making lignocellulose the
main material for the next generation of the biological and chemical engineering
industry. This process is achieved by choosing the right production route as well as
integration of efficient technologies, which results in the fractionation of components
and maximized use of whole materials to obtain major products and valuable by-
products, in order to achieve the full utilization of lignocellulose. In fact, finding a
suitable production process and taking the waste generated from production as mate-
rials for other aspects, is the reflection of the recycling economy and ecological engi-
neering in the lignocellulose industry. Lignocellulose biorefining, conversion, and
process engineering have been discussed in preceding chapters, the current chapter
therefore mainly focuses on integrated industrial refining modes for lignocellulose
based on the above ideas.
7.2 Biorefinery modes for herbaceous plants

7.2.1 Integrated industrial chain modes for agricultural straw
biorefining
With the development of society, the conflicts between population growth, economic
growth, and a shortage of energy and resources have become increasingly prominent.
Meanwhile, environmental pollution has become a serious threat to the sustainable
Integrated industrial lignocellulose biorefinery chains 221
development of human society. For a long time, fossil resources (coal, oil, natural gas)
have been the major driving force for social development. More than 80% of primary
energy is acquired from fossil resources. However, petrochemical resources are non-
renewable resources. With population growth and industrial development, the huge
demand for energy accelerates the large-scale exploitation and consumption of various
resources, gradually weakening and degrading the precious nonrenewable resources.
Meanwhile, the exploitation and utilization of fossil resources causes serious environ-
mental pollution and irreversible ecological damage. For the sustainable development of
human society, this excessive dependence on nonrenewable resources for energy must
be radically changed. Gradually substituting renewable resources for nonrenewable
resources is the only way to achieve sustainable development of human society.
Lignocellulose is the most important renewable resource and is also a solar energy
converter and storer. Plant biomass is synthesized by plant photosynthesis from solar
energy, water, and carbon dioxide, including wood, straw, and water plants. The
worldwide production of plant biomass each year has been up to one trillion tons,
enough to supply the needs of a population of 150 billion, which is far higher than
the current world population. However, according to rough statistics, currently
89% of the world’s plant biomass resources are not exploited; only 11% is used for
agricultural products, animal feed, paper, and building materials.
Straw is an important part of plant biomass, and accounts for more than half of the
raw material annual production, which is a great renewable resource. The term straw
specifically refers to inedible roots, stems, leaves, and other waste in the crop residues.
Its chemical composition is an organic mixture of cellulose, hemicellulose, and lignin
together, which is mainly composed of carbon, oxygen, hydrogen, but also small
amounts of nitrogen, sulfur, phosphorus, potassium, and other elements. A very
important characteristic of the straw itself is heterogeneity (Chen et al., 2011), which
limits the full use of lignocellulose by a single technology. Take corn stalk, for exam-
ple. Corn stalk consists of leaves, cortex, pith, and other component parts, reflecting
the heterogeneity of each part as well as the heterogeneity of the composition in var-
ious parts. There follows an analysis of the structure and composition of corn stover,
fully reflecting the heterogeneity of the different structural levels.
7.2.1.1 Characteristics of corn stalk

In gramineous plants, corn stalk is thick and strong; it is about 0.8–3 m long and
2–4.5 cm wide (diameter) with obvious nodes and internodes. An acre of soil can pro-
duce 400–500 kg of dry corn stalks. Corn stalks are composed mainly of leaves and
stems, the latter consisting of cortex and pith. Large amounts of pith in the stem is one
of the characteristics of corn stalks. The leaf, cortex, and pith contents in the total
weight of stalks are 40%, 35%, and 15%, respectively.
Corn stalks have nutritional value in both immature and mature periods. In mature
corn stalks, the leaves contain the greatest amount of crude protein, followed by the tassels
and stalks, with the lowest amount in the bracts. For crude fiber, bark has the maximum
content, pith has a lower content and the minimum occurs in the leaves. For crude fat, the
leaves have the highest amount and the tassels the lowest amounts. The nutritional value
of the different parts is, from highest to lowest, in the order: leaves, tassels, stalks, bracts.
In the stems, the bark accounts for 64.8% and the pith is 35.2% according to weight.
The protein content of straw is very low (generally between 2% and 4% for mass ratio)
and the composition of amino acids is inconsistent, so the direct application of straws
as a feedstuff for ruminants leads to low nutritional values. After fermentation of corn
stalk, it can be used as a protein source to feed to rats and rabbits. A toxicological and
nutritional value analyses showed that the fermented corn stalk was safe, with the
crude protein being digested and the residual crude fiber being difficult to digest.
Therefore, it is suitable as a partial substitute for crude protein for ruminants.
Leaf accounts for 40% of corn stalk by weight and the amount of fibers is 30%; the
leaves are narrow, have a relatively large surface area, a smooth waxy layer on the sur-
face, low mechanical strength, and easily form a powder on crushing. Therefore, leaf is
not suitable for use as a raw material for man-made board and pulp production. Com-
pared with the whole stalk, leaf has no significant differences in nutritional value, and
some nutritional indicators are even higher than other parts.
The mass ratio of pith is 15% and the fiber content is 20%. Pith is composed of
parenchyma and vascular bundles scattered among the parenchyma. It is fluffy and
soft and has low density, strong absorbance, and low mechanical strength. Leaves
and pith account for more than 55% of corn stalk. Owing to the above features, pith
is not suitable for producing wood-based panels and paper. However, its fluffy and
soft texture makes it suitable for the production of packaging materials for vegetables,
eggs, ceramics, glass, etc.
The thickness of the rind of corn stalk is about 0.04 mm, mass ratio is about 35%,
and the fiber content is 50%. Rind is the best part of the corn stalk in terms of mechan-
ical strength. Its morphological fiber structure is similar to that of bagasse and cotton
stalk, which makes it a better raw material for man-made panels and paper. Medium
density particleboard produced from the cortex of corn stalk can meet the class A
national standard. Because the rind is a relatively small part of the corn stalk content,
exclusive utilization of the rind with the abandonment of other parts of the corn stalk
would lead to a rising cost of raw materials.
Therefore, either in the different parts of the stalk or in the same part, the physical
properties and the chemical compositions of corn stalk vary widely, as does their nutri-
tional value. Moreover, the three major components (cellulose, hemicellulose, and
lignin) are cross-linked closely together in untreated corn stalk, resulting in the natural
biomass recalcitrance (Himmel, 2009). The complex structural characteristics make
the stalk difficult to use directly. Therefore, the condensed structure must be destroyed
or changed partially by pretreatments in order to achieve the combined result of the
application of the main components and the conversion of other components, conse-
quently improving the high-value utilization of corn stalk.
7.2.1.2 Utilization patterns of corn stalk and existing problems

As previously noted, the main components of straw and other lignocellulosic feed-
stocks are cellulose, hemicellulose, and lignin. Lignin itself is a widely used chemical
raw material, and cellulose and hemicellulose can be directly converted to produce
furfural, organic acids, and other chemical products, as well as paper. Through hydro-
lysis, cellulose and hemicellulose can be converted into glucose, xylose, and other
fermentable sugars, producing many kinds of bio-based products. Figure 7.1 shows a
classification of products according to the utilization patterns of corn stalks. However,
in the processing of lignocellulosic feedstock, people often use a single technology or
only one component with other components being ignored, resulting in material waste
and environmental pollution, such as the tar problem in the gasification of corn stalk,
the generation of acidic substances during pyrolysis, the mechanical barrier of lignin
in the enzymatic hydrolysis of fibers, the ineffectivness of cellulase adsorption, and so
on. On the one hand, this is attributed to the lack of a proper and effective fractionation
method for corn stalk and other lignocellulosic feedstock. On the other hand, the con-
version technology is both singular and simple, leading to the above problems already
noted. Due to the deficiency of the concept of multilevel utilization, biological or
chemical methods cannot obtain the whole corn stalk or the simultaneous utilization
of its three major components. A major expansion is needed in process engineering
theory applied to solid phase materials to drive a breakthrough in the key processes
during the conversion of corn stalks. Furthermore, in the important area of bioconver-
sion of lignocellulosic feedstock for fuels, technical breakthroughs in the critical pro-
cess, integration, and optimization of key technologies are needed. In the area of raw
material pretreatment, the use of a contaminated technique in the paper industry (i.e. a
technique that produces dust pollution and the wet method of de-pithing which pro-
duces waste water) and the conventional technique of acid hydrolysis leads to high
costs and environmental pollution. In cellulase and alcoholic fermentation, the tradi-
tional technologies and process of alcoholic fermentation from starch result in a large
amount of cellulase, low alcohol conversion efficiency, high investment costs, and
high direct production costs for the alcohol.
In the light of the heterogeneity of corn stalk composition and the abovementioned
problems in the utilization process, Prof. Chen established a multiproduct-oriented
fractionation process and multilevel utilization patterns based on steam explosion
Corn
stalks
Industrial chemicals
Husbandry Energy Materials
and biological products
Feedstuff Returning Other Solid fuel Liquid fuel Gas fuel Hydro- Building
to field carbons materials
Alcohols Straw
Fertilizer Molding Methanol Methane Aldehydes products
Ketones
Soil conditioner Carboni- Ethanol Hydrogen Esters Paper

zation making
Bio-oil Dimethyl Citric acid

ether
Biodiesel Syngas Lactic acid
Synthetic Xylitol
gasoline
Figure 7.1 Corn stalk utilization modes.

and solid fermentation technologies (Chen, 2009; Chen and Li, 2003; Chen and Liu,
2007). Based on a foundation of decades of research, the production of several kinds of
products from corn stalks has been realized, including paper, oligosaccharides, lignin
polymer materials, and new biodegradable fiber materials. The example below
describes a production line processing 300,000 tons of straw per year.
7.2.1.3 An industrial production line for straw refining with a

capacity of 300,000 tons/year
A 300,000 tons/year industrial production line for straw refining was established in
September 2010 by Songyuan Laihe Chemical Co. Ltd in Jilin Province, China. Song-
yuan Laihe Chemical Co. Ltd is a private enterprise in China focused on the research
and utilization of agricultural wastes. Since 2007, the company began technical coop-
eration with the Institute of Process Engineering, Chinese Academy of Sciences. They
established a demonstration project for the fermentation of straw hemicellulose to pro-
duce butanol and its utilization technology. In this project, a pilot plant of 600 tons/
year was approved following expert appraisal in October 2009, with the claim that the
entire technology and equipment represented an international advance. The demon-
stration project, based on the structural properties of the materials, involved the multi-
level conversion of cellulose, the fermentation of hemicelluloses for butanol
production, and the high-value utilization of lignin. The process route is shown in
Figure 7.2. The technical characteristic of the route is the maximum utilization of cel-
lulose and hemicelluloses of corn stalks for butanol fermentation, in order to improve
the utilization of straw as a fermentation substrate. After grading of fibers, short fibers
can be used as fermentation substrate or can be liquefied to prepare polyether polyol
and polyurethane, and long fibers can be used in the preparation of microcrystalline
cellulose and dissolving pulp, increasing the added value of the straw fiber products.
After alkaline extraction, the lignin obtained may be used as a raw material for carbon
fiber, phenol resin, and other high-end products. The major types of products are
shown in Figure 7.3.
The butanol fermentation process of hemicelluloses and the comprehensive utili-
zation of cellulose and lignin is shown in Figure 7.4 and is described as follows:
1. Pretreatment process. After steam explosion, the corn stalks were put into the hydrolysis
tank, and then 0.3–0.5% of the dilute sulfuric acid was added with the solid-to-liquid ratio
controlled at 1:5 to 1:7. Then materials were hydrolyzed at 110–120 C for 0.5–1 h. After the
hydrolysis, a screw extruder was used to separate the liquid fraction and solid fraction of
hydrolyzed materials to obtain the hydrolysis residues and hydrolysis liquid.
2. Butanol fermentation of hydrolysis liquid. Hydrolysis liquid was first filtered to eliminate
large particles, and then distilled in a vacuum tower for the removal of furfural. The acid
ions in the condensed liquid obtained were removed via electrodialysis, and then the liquid
was added to activated carbon to remove the fermentation inhibitors. The liquid was mixed
with a certain amount of corn juice and sterilized at 120 C for 40–60 min, then cooled and
conveyed to the fermentation tank. In the fermentation tank, the substrate was inoculated
with domesticated strains and fermented at 35–40 C for 40 h. Finally, butanol, acetone,
and ethanol were produced through the subsequent differential distillation and rectification.
Corn straw
Steam explosion
Hydrolysis liquid Solid residues
Activated carbon
Lignin extraction
adsorption
Fermentation Solid residues Lignin liquid
Distillation Butanol Cellulose Lignin
Acetone
Distillation
Ethanol
Wastewater
treatment
Marsh gas Water recovery
Figure 7.2 Straw biorefining industrial production route.
H2, CO2
Butanol
Hemicellulose
Corn straw Acetone
Ethanol
Special lignin
Corn straw Lignin Carbon nanofibers

Phenolic resin
adhesive
Phenolic resin
Rubber reinforcer
Cellulose Paper pulp
Polyether polyol
Sodium
carboxymethyl
cellulose
Figure 7.3 Product of the straw biorefining.

Steam explosion
Corn
straw
Short fibers
Hydrolysis tank
Pulverizer Wash tank
Extraction
Condenser solids
Alkali Carding
Furfural Long fibers
extraction machine
tank
Decompression
distillation device
Extraction
NaOH solution
NaOH solution liquids
Decompression Ultrafiltration
membrane
distillation tower
Agitation tank Electrodialysis
Activated carbon adsorption Acid

Furfural
Drying machine Centrifuge Blender
Sewage plant Waste liquor
Butanol, acetone, ethanol
Differential Butanol Acetone Ethanol

distillation tower tower tower tower
Figure 7.4 Process flow diagram of butanol production by corn straw hemicellulose fermentation and comprehensive utilization of cellulose and
lignin.
3. Separation of cellulose and lignin. Hydrolysis residues were put into an alkali extraction
tank and 0.5–2% sodium hydroxide solution was added with five- to sevenfold mass of
the hydrolysis residues. The mixture was kept at a temperature of 150–160 C for 2–3 h.
After cooling to the ambient temperature, the mixture was separated through a plate-and-
frame filter press to obtain extracts and extracted solids. The extracts were filtered by ultra-
filtration and then a nanofiltration membrane system to obtain two liquids. The liquid
throughout the nanofiltration membrane was sodium hydroxide solution, which could be
recycled into the extraction tank; the liquid that had not gone through the ultrafiltration mem-
brane was conveyed into the neutralization tank. Sulfuric acid was added in the neutraliza-
tion tank to adjust the pH to 4.5–5.0, followed by centrifugation. The clear liquid was sent to
a sewage plant, and the solid was washed with a threefold volume of water and centrifuged
again. The residual solid was dried to obtain high-purity lignin. The concentrated liquid after
membrane separation was dried to obtain lignin. The extracted solids were conveyed to the
sieving machine and separated into long and short fibers. Long fibers were used to prepare
dissolving pulp, and short fibers were used for butanol fermentation or liquefied to prepare
polyether polyol.
Mass balance was calculated using the following parameters. Corn stalk was calcu-
lated as absolute dry material, the ratio of butanol to acetone to ethanol in fermentation
liquid was 7:2:1, the material loss after electrodialysis and active carbon treatment was
5%, the ratio of corn stalk to hydrolysis liquid was 1:10, the butanol yield from Clos-
tridium acetobutylicum fermentation was 0.35 g/g, the material loss after alkali
extraction was 5%, the lignin yield was 80%, and the cellulose yield was 70%. The
mass balance of the whole process is shown in Figure 7.5.
NaOH
267 t
Extract liquor Lignin

1600 t 1280 t
Solid content
5052 t Long fiber
1280 t
Resudues
3200 t
Short fiber
1280 t
Corn straw
Steam explosion
7620 t
Butanol
600 t
Distillate Xylose Acetone
residual liquid 2340 t 171 t
Hydrolysis Ethanol
liquid Corn 86 t
223 t
Hydrogen
43 t
Distillate Furfural
Carbon dioxide
600 t
Sulfuric acid
70 t
Figure 7.5 Material balance of the butanol production process from corn straw hemicellulose
fermentation and comprehensive utilization of cellulose and lignin.
In summary, the 300,000 tons/year straw refining industrial production line is a

multiproduct, recycling, and high-value utilization route for corn stalks, in which
butanol, acetone, and ethanol are produced by the fermentation of hemicelluloses,
long fibers are used for paper making, and short fibers and lignin are used to prepare
polyether, phenolic resins, and other products. A variety of bio-based products
obtained by this route can be applied in the energy, plastics, materials, and chemical
industries, and so on, providing a new pathway for the high-value utilization of corn
stalk resources. In 2009, the 300,000 tons/year straw refining industrial production
line was established in Jilin Province. The annual design capacity was 50,000 tons
of butanol, acetone, and ethanol; 30,000 tons of high-purity lignin; and 120,000 tons
of cellulose. Taking the lignin and cellulose obtained as raw materials, a production
line for 50,000 tons of biopolyether polyols and 20,000 tons of phenolic resin will
soon be put into operation. After commissioning, the project can generate an annual
income of 1.2 billion yuan and a profit of about 100 million yuan. Currently, the oper-
ation of a 300,000 tons/year straw refining industrial production line marks the break-
through in overcoming several technical problems in butanol fermentation and
comprehensive utilization of straws, achieving validation of the industrial technology.
Technologies in this route have completely independent intellectual property rights. It
is the first low-cost, high-value, large-scale biorefinery production line for straw feed-
stock at an international level.
7.2.2 Integrated industrial chain modes of bamboo biorefining

Bamboo is one of the most primitive subfamilies of Gramineae and also has the most
diverse populations. It is characterized by a ligneous stem, a well-developed root sys-
tem, and it seldom blooms, which distinguishes it from other plants in the same family.
There are around 150 known genera, 1225 kinds in the world, and the plant area is
about 14 million ha. It is mainly concentrated in the vast region between the south
and north tropics (Jin and Chen, 2006).
The main components of bamboo include cellulose, hemicellulose, and lignin, in
which the content of holocellulose (cellulose and hemicellulose) accounts for about
65%, lignin and pectin constitute 32%, and ash content is about 3%. Due to the high
content and good performance of cellulose, bamboo is widely used in the processing
of bamboo fiber. Bamboo fiber is divided into natural bamboo fiber and recycled bam-
boo fiber. Natural bamboo fiber is directly separated from bamboo by a special pro-
cess. The process is usually dependent on the different spinning systems, sawing
bamboo to the required length in production, and removing lignin, pentosan, bamboo
powder, pectin, and other impurities in order to extract natural bamboo fiber from
bamboo. This kind of fiber is distinguished from bamboo pulp viscose fiber produced
by chemical treatments. The former is a pure natural fiber, a green and environmen-
tally friendly fiber with good cellulose performance. It has exceptional style, excellent
wearability, and significant health benefits. For bamboo pulp viscose fiber, some
excellent performance and health components in the bamboo fiber can be affected
by the chemical processing. Combined with the pollution in its chemical processing,
bamboo pulp viscose fiber is really not an environmentally friendly fiber. The natural
bamboo fiber using natural bamboo as a raw material is a green fiber that keeps the
natural characteristics of the original bamboo.
The microstructure of natural bamboo fiber is similar to hemp fiber with high fiber
strength. Natural bamboo fiber for coats is directly separated from bamboo through a
unique process and processed into fabrics. Clothes made from natural bamboo fiber
are comfortable to wear, have excellent dyeing properties, and exhibit gorgeous gloss.
Such unique qualities provide broad application prospects for natural bamboo fiber
in the textile industry. Natural bamboo fiber has the following general characteristics.
(1) The softness and warmth of silk. The fiber is shiny with drapability and abrasion
resistance. (2) Good hygroscopicity and breathability. Natural bamboo fiber is hollow,
experts call it the “breathing” fiber. And this good breathability meets the demand for
natural, cool fabrics. (3) Natural health protection. Natural bamboo fiber contains pec-
tin components, which are beneficial to skin health. Natural bamboo fiber also has
good antibacterial properties. (4) Good environmental performance. It is a nonpollut-
ing, environmentally friendly fiber. (5) It has good restorability and dyeing ability, and
is machine washable and does not need ironing.
Currently, bamboo is mainly used in agriculture, handicrafts, construction, wood-
based panels, paper, and bamboo charcoal processing. Its applications in agriculture,
handicrafts, man-made board, and so on still mostly rely on traditional processing
methods. Its processing level is limited, resulting in low value-added products and
the serious waste of resources. Domestic and foreign enterprises are now using the
viscose fiber production process to produce bamboo fiber, which is in line with the
production process of linters and wood pulp as raw materials. The process is shown
in Figure 7.6. Papermaking from bamboo is limited to the use of its cellulose, wherein
its hemicellulose and lignin are emitted in the form of black liquor. This process does
not take the comprehensive utilization of bamboo into consideration, leading not only
to serious pollution of the environment but also waste of resources. Therefore,
research and development of an efficient utilization technology for bamboo has broad
prospects.
In order to achieve environment-friendly, high-value utilization of bamboo,
Prof. Chen developed a new process for comprehensive utilization of all the components
in bamboo, on the basis of its specific structural characteristics. In this process, natural
bamboo fiber is produced as the major target product; meanwhile, xylo-oligosaccharide,
pulp, ethanol, alcohol soluble lignin and residues for biomass power generation
Bamboo Pulp Crush and Alkalization Sulfonation Dissolution

soak
First Second Filtration before Spinning

Ripening
filtration filtration spinning
Drying and
Plasticization Wash Cutting Refining
packing
Figure 7.6 Bamboo fiber production process.
are simultaneously produced, to realize the maximum utilization of all the separated
components and overcome the shortcomings of environmental pollution and single-
component utilization of the traditional production process. The concrete steps in this
process are as follows: the steam-exploded bamboo was firstly degummed by a cook-
ing treatment; after filtration, the obtained cooking liquor was used to produce xylo-
oligosaccharide, the bamboo fibers after steam explosion and cooking treatment
become disperse and fully exposed. These fibers are separated into long fibers (fiber
length is over 3 cm) and short fibers (fiber length is below 3 cm) for further utilization.
Then short fibers are screened through 30 mesh and 60 mesh. The short fibers not
passing through the 60 mesh are fermented to produce ethanol and others are used
for auto-catalyzed ethanol-water pulping. The long fibers are used in the subsequent
pulping and natural-bamboo-fiber-producing process. In this process, the multi-
production of natural bamboo fibers, bamboo pulp, ethanol, alcohol soluble lignin,
xylo-oligosaccharide and residues for biomass power generation are realized with
the aim of achieving efficient and comprehensive utilization of the bamboo resource.
The production route of this process is shown in Figure 7.7. It has the following advan-
tages: (1) According to the tight structural features, bamboo is pretreated by steam
explosion to increase the degree of dispersion of fibers, which benefits fiber separation.
(2) To overcome the shortcomings of single-component utilization of bamboo in the
traditional process, this process focuses on the comprehensive utilization of all the
components in bamboo to greatly improve the utilization efficiency of bamboo and
conserve the bamboo resource. (3) The production of xylo-oligosaccharide, bamboo
pulp, ethanol, alcohol soluble lignin and biomass fuels for power generation is coupled
with the production process of natural bamboo fibers, which optimizes the comprehen-
sive utilization route of bamboo resource and results in no waste discharge in the pro-
duction process. (4) This method overcomes the pollution and single-component
utilization problems in the traditional process to realize the clean and comprehensive
utilization of the bamboo resource.
Steam
explosion
Xylo-
oligosaccharide
Water washing Hydrolysate Oligo-

for degumming liquid /monosaccharides
Solids
Grading of long Simultaneous saccharification Fermentation Electricity

Short fibers Fuel
and short fibers and fermentation for ethanol residues generation
Ethanol Residues
Long fibers
Bamboo
pulp
Bleaching and Short fibers Auto-catalyzed ethanol-
Carding
softening after carding water pulping
Alcohol soluble
lignin
Natural Textile
Long fibers
bamboo fiber manufacturing
Figure 7.7 Process route for comprehensive utilization of bamboo.

7.2.3 Integrated industrial chain modes for hemp biorefining

Hemp and its products have very unique advantages and the comprehensive utilization
of hemp has achieved a breakthrough using advanced technologies in which hemp is
processed by steam explosion and then used for textiles, resulting in high-valued
by-products and in line with the circular economy. Hemp is a featured resource in
Liu’an, Anhui Province, China. The Institute of Process Engineering, Chinese Acad-
emy of Science, developed the extensive processing of hemp, achieved more than
20 patents centered on steam explosion, and combined hemp resource advantages with
high-tech processes to produce sizable economic and social benefits. The extensive
processing of hemp is in accordance with national industrial policy.
Hemp cultivation formed its peak at the beginning of the 1980s, the total cultivated
area was 150,000 ha., and has been stable at 170,000–180,000 ha. since the 1990s.
Because extensive processing technologies of hemp have had no breakthroughs
and multichannel use is not implemented, the planting area is shrinking, and the eco-
nomic efficiency of hemp is poor.
Utilization of hemp is mainly concerned with the fiber. Hemp is traditionally used
for making ropes, sacks, and linen. In the 1980s, many companies tried to explore
ways to use hemp fiber, especially degumming technology research from chemical
degumming to biological degumming, and made some progress. But the high cost
of degumming and pollution problems have still not been solved.
Steam explosion processing leads to the break down of hemicellulose and lignin as
well as rearrangement of cellulose hydrogen bonds under certain pressure conditions,
resulting in production of materials with new properties. The basic technical route is as
follows: raw hemp is harvested by farmers and is first steam-exploded to separate peel
fibers and stalk fibers; after water extraction the peel fibers go through a finishing pro-
cess; the liquid is extracted to get xylo-oligosaccharides, and the pectins obtained from
stalk fibers and peel fibers after water extraction are once again steam-exploded to
produce ecological fiberboard and organic fertilizers. In this way, raw hemp is pro-
cessed without any additional chemical reagents to obtain five products, also with
no waste emissions. The integrated development process for hemp is shown in
Figure 7.8.
7.2.3.1 Steam explosion degumming of hemp fiber

The development of hemp fiber has been stagnated by traditional chemical degum-
ming methods which cause environmental pollution and have seriously affected the
development of the hemp textile industry. Research into microbial degumming has
been conducted since the 1950s; progress has been made in the microbial degumming
of hemp peel but the processes still cannot meet the requirements of industrial produc-
tion. The methods have low degumming efficiency and high processing costs, and a
new technical breakthrough is awaited.
Steam explosion aims to solve the above problems. It partially degrades hemp
hemicelluloses and lignin, then the hemp fibers obtained are bleached by hydrogen
peroxide to prepare degummed hemp for further carding and processing into pure
Hemp
Steam
explosion
Washing Steam
and Peel from
separation stem explosion
Water Hot
extract Fiber Bark Crushed pressing
particles
Purification Bleaching Steam

explosion
Xylo- Organic
oligosaccharide Fine fiber fertilizer Eco-board
Figure 7.8 Process route of comprehensive utilization of hemp fiber.
yarn. Steam explosion treatment first degrades 80% of the hemicellulose and pectin,
not only providing the necessary nutrients for microbial fermentation, but also
destroying the natural structure of hemp; this is conducive to the removal of gums
by enzymatic hydrolysis and to achieve hemp degumming. It provides a new, clean
degumming method preventing the contamination caused by chemical methods,
and also overcomes the disadvantages of the high cost and low efficiency of enzymatic
degumming.
7.2.3.2 Steam explosion treatment of hemp fiber to produce

ecological board
The forest cover in the world is decreasing and wood resources are experiencing seri-
ous shortages. More attention is centered on straw as a substitute for parts of trees, but
recently farmers have tended to burn straw, which wastes resources, pollutes the envi-
ronment, and poses a threat to aviation safety. Thus, how to make comprehensive use
of straw has become a prominent resource utilization and environmental protection
problem. Comprehensive development and utilization of straw solves problems for
farmers, adds new resources for the building materials and decorating industries, con-
tributes to environmental protection, and helps aviation safety.
At present, the utilization process for straw requires thermosetting resins and form-
aldehyde in order to produce green wall materials, fiberboard, packaging materials,
disposable cutlery boxes, nursery products, and so on. In this process, the addition
of sizing material accounts for a large proportion of total production costs (60%),
making it difficult to compete with plastics and other decorative materials in terms of
technical and economic factors, and it can easily pollute the environment. Therefore,
ecofriendly hemp material without the addition of sizing material is attractive for tech-
nical and economic reasons. Not adding the sizing material simplifies the whole pro-
duction process, saves the gum mixing step and related equipment, and reduces
production costs. The produced material is completely biodegradable, so there is
no environmental pollution.
Based on the similarities and differences between straw and wood in terms of
chemical composition and structure, Prof. Chen has proposed a new concept of mod-
ified straw and has developed new technology using modified fibers to produce eco-
friendly materials (Chen and Li, 2001). Modified straw refers to straw with its natural
structure and properties altered by physical, chemical, and biological methods. Hemi-
celluloses and lignin are degraded and converted, and the hydrogen bonds in cellulose
are rearranged, all creating straw materials with new properties that are easily pro-
cessed into various products. For instance, in the steam explosion process, the active
groups of straw lignin are greatly increased, which makes the lignin have similar char-
acteristics to polyhydric phenols and able to be used as natural binders; hemicellulose
is degraded into soluble sugars, dehydrated carbohydrates, and furfurals, which can
replace formaldehydes and have a cross-linking reaction with lignin; and cellulose
itself is not degraded, while it retains higher crystallinity. In the thermal curing pro-
cess, water molecules disrupt hydrogen bonds and destroy the original, sturdy and
ordered structure of cellulose, leading to redistribution of cellulose. By this technol-
ogy, the hemp stalk obtained after steam explosion and wasted hemp fibers can be
processed into fiberboard, further increasing economic efficiency and reducing pol-
lution and waste.
7.2.3.3 Xylo-oligosaccharide and pectin recycling during steam

explosion of hemp fibers
The special physiological activities of active oligosaccharides have attracted attention
from academia and industry, with special attention given to the development of bifidus
factor. Oligosaccharides as bifidus factor have several advantages such as tolerance of
oxygen and acid, using together with antibiotics, resistance to deactivation, and low
production cost. Taking straws as raw materials, steam explosion can selectively sep-
arate and degrade xylan substances (the structural framework of hemicellulose) to
generate small molecules of xylan and monosaccharides that can be separated from
cellulose and lignin by water dissolution. The obtained extraction liquid of xylan is
separated and purified by column chromatography, finally obtaining xylan with a
purity of 70%. The appearance and performance of xylan is superior to domestic prod-
ucts and comparable to imported products.
In contrast to present production methods (mainly enzymatic production) of xylan,
this method has several advantages such as a simple production process, no pollution,
low production and materials cost, and high product yield. The main equipment in this
method includes steam explosion apparatus, chromatography system, concentrating
device, and others, indicating that production conditions are simple and it is easy to
form large-scale industrial production.
7.2.3.4 Production technology of organic fertilizer from hemp

fiber and solid waste
Currently, the main materials for organic fertilizer production are peat, oil cake, and
municipal waste, which are limited by origin distribution and storage, resulting in dif-
ficulties in large-scale production. When using straw as a material for organic fertil-
izer production, the simple grinding treatment leads to long retting times, low
conversion rate of organic matter, and unsatisfactory fertilizer efficiency. Processing
materials by steam explosion and then naturally retting and mixing with natural inor-
ganic fertilizer also has disadvantages. First, monosaccharides generated during the
steam explosion process are largely wasted and cause environmental pollution; sec-
ond, straw only plays the role of a carrier, resulting in a low conversion rate; and third,
major fertilizer efficiency comes from inorganic fertilizer, a role that straw fails to
play, which increases the processing cost, thereby constraining the promotion of straw
to produce organic fertilizer.
Using hemp waste as the main material is a novel production technology for
organic mixed fertilizer that overcomes the deficiencies of existing production tech-
nologies for making organic fertilizer from straw. Hemp is first ammoniated by steam
explosion, causing a large change in the natural structures. In the steam explosion pro-
cess, lignin and generated monosaccharides from hemicelluloses hydrolysis react with
ammonia to produce humic substances. After fermentation, the fermented products
are dried, grinded, and prepared into organic fertilizer.
7.3 Biorefinery modes for softwood

Refining of softwood biomass is receiving increasing attention in the twenty-first cen-
tury (Duan et al., 2013). As a herbaceous biomass, refining methods for softwood bio-
mass also include thermochemical and biological methods. The thermochemical
method refers to thermally decomposing and converting lignocellulose biomass into
several small molecular chemicals (Lin et al., 2007), and the biological method (Peng
and Liu, 2009; Wang and Chen, 2011) refers to the conversion of polysaccharides to
small molecular substances through biological methods while lignin is extracted and
further used. The research on refining of softwood biomass for multiple products is
moving from the laboratory to industry, or into the prototype stage of industrialization.
The traditional application of softwood biomass is primarily in the pulp and paper
industries. Domestic pulp production is still based on the Kraft process, and in recent
years, alkaline sodium sulfite pulping has emerged (Zhan, 2009). With increasing
environmental awareness, pollution problems in the softwood pulping industry are
receiving more attention; for example, wastewater in the paper industry raises the
following concerns (Chen and Li, 2007).
1. Waste liquid in the cooking process, which refers to the black liquor from alkaline cooking
and the red liquor from acid cooking. Alkaline cooking is applied by a majority of pulp mills,
and the solids in black liquor are from inorganic substances added in the cooking liquor and
from dissolved organic substances like lignin during the cooking process.
2. Chlorine bleach effluent, which most small and medium pulp production lines are still
using, contains low-concentrations of CEH bleaching, which generates waste liquid contain-
ing chemical oxygen demand, biological oxygen demand, and other toxic substances.
Although the amount of chlorine bleach effluent is far less than that of black liquor from
the cooking process, the highly-toxic substances in chlorine bleach effluent need much more
attention.
3. Waste liquid emitted from other sections of the pulp and papermaking process also causes
pollution of the environment, and this issue has not been well addressed.
Although the value of paper waste liquid is now taken seriously, and a variety of
methods for recovering components in waste liquid are being developed (Wang
and Chen, 2011; Yang et al., 2013), this approach presents a severe problem: softwood
biomass is simply used as a raw material for paper and the processing of waste liquid is
passive. Therefore, the concept of development and utilization must first be altered.
That is to say, softwood biomass should be regarded as a renewable material having a
specific structure consisting of multiple components that can be converted to a variety
of high-value products, and in the initial design of the conversion process, the func-
tional conversion of multiple components should be regarded as the basic concept to
achieve the maximum utilization of the whole biomass. Finally, raw materials should
be converted to various products by integrated refining. In this way, the waste disposal
amount is decreased, and more importantly, the intrinsic characteristics of softwood
biomass are fully used to maximize its value, in line with the concepts of clean pro-
duction and sustainable development. Based on the above ideas, the following soft-
wood and hardwood refining modes are introduced.
7.3.1 Characteristics of softwood

Needlebush is generally soft, a so-called softwood. Softwood mainly includes Korean
pine, white pine, scotch pine, linden, poplar, and others. Softwood is composed of flat
cells in a radial structure. The cell lumen always contains resin and tannin compounds
and is full of air. Softwood is colorful, soft, flexible, waterproof, and unsusceptible to
chemicals, and is a poor conductor of electricity, heat, and sound. The typical cell has
a diameter of 30 mm and thickness of 1–2 mm. There are vessels between cells. Five
layers exist in the joint cells, in which two layers have fiber properties, two layers are
phellem layers, and the middle layer is lignified. Each cubic centimeter has more than
50 million cells. The fibers of softwood contain tracheids, ray cells, ray tracheids, and
others, and tracheids account for more than 90% of the timber volume with a length of
1.5–5.6 mm and a width of 30–75 mm.
The main components in softwood are cellulose, hemicellulose, and lignin, which
account for 55%, 11%, and 26%, respectively. The minor components are resin, tan-
nin, essential oils, pigments, alkaloids, pectin, protein, starch, inorganic substances,
and so on. In softwood, hemicelluloses mainly consist of galactosyl glucomannan.

One of its characteristics is that the main chain of mannose and glucose is partly
substituted with acetyl groups. An average of 3–4 hexose units have a substituent
group. The other hemicelluloses are composed of arabinose glucuronic acid and xylan.
And the lignin in softwood mainly contains guaiacyl groups. In comparison with hard-
wood, softwood has a similar cellulose content, a higher content of lignin, and a lower
content of hemicelluloses.
The main constituents of softwood are axial tracheids and wood rays. Pinaceae
plants have normal resin canals. Cupressaceae and other minority plants have a
few parenchyma cells. The structural characteristics of softwood fiber are listed as
follows:
1. Simple composition: softwood fiber mainly consist of tracheids, accounting for 89–98% of
wood volume, followed by wood ray of 1.5–7%, axial parenchyma cells of 0–4.8%, and
secretory cells of 0–1.5%.
2. Neat arrangement: main cells are arranged neatly in horizontal sections; the structure is tight
and is called nonporous wood.
3. Homogeneous texture: the simple composition and neat arrangement make its texture
homogeneous.
The permeation path of liquid in softwood is: fracture at the end of tracheid ! cell
lumen ! pit of cell wall ! neighboring tracheid ! cross field pits ! ray cell ! trac-
heid. Solvent primarily permeates from cell lumen to the S3 layer, and finally reaches
the S1 layer and cell corner. The pits on tracheids of early wood are much larger than
those of late wood, and the percentage of connective pore volume to total wood vol-
ume is large.
7.3.2 Softwood biorefinery industrial process

The development of a new industry is often based on the gradual upgrading of an exist-
ing traditional industry. On the basis of the lignocellulose refining platform estab-
lished by Prof. Chen, Shixian paper mill in Tumen City, Jilin Province, China,
achieved high-value utilization of lignin and hemicelluloses by degrading products
from red liquid during the softwood papermaking process. A description of the main
process line follows (Figure 7.9).
This technology is based on the lignosulfonate and sugars as the main components
in red liquor, and uses a combination of ultrafiltration and nanofiltration to remove
lignosulfonate of different molecular weights and applies ion exchange resins and
activated carbon adsorption to remove inorganic substances. After decoloration and
desalination, the sugar liquor obtained from nanofiltration reaches a sugar content
of 90%, and this liquor can be fermented to prepare acetone, butanol, ethanol, biogas,
biopesticides, or catalyzed to generate ethylene glycol, propylene glycol, and other
polyhydric alcohols. It also can be used to prepare mannose and xylose through con-
centration and purification using simulated moving bed chromatography.
Sugar liquor
Filtered Nanofiltration
liquor (NF4-34396)
Acid liquor
Filtered Nanofiltration
red liquor (NF6-34395)
Concentrated
liquor
Concentrated
liquor > 0.1 µm Carbon fiber
Ultrafiltration
Concentrated
(MIF-503)
liquor
Coal dust
Filtered Ultrafiltration 20 kDa–0.1 µm
liquor dispersant
(UPIS-503)
Filtered
liquor
Cement water-
6000–20 kDa
reducing agent
Ultrafiltration
(UEOS-503)
Filtered
1000–6000 Vanillin
liquor
Figure 7.9 Comprehensive utilization of hemicellulose and lignin in pulping waste liquor.
7.4 Biorefinery modes for hardwood

7.4.1 Characteristics of hardwood
Broadleaf wood is named for the broad leaves of its trees. Because of its more rigid
timber, it is generally also known as hardwood. Fibrous materials of hardwood contain
three fibrous cells: libriform wood fiber, fiber tracheid, and tracheid (collectively
called wood fiber). Wood fiber is 0.7–1.7 mm long and 20–40 mm wide and accounts
for 25–35% of wood volume, wherein libriform wood fiber is the most common type.
Because of its tight structure, its lignin content is usually between 20–24% and is
lower than softwood, while its pentose content is usually as high as 21–24%. The main
components of hardwood are cellulose, hemicelluloses, and lignin, and constitute
55%, 25%, and 22% of hardwood, respectively. Minor components are similar to soft-
wood. Hemicelluloses in hardwood mainly consist of O-acetyl-4-O-methyl-glucuronic
acid-D-xylan. The lignin monomer of hardwood includes guaiacyl and syringyl units.
Hardwood microstructure features the following:
1. Complex composition. Main cells are wood fiber 50%, vessel element 20%, wood ray 17%,
and axial parenchyma cell 13%.
2. Irregular arrangement. Major cells arrange irregularly and loosely on the cross section,
which is called porous wood.
3. Wood ray is developed, mostly occupies two or more columns, and completely consists of
ray parenchyma.
4. Rich axial parenchyma. Most plants have a lot of axial parenchyma, which have various
distributions.
The liquid permeation of hardwood is for sapwood: vessel ! pits on cell wall ! wood
fiber, liquid can also permeate into fractures of other kinds of cells. Thylose in vessels
decreases the permeation velocity, which can be improved by adding cooking liquor
(sulfurous acid, hot alkali) to enhance the permeability. The percentage of connective
pore volume to total pore volume is low.
7.4.2 Hardwood biorefinery industrial process

To completely solve the pollution problems of the traditional paper industry based on
hardwood plants, and to fully use the lignocellulosic resources, Prof. Chen constructed
a flow diagram of the lignocellulose biomass refining process based on the steam
explosion technology platform and the solid-state fermentation platform (Duan
et al., 2012; Xu et al., 2002) (Figure 7.10). This process has the following
characteristics:
1. Cellulose, hemicelluloses, and lignin in lignocellulosic feedstock can be converted to differ-

ent products through various unit operations, which achieves the high-value conversion of
various components, increases product variety, and solves pollution problems.
2. Lignocellulose biomass refining mills are transformed from traditional paper mills, increas-
ing product output and enhancing technological competitiveness.
3. Steam explosion is applied to solve the pollution problems in chemical methods (and also a
small number of physiochemical methods) of the paper industry. After steam explosion
treatment, part of the hemicelluloses is degraded, and cells (especially fiber cells and their
surrounding cells) are separated. So a small amount of chemical agents added can achieve
the original purpose of the cooking process.
7.5 Biorefinery modes for lignocellulose rich

in active ingredients
Under the influences of an aging population, worldwide medical system reform, and
the “back to nature” movement, the influence and application of traditional medicine
is increasing in the world, displaying many development opportunities.
Wood
Hydrolysate liquor Acetone/

Rosin Extraction (hemicellulose) butanol/ethanol
Short
fiber
Steam explosion
and wash Solids Mechanical
(cellulose) carding
Solids Alkali Long Pulping and

(lignin and cellulose) wash fiber papermaking
Liquor Precipitate Phenolic

neutralization Lignin
(lignin) resin
Figure 7.10 Lignocellulose refinery process route for hardwood.

Currently, traditional processing methods for traditional medicine cannot meet

global development needs. The utilization of just a single component, as well as sim-
ple and outdated extraction, preparation, and conversion technologies in the proces-
sing of traditional medicine, cause an enormous waste of resources and pollution in the
conversion process. To produce a particular medicine, the common process involves
crushing, then extracting active ingredients, and finally discarding medicine residues
or using them for mushroom cultivation and fertilizer fermentation. Each operational
unit is quite separate from the others and the features and interrelation of each oper-
ational unit are always ignored. This leads to the isolation of each technology and the
lack of coordination and complementary use among technologies, resulting in extra
energy consumption and a reduction in work efficiency.
Therefore, to achieve the conversion of herbal extracts from a single type to mul-
tiple types of products and to realize the high-value comprehensive utilization of tra-
ditional medicine resources, new technologies and the integration of key technologies
are needed. Based on years of research, Prof. Chen’s team established a steam explo-
sion refining platform for traditional medicines. Steam explosion, ultrafine grinding,
organic solvent extraction, solid-state fermentation, and combined treatment of
various technologies are applied in materials from different origins and parts with
different active ingredients, such as kudzu, turmeric, ginkgo leaf, Eucommia leaf,
sumac, Radix zanthoxyli, pollen, and others. Experimental results show that the steam
explosion process can effectively destroy the cell structure of raw materials, decrease
the dense structure of the cell wall which acts as an extraction barrier for active ingre-
dients, increase the specific surface area of raw materials, and shorten the extraction
time. Such advantages help to save on solvent usage, decrease energy consumption,
and control production costs. The core of the steam explosion refining platform of
traditional medicines is in the key technologies used, including pretreatment, extrac-
tion and purification, conversion and comprehensive utilization of residues and their
optimization and combination, and the establishment of a scientific and rational eco-
logical industrial chain based on the characteristics of materials. All of the above tech-
nologies are employed to realize the rational development and effective preservation
of traditional medicine resources, to achieve the unity of ecology and society, and to
provide a solid material foundation for the modernization of Chinese medicine and
sustainable development of the industry.
7.5.1 Ecological industrial process for kudzu

Kudzu is the dry roots of Pueraria lobata of leguminosae plants. There are about 20
species of Pueraria plants in the world, mainly in temperate and subtropical regions
with an elevation between 100–2000 m. They always grow in bushes near the forest
edge or streamside. Kudzu is mainly composed of starch, cellulose, protein, and iso-
flavones (Zheng and Zhao, 2006), and also contains a small amount of fat, pectin, tan-
nins, and alkaloids. The moisture content of fresh kudzu is 50–60%, and the starch
content is 18.5–27.5%, which can be equivalent to 50–60% in dry kudzu. In addition,
dry kudzu also contains cellulose of 9–15%, crude protein of 5–8%, and isoflavones of
3–5%. So, it can be used as starchy feedstock to produce ethanol. Besides, P. lobata
has the feature of drought resistance and is adapted to environments that are poor in
nutrients. Therefore, planting kudzu not only can create economic benefits, but also
produce good ecological benefits. Kudzu has become an important commercial crop
in many places in China, resulting in a large area of artificial cultivation. Because it is
rich in starch, it can be used as a raw material for fuel ethanol production, so solving
the problems of cereals fermentation, which is restricted by the limited food sources
and expensive cost. In fact, food fermentation is high-cost and of low competitiveness,
and excessive food consumption causes the reduction of per capita availability of
food, threatening national food security. In addition to the above advantages, planting
kudzu is conducive to agricultural production and creates good income for farmers.
The existing ethanol production process from starchy feedstock is material
grinding ! cooking ! liquidation ! saccharification ! fermentation ! primary dis-
tillation ! rectification. Kudzu contains a lot of fibers, leading to high energy con-
sumption in the mechanical crushing and a complicated strach extraction process,
so it is difficult to use the above technology route. Additionally, a large volume of
highly concentrated organic wastewater would be generated in the abovementioned
ethanol production process, causing environmental pollution. In the application of
kudzu, the kudzu itself is merely used as a starchy feedstock to extract starch or as
a flavonoids feedstock to extract flavonoids, this makes it difficult to consider the
comprehensive utilization of starch and flavonoids in kudzu. Therefore, in order to
eliminate the pollution of organic wastewater in liquid fermentation and fully utilize
the starch and flavonoids components, a new and clean processing route for kudzu to
co-produce starch and flavonoids needs to be established based on the characteristics
of kudzu.
Prof. Chen et al. proposed a kudzu processing ecoindustrial process taking fuel eth-
anol from fermentation as the major product. According to the results of the develop-
ment of a kudzu ecoindustrial chain, the process of simultaneous saccharification and
fermentation of steam-exploded kudzu to co-produce starch and flavonoids was put
forward. Steam explosion technology can be used to decrease the dissolution barrier
of celluloses and other constitutive components to starch and flavonoids. Then, after
simultaneous saccharification and fermentation, ethanol is produced and residues are
used to extract flavonoids. The technology route of the process is shown in
Figure 7.11.
This technology has the following advantages: saving water and saving energy.
Compared with traditional ethanol production from starch fermentation, the fermen-
tation of steam-exploded kudzu could decrease the amount of water in the liquidation
unit three- to fivefold and the solid–liquid ratio of continuous solid fermentation to 1:5
(for liquid fermentation, this ratio is 1:10). To produce 1 ton of ethanol in this way
could save 10 tons of water. Steam explosion pretreatment of kudzu could replace
the traditional grinding process, which consumes a large amount of energy, and sub-
stitute the traditional liquidation method of high-temperature cooking (which
accounts for 30–40% of the total energy consumption). Continuous solid fermentation
is coupled with heat pump separation, so that the separated ethanol (30–50%) can be
directly rectified to reach 95% ethanol, lowering the high energy consumption of dis-
tillation by 30–40%.
Radix pueraria
Steam explosion (0.8–1.0 MPa, 2–4 min)
Yeast Saccharifying enzyme
Solid-state fermentation 50% ethanol Distillation Ethanol
Residues
Liquid Vacuum Solid

concentration
Ethanol precipitation Ethanol reflux
Ethanol supernatant
Fiber waste
Concentration
Purification by
macroporous
Fiber Protein
adsorption resin (paper materials) (protein feed)
Total isoflavones
Figure 7.11 Production of ethanol and isoflavones from steam pretreated Radix pueraria by
solid-state fermentation.
7.5.2 Ecological industrial chain mode of Rhus resource

Rhus chinensis is one of the economic tree species in China. Rhus is widely distributed
and abundant, but is still underused and underdeveloped. According to statistics, there
are about 500,000 ha. of wild Rhus in the west of Anhui Province, which is equal to
500 million plants. If each plant can produce at least 2 kg of fruits every year, the total
yield is significant.
Sumac is an oil-rich plant with an oil content of 15–20% in the fruit. The oil in the
fruit mainly contains five kinds of fatty acid, including palmitic acid, stearic acid, lino-
leic acid, oleic acid, and linolenic acid. Linoleic acid accounts for 40–48% of the total
amount, and is recognized as one of the most important essential fatty acids. It can
reduce blood cholesterol and prevent atherosclerosis. The absence of linoleic acid
causes poor animal development, skin and kidney damage, as well as infertility. In
addition, sumac fruit is rich in flavonoids. About 2 kg of flavonoids can be extracted
from 100 kg of sumac fruit, mostly quercetin-3-O-rhamnoside, and the hydrolysis
product of this is quercetin. It has been proven that quercetin has a very wide range
of physiological and pharmacological activity: it can expand the coronary blood ves-
sels, lower blood lipids and blood pressure, and has an antiplatelet-aggregation effect;
it has cough relieving, phlegm removing, anti-inflammatory, antiviral, anti-allergic,
and antioxide free radical effects; and it also has significant prevention and treatment
effects on tumors. Thus, sumac fruit is a good medicinal resource that has great value
for potential development.
Because oils and flavonoids are present in the cells of sumac fruit, the fruits need to
be crushed before extraction. The traditional pretreatment method for sumac fruits is
mechanical pulverization to facilitate the extraction of effective constituents. As oil
seeds have high resistance to exogenic action, the effect treatment on the material
is limited. In recent years, steam explosion has been widely applied in papermaking,
feed processing, and other industries, in particular generating excellent effects in cell
wall breakage and material smashing. When sumac fruits are pretreated by steam
explosion, sumac materials are maintained in the high-temperature and high-pressure
environment for a period of time, then the pressure is suddenly released, resulting in
damage of the material structure. After pretreatment, the fruit cell is totally disrupted,
and steam-exploded materials present slice shapes or porous granulous shapes with
more porosity and smaller particle size.
Extracting oils from steam-exploded materials would enhance the permeation of
the solution in the porous structure of solid materials, thereby increasing extraction
efficiency and yield with shorter extraction times, and decreasing the residual oil left
in the oil cake. In addition, steam explosion treatment can achieve the effects of heat-
moisture treatment and material crushing, avoiding some complicated, energy-
consuming, time-consuming problems caused by cracking, flaking, heat-moisture
cooking, and other conventional steps. This improves production efficiency and saves
equipment investment, thus reducing production costs. According to some studies,
quercetin-3-O-rhamnoside could be hydrolyzed to quercetin during the steam explo-
sion process. So, quercetin is directly extracted from steam-exploded materials, which
saves the trouble of the hydrolysis process of quercetin-3-O-rhamnoside (Chen and
Chen, 2011). Finally, residues after oils and flavonoids extraction can be converted
to active carbon by a simple heat treatment, realizing the comprehensive utilization
of sumac fruit. Its process is shown in Figure 7.12.
The sumac fruit ecological industrial chain has the following characteristics: (1) the
introduction of steam explosion technology simultaneously achieves the crushing and
heat–moisture treatment process in the traditional oil extraction industry, and establishes
a novel and high-efficiency oil materials processing technology, decreasing oil extrac-
tion time by 50%; (2) the establishment of a clean quercetin production process, achiev-
ing the conversion from quercetin glycoside to quercetin without the addition of acid and
alkali, reaching a conversion rate of 90%; and (3) the construction of a sumac fruit ecoin-
dustrial chain through technical integration and innovation, fulfilling the goal of compre-
hensive utilization of sumac fruit, and also providing a reference template for the
development of a large number of medicinal plants that produce oil-rich seeds or fruit.
7.5.3 Comprehensive integrated biorefining of medicinal

plant resources
High-value utilization of biomass resources for energy, materials, and chemicals pro-
duction, is the common focus of academia and industry. Medicinal plants are an
important raw material resource, and their value is not only as drugs but the utilization
Sumac fruit
Steam
explosion
Drying
Extraction
Filtration
Solvent recovery
Oil meal Oily solution
Ethanol reflux Evaporation

extraction
Ethanol recovery
Fruit/seed oil
Filtration
Flavonoid Pomace
solution
Concentration
Active carbon
Column
chromatography
Quercetin
Figure 7.12 Process route of comprehensive utilization of sumac fruits.
of each component in the plant, which should be a future development trend. The key
to this is technology integration, which involves comprehensive refining integration
of medicinal plant resources. Figure 7.13 shows a typical use pattern: after steam
explosion of medicinal plants, the cellulose, hemicelluloses, and lignin in them are
converted to produce energy, materials, and chemicals; then fermented solid materials
are extracted with active ingredients; and finally, extracted solid residues are prepared
to produce feed, fertilizer and, fuel.
The comprehensive refining industry chain for medicinal plants has the following
characteristics.
1. The integration of various key technologies such as steam explosion (Chen, 2010; Yuan and
Chen, 2005) and solid fermentation (Qiao et al., 2013; Zhuang and Hong, 2006).
Medicinal plant Butanol Fuels
Ethanol Chemical
Solid state
Steam explosion
fermentation
Lactic acid Materials
Extraction of
Residues
active chemicals
Others Others
Solid residues
Butanol Feed Fertilizer Others
Figure 7.13 Process route for comprehensive utilization of medicinal plants.
2. A flexible process: the concrete operational process can be changed based on different char-
acteristics of materials or new technologies added to further enrich and develop this chain.
For instance, steam explosion can be used in combination with enzymatic treatment, micro-
wave, ultrasonic, supercritical fluid, and other extraction methods, while separation and
purification of products can make use of ultrafiltration, membrane separation technology,
and so on.
3. The wide range of applications: this process could be applied to most medicinal plants and
other oil/flavonoids-rich natural plant resources.
4. Diversity of products: this process achieves the goal of the conversion from simple product
to multiple products; that is to say, it is not only utilized to extract medicinal ingredients, but
also to develop a variety of high-value-added products, improving economic efficiency.
With the abovementioned theoretical and technical system applied in current compre-
hensive utilization of medicinal plants, the study of medicinal plants could be
expanded from the pharmaceutical industry to the food, materials, energy, and other
multiple disciplines by absorbing various techniques to form a unique ecoindustrial
chain for medicinal plants, to fulfill the aim of increasing the utilization rate of medic-
inal plants, decreasing emission of pollutants, and realizing the diversity and high
value of products; consequently promoting the modernization and development of tra-
ditional medicine. A comprehensive integrated refining ecoindustrial chain for medic-
inal plant resources addresses resource utilization and environmental pollution during
the conversion of mass and energy, in order to simultaneously realize economic, envi-
ronmental, and social benefits, transforming the medicinal plants industry from a tra-
ditional Chinese medicine extraction industry to a medicinal plants refining industry
with multiple products including pharmaceuticals, materials, and energy.
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Chen, H.Z., 2010. Medicinal Plants Process Engineering and Eco-Industry Integration. Science
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Chen, G.Z., Chen, H.Z., 2011. Extraction and deglycosylation of flavonoids from sumac fruits
using steam explosion. Food Chem. 126 (4), 1934–1938.
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Technol. Market 32 (7), 28–32.
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Processing. Science Press, Beijing.
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Future perspectives for
lignocellulose biorefinery 8
engineering
8.1 The role of lignocellulose in society and the economy

Solar energy is the source of almost all energy on the earth, and biomass is the carrier
of the solar cycle conversion process. Coal, oil, and natural gas, which were made
from biomass buried in the ground eons ago by the combined action of microorgan-
isms and geochemical evolution, are the energy basis of modern industrial develop-
ment. Energy use should be biomass ! coal ! oil ! coal ! biomass. Replacement of
coal, oil, and natural gas by conversing biomass into bioenergy should be feasible due
to the balance of CO2 utilization and emission, forming a theoretical CO2 recycling of
zero net emissions. If biofuels from biomass could completely replace fossil fuels, CO2
emissions of biofuels utilization processes would be equivalent to the exploitation of fos-
sil fuels, which means that the energy utilization efficiency would be improved and CO2
emissions would be reduced. In addition, N, S, and other impurities would be removed in
the biofuels production process to the greatest extent. Therefore, more attention should
be paid to biofuels due to the reduction of CO2 emissions, the decrease of atmospheric
pollution concentration, and the importance for environmental protection.
BP Statistical Review of World Energy 2011 (‘BP statistical review of world
energy June, 2011’, 2011, Available from: www.bp.com/statisticalreview) reported
that the fixed years of the development of oil, gas, and coal were estimated at
46.2 years, 58.6 years, and 118 years, respectively, according to the world’s proven
reserves of these resources at the end of 2010. Fossil energy resources, especially
oil and natural gas resources, are very insufficient in China. Meanwhile, due to the
rapid development of the economy, energy consumption rapidly increases in China,
accounting for 20.3% of the total global energy consumption in 2010. China surpassed
the Unite States as the world’s largest energy consumer, whose coal consumption
accounted for 48.3% of total global consumption. Despite the rapid growth of new
energy, coal is still China’s primary energy source. The situation is unlikely to change
in the short term, resulting in China being first in emissions of SO2 and second in emis-
sions of CO2 in the world. Therefore, looking for environmentally friendly clean
energy to replace oil and coal, and hence to meet the large demand for human liquid
energy, continues in an irreversible direction. Just as the end of Stone Age is not due to
the exhaustion of stone, the end of the Oil Age will occur long before the oil runs out.
When people find a cheaper alternative energy, the Oil Age will bid farewell naturally.
Advocating the development of a green economy and low-carbon economy in China,
particularly by carbon trading, tax concessions, tariffs, and other environmentally
related policies would create a favorable macro environment for the development
of a biomass refining project, which should indicate a bright future for biomass
refining.
Lignocellulose is a renewable and plentiful resource that can be used as feedstock for
fuel, feed, and fertilizer (Wang et al., 2014). Lignocellulose refining project is an emerg-
ing industry using environmentally friendly renewable resources to produce clean energy
and bio-based chemical products. From the point of resource depletion, energy security,
environmental protection, and sustainable development, establishing a low-carbon
lignocellulose refining project is a trend in the development of the circular economy.
Currently, most of the energy used in the world is oil, coal, natural gas, and other
fossil fuels. With the depletion of fossil fuels and increasingly serious environmental
pollution, the development of clean and renewable energy is imminent. Biomass
energy consumption accounts for 14% of total global energy consumption, which
is only next to oil, coal, and natural gas. Biomass energy is not only different from
conventional fossil energy, but also different from other new energy sources, and it
has the features and advantages of the two energy forms. Biomass is organic matter
produced by plants through photosynthesis, which originally comes from solar energy
with a high volatility component and low sulfur and ash content. Development and
utilization of biomass with economical and efficient methods is a very important strat-
egy around the world. The efficient utilization of biomass is proposed as an important
position in technology development when many countries adjust their national energy
development strategy. Biomass energy will become a major energy source in the
twenty first century, and 40% of global energy consumption will be from biomass
by 2050 (Xiao et al., 2006).
In recent years, the harm of the greenhouse effect has been increasingly apparent.
Carbon dioxide accounts for about 60% of the greenhouse effect from all greenhouse
gases. Therefore, reduction of carbon dioxide emission becomes the control priority of
the greenhouse effect. Original solid carbon in fossil fuels becomes fluidized carbon by
burning, which is in the form of carbon dioxide accumulated in the atmosphere. Bio-
mass fuels play an important role in the reduction of greenhouse gas emission because
the carbon in biomass comes from carbon dioxide in air. If the utilization of biomass
moves ahead with reasonable and appropriate speed, carbon can even reach equilib-
rium through carbon dioxide recycling. Therefore, we can achieve zero carbon dioxide
emissions, resulting in reducing the greenhouse effect caused by fossil energy con-
sumption, and hence fundamentally improving the ecological environment.
Lignocellulosic biomass will provide renewable fuels, bio-based materials, and
chemicals in the future. The U.S. Department of Energy (DOE) has proposed that
5% of electricity, 20% of transport fuels, and 25% of chemicals be replaced by related
products from biomass, which is equivalent to 30% of the current oil consumption in
2030. By then, 1 109 tons of dry raw material would be consumed annually, which is
five times the current biomass consumption. Royal Shell Company estimates that bio-
mass will provide 30% of the world’s chemicals and fuels in the first 50 years of the
twenty first century, and the world’s market share will reach $150 billion. Agricultural
crops may gradually replace oil as the source of chemicals, energy, and materials, and
“black gold” will be replaced by “green gold.”
Future perspectives for lignocellulose biorefinery engineering 249
8.2 Problems of lignocellulose biorefining

Resources shortages, energy depletion, environmental pollution, food shortages, and
other crises have become more and more serious in the world. In order to solve these
problems and achieve sustainable development of society, we must find new and
renewable resources, materials, and processes as alternatives. Lignocellulose biomass
is a kind of renewable and abundant resource. Replacement of fossil resources by bio-
mass and replacement of petrochemical products by bio-based products are the only
way to achieve sustainable development of society (Himmel et al., 2007). Currently,
the utilization of crop straw is a simple way to convert lignocellulosic feedstock into
low-value products. High-quality, high-value production technologies of biomass
resources for bio-based chemicals and bio-based materials are still faced with the
following questions.
1. Inferior product performance: Some properties of the product prepared from biomass cannot
compete with petroleum-based products, such as the difficulty of polyhydroxyalkanoate
(PHA) preparation due to the brittle, poor mechanical properties and the narrow temperature
range of PHA. If the key spinning process technology is broken, cost control and other
aspects of dyeing properties would be greatly improved.
2. High manufacturing cost: In most cases, the utilization cost of lignocellulose is high, which
makes it difficult for it to compete with a production process based on hydrocarbon feed-
stock. Currently, the capital cost of cellulosic ethanol is $0.7 to $1.0 per liter, which is
50% higher than that of oil. Environmentally friendly materials, such as PLA and PHA,
are emerging materials. In terms of price, polypropylene price is below $1.0/kg, while
the cheapest biodegradable plastic also costs $3.0 to $6.0/kg. Thus, bio-based materials from
biomass cannot be indirectly competitive with petroleum-based plastic materials.
The high capital cost of bio-based material is due to various factors. First, large-scale
industrial technology is not mature enough for the production processes from biomass. Sec-
ond, production costs need to be significantly reduced, and the processing technology cannot
meet the needs of product performance.
3. Limited industrial products: Currently, successful industrialized development of products is
limited. Most crop stalks raw materials are used for pulp and paper. Besides, other raw mate-
rials, such as corncob, are used to product xylose, xylitol, furfural, and artificial panel.
4. Difficulties of bulk product development: Crop straw resources are abundant, so bulk prod-
ucts should be developed in order to truly replace fossil resources. Thus, industrial develop-
ment and utilization of straw resources should be achieved and the bottleneck problem of
converting straw resources will be fundamentally solved. The development of bulk products,
such as energy (fuel ethanol, butanol), materials (ethylene glycol, 1, 3-propanediol, succi-
nate), chemicals (phenolic compounds), and so on, are currently unable to overcome the cap-
ital cost problems. For some product chemicals, such as phenols, the technology is still
immature.
5. Immature key technology: Bio-based material is an emerging industry, and the refining tech-
nology is not mature. Because the raw materials are various and differ from each other, the
refining technology cannot simply be applied to different materials. In the bio-based mate-
rials development process, the problems of bio-based raw material pretreatment, bioconver-
sion, chemical conversion, modification and composite molding, and other key technologies
should be broken.
6. Poor equipment: The equipment should meet the needs of technology development in the
lignocellulose refining project. Therefore, it cannot rely on the existing equipment. Current
research and development of both equipment and technology for biomass refining is still
lagging.
7. Lack of technology integration: Currently, most straw conversion technologies lack eco-
nomic viability, mainly due to the use of the whole harvested straw. In fact, only a certain
part of the straw is used, resulting in new pollutants and a waste of resources. Biomass refin-
ing technology should be integrated by converting different components, and achieving full
utilization of biomass resources.
8. Small-scale industrialization: Most bio-based products production is still done at a labora-
tory scale. Many key technology issues need to be overcome before large-scale production
can be achieved. Therefore, it is important to promote demonstration-scale production at low
cost and to build a bio-based materials research and development platform.
8.3 Future trends in lignocellulose biorefining

The biomass industry is neither the energy industry in a traditional sense, nor the agri-
culture and agroindustry. It is a new emerging interdisciplinary industry, which needs
the collaboration of relevant departments, sectors, and disciplines, such as the agricul-
ture, oil and chemical, biological chemical, and materials industries. Key aspects of a
particular system should be investigated based on the specific needs of each discipline
system according to its own advantages. For example, the straw cellulosic ethanol sys-
tem includes straw production, collection, transportation, storage, pretreatment, cellu-
lose hydrolysis, ethanol fermentation, separation, purification, waste disposal, and other
sectors. Even if each sector is studied well, the issue of the entire system is a difficult
problem to solve. The desired effect should be achieved by evaluating the respective
advantages of specific research institutes for investigating the specific system, making
breakthroughs in key technologies, and integrating enterprise technology.
Lignocellulose biorefinery projects undertake green, recycling, and sustainable
development as a concept. It is committed to the development of renewable resources
and energy and the maximum utilization of resources and energy. The comprehensive,
integrated, large-scale, and systematic development of lignocellulosic resources
should be carried out by the means of product multigrades development and maximum
resource utilization. Therefore, a lignocellulose products comprehensive deep proces-
sing industry would be achieved, and bio-energy, biomass chemistry, and new indus-
trialized economies of chemical renewable resources would be established, providing
a series of green products for the market.
Overall, lignocellulosic biomass is the most abundant renewable resource on the
earth, which plays an irreplaceable role in the process of sustainable development
of human society, especially in the process of sustainable development of the chemical
and energy industry. The lignocellulose biorefinery is the key technology for the com-
prehensive and effective utilization of biomass resources. For a series of problems cur-
rently existing in the bio-based products preparation process, Chen and Wang
proposed a concept of bio-based product process engineering and ecoindustrial chain
Future perspectives for lignocellulose biorefinery engineering 251
integration, and established a multistage stratified biomass conversion technology

system and the key technology platform, providing a viable route for the achievement
of lignocellulose biorefinery technology (Chen and Wang, 2008). Multidisciplinary
collaboration and development will accelerate the development course of lignocellu-
losic resources industrialization.
In short, preparing chemicals, energy, and materials from lignocellulosic raw mate-
rials is an irreversible trend, and lignocellulose will have a brighter tomorrow by join-
ing multidisciplinary and multi-industry efforts.
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Index
Note: Page numbers followed by f indicate figures and t indicate tables.
A Bio-based chemicals
Acetobacter xylinum, 96 furfural, 147–149
Acetone-Butanol-Ethanol (ABE) levulinic acid, 146–147
fermentation, 131, 132, 135f organic acids, 143f
Acid-catalyzed hydrolysis, 90 oxalic acid, 143–145
Acid hydrolysis, 72, 73 Bio-based desert soil amendment materials
Activated carbon, lignin, 83 application and market, 152–153
Adsorption carrier solid-state fermentation organic content, 154
method, 95–96 preparation, 154f
Agricultural lignocellulosic resources, 6 pretreatment methods, 153–154
Agricultural straw biorefinery Bio-based materials
applications, 10, 11f bio-based desert soil amendment
corn stalk characteristics, 221–222 materials, 152–154
lignocellulosic ethanol, 15–17, 16f cellulose acetate, 150
straw refining industry chain, 224–228 lignocellulose board, 154–156
utilization patterns of corn stalk, 222–224, sodium carboxymethyl cellulose,
223f 151–152
Air classifier, 190, 191f Biobutanol/bio-based butanol
Airflow grading device, 57–58 fuel, 131
Alkali method, 72 Bioconversion enzymes, 97
Analytical lignin Bioconversion technologies, 19–20
Klason lignin, 78 characteristics, 87–88
milling wood lignin, 78 description, 87
Annual plants, 9 features, 87–88
Antoine equation, 182–183 gas double dynamic solid-state
Apoplastic pathway, 25–26 fermentation bioreactor, 92–93
Atomic force microscopy, 24f, 31–32 interface property, 89–90
Autohydrolysis method, 72–73 liquid bioconversion technology,
Automatic control system, 201–203 90–91, 92f
nutrition, 88
B solid phase enzymolysis coupled with
Bacterial cellulose production, 96 liquid fermentation, 93–95
Bamboo solid-state bioconversion technology,
advantages, 229–230 91, 92f
comprehensive utilization, 230f Bioenergy
fiber production process, 229f biogas, 135–137
natural bamboo fiber, 228–229 biomass briquettes, 139–140
Bast fibers, 9 bio-oil, 141–142
Batch steam explosion equipment BP statistical review, 127–128
industrial application, 51–53, 51f butanol, 131–135
schematic illustration, 50–51, 51f ethanol, 128–131
254 Index
Bioenergy (Continued) Bound water, 170

hydrogen, 137–139 Breathing fiber, 229
solar energy, 126 Breathing solid-state fermentation
Biofuels production, 126–127 bioreactor, 195–196, 196f
Biogas Brittle fracture criterion, 177–179
application and market, 135–136 Brown rot fungi, 145
household energy consumption, 136–137 Butanol
straw, 137 application and market, 131
Biomass, 125, 126, 128 biobutanol, 131
description, 5 fermentation, 131, 132
ecological carbon balance, 127f gas chromatography, 34
energy, 7–8, 248 necessity and problems, 131–135
fermentation technology, 128–129
lignocellulosic, 5–6
recycling, 4 C
Biomass briquettes Carbohydrate oxidation method, 144
application and market, 139 Carbon fiber, 83–84
combustion properties, 140 Carbon monoxide coupling method, 144
hearth corrosion and scorification, 140 Carding fractionation equipment
Biomass briquettes-pellet fuel, 140f air classifier, 190, 191f
Bio-oil hydraulic carding fractionation
acidity, 108 equipment, 188–189
ash, 108 mechanical carding fractionation, 190,
calorific value, 101–102 191f
classification, 141 Paul screening instrument, 188–189, 190f
commercial value, 141 Carding process, two-phase steam
component analysis, 142t explosion, 63
composition, 108–109 2,3-butanediol yield, 67, 68f
heat value, 108 cellulose enzymolysis rate, 66, 66f, 67, 67f
hydrogenated deoxidization, 109–110 feasibility analysis, 63, 64–65, 64f
modification process, 109–112 inhibitor content, 65–66, 65f
organic compounds, 108–109, 109t Catalysts, 148–149
oxygen content, 107–108 Catalytic cracking, pyrolysis gas, 110–111
problems, 141 Catalytic reforming, 141
pyrolysis, 107–109 Cell level selective fractionation technology,
refinery technology, 141 39–40
viscosity, 108 Cellulase, 20
water, 107 Cellulose
Biopesticides production, 97 acetate, 150
Biorefinery process, 125 acid hydrolysis, 73
compositions and structures, 29–30 cell, 16
interfacial properties, 33 enzymatic hydrolysis, 75
mass transfer parameters, 32 microfibril, glucan chains, 24
mechanical properties, 32 products, 75
morphological and structural features, Cell wall surface, parenchyma cells, 24, 24f
33–34 Cell wall synthesis, 22
rheological properties, 33 Chinese herbal medicine, 87
temperature detection method, 33 Cigarette filter, 150
Bond water, 88–89 Clavulanic acid, 95–96
Index 255
Clostridium acetobutylicum, 227 Ecological crisis, 3

Clostridium butyricum, 138 Emulsion, 111–112
Coal formation process, 19 Energy crisis, 2
Combustion technology Energy utilization, 7–8
power generation, 122 Ensiling, 162–163
stages, 121–122 Environmental parameters, biorefinery
Component separation technique, 37–38 process, 196
Concentrated acid hydrolysis principle, 73 Enzymatic hydrolysis, 90
Continuous steam explosion equipment cellulose, 75
feeding system, 53, 53t lignin, 80
one-section and two-section types, 55 Ephedra herb, steam explosion condition, 62
stake technology digester, 53, 54f, 54t Ephedra spp., 62
Convection, 169, 173 Epidermal tissue system
Convective mass transfer, 169 classification, 21
Conversion engineering, 13–14 corn stover, 23
CO2 recycling, 247 function, 21–22
Corn stalk porous structure, 23
carding process, two-phase steam Equivalent ratio, lignocellulose air
explosion, 63, 65, 66 gasification, 114
characteristics, 221–222 Ethanol
description, 129–130 advantages, 129
fuel ethanol production, 130f bioenergy system, 128–129
in vivo digestibility, 161, 162f fermentation process, 19–20, 129–131
porous structure analysis, 24, 25t flowchart, 130f
soluble sugar content, 161, 162f gas chromatography, 34
utilization patterns, 222–224, 223f lignin, 80
vascular tissue fraction, 41 production, 241f
Cultivation industry, energy recycling mode, straw cellulosic ethanol system, 250
4, 4f Extracellular external water, 88–89
Cuticular transpiration, 25–26
Cutin layer, 40–41
F
D Fast pyrolysis, 101–102
Feeding stuff
Dermal tissue system, 40
application and market, 159–160
Desertification, 152–153
degeneration and desertification,
Detection methods, lignocellulosic
160–163
materials, 31
Feedstock engineering, lignocellulose
Diffusion
biorefinery, 13
definition, 26
Fermentation process
mechanism of vapor, SSF process, 172
Chinese herbal medicine, 87
molecular, 169
ethanol, 19–20, 129–131
Digital image analysis, 196–201
stalk, 39
Dilute acid hydrolysis, 74
Fiber restructuring molding technology,
Direct liquefaction process, 116–118
100
Fick’s law, 172
E Fixed bed gasification, 112
Eco-industrial park, 5 Flexible fuel vehicles (FFV), 128–129
Eco-industry, 4–5 Fluidized bed gasification, 112
256 Index
Food Greenhouse effect, 248

crisis, 2–3 Ground tissue system
vanillin, 158–159 classification, 21
xylose and xylitol, 156–158 function, 21–22
Forestry lignocellulosic resources, 6
Fractional orientation conversion process, 15
Fraxinus mandshurica pyrolysis, 108–109 H
Free surface water volume, 170 Hardwood
Functional components, lignocellulosic characteristics, 237
feedstock, 29 refining process, 238, 238f
Fundamental tissue system, 40 Heat conduction, 173
Furfural, 147–149 Heat transfer
porous media, 169
SSF process, 173
G Hemicellulose, 186–187
Gas double dynamic solidstate fermentation acid hydrolysis, 72
bioreactor (GDSFB), 191–196 alkali method, 72
intensification effects, 93 vs. cellulose, 72
periodic stimulation principle, 92 degree of polymerization, 72
Gas double dynamic solid-state fermentation hydrolysis, 49
(GDSSF) technology product development, 73
breathing solid-state bioreactor, pyrolysis, 106–107
195–196, 196f structure, 71–72
cellulase productivity, 192, 193t sugar platform establishment, 71–73
characteristics, 192–194 Hemp
process, 194–195 advantages, 231
Gasification chemical degumming methods,
alkali metal content, 115 231–232
ash content, 115, 115t hemp fiber, 232–233
chemical reaction equations, 114 organic fertilizer, 234
vs. combustion, 112 pectin recycling, 233–234
definition, 101, 112 utilization, 231, 232f
devices, structures and reaction zones, xylooligosaccharide, 233–234
112–114, 113f Hemp fiber
equivalent ratio, 114 ecological board, 232–233
gas quality, 114 organic fertilizer, 234
oxidation stage, 113 pectin recycling, 233–234
pyrolysis stage, 112 xylooligosaccharide, 233–234
reduction stage, 113 Herbaceous fiber, 9
tar content, 114–115, 115t Herbaceous plants, biorefinery modes
Gasifier types and features, 112, 113t agricultural straw biorefinery, 220–228
Gas-phase explosion technology, mixed bamboo, 228–230
medium hemp, 231–234
description, 62 Heterogeneous bioconversion property,
Ephedra spp., 62 stalk, 38
features, 62 High-boiling ethanol method, 80
Glyoxylic acid, 144 High-boiling solvent lignin, 80
Gramineous plants, 221 High-performance liquid chromatography
Green economy, 247–248 (HPLC), lignocellulosic materials, 31
Index 257
Hydraulic carding fractionation equipment. Lignin

See Paul screening instrument agricultural field application, 81–82
Hydrogen analytical, 78
application and market, 137–138 blending modification, 83
detection, 34 carbon content, 83
high cost, 138–139 carbon fiber, 83–84
modern economy and sustainable vs. cellulose and hemicellulose, 76
development, 138–139 description, 75–76
Hydrogenated deoxidization, 109–110 feed binding agent, 81
Hydrolysate, 149 fertilizer modifier, 81
Hydrolysis history, 76
cellulose, 20 industrial, 78–80
hemicellulose, 49 liquid film, 81–82
stalk, 38 pesticide release agent, 81
polymerization reaction with monomer
I polymer materials, 82–83
Indirect liquefaction process, 116 separation reagents and applications,
Industrial lignin 76–77, 77t
alkali lignin, 79 soil ameliorant, 82
enzymatic hydrolysis, 80 structure, 76, 77f
Kraft lignin, 79 Lignocellulose biomass, 147–148
organic solvent lignin, 80 Lignocellulose biorefinery
steam exploded lignin, 80 conversion engineering, 13–14
Integrated industrial chains difficulties of bulk product development,
agricultural straw biorefinery, 220–228 249
bamboo, 228–230 feedstock engineering, 13
marijuana, 231–234 fractional orientation conversion
Intermittent steam explosion device, 188 process, 15
Intracellular water, 88–89 high manufacturing cost, 249
Isoflavones, 241f immature key technology, 249
inferior product performance, 249
integration process, 15–17
K
lack of technology integration, 250
Klason lignin, 78 limited industrial products, 249
Knudsen diffusion, 172 necessity, 10–12
Kudzu poor equipment, 250
advantages, 240 process engineering, 14–15, 14f
ecoindustrial chain, 240 product engineering, 14
ethanol production, 241f small-scale industrialization, 250
isoflavones, 241f theoretical basis, 12
moisture content, 239–240 Lignocellulose board
starchy feedstock, 240 application and market, 154–155
cellulose recombination and molding
L technology, 155–156
Leaf transpiration, 25–26 green building material, 155
Levulinic acid (LA) green tackifier, 155
necessity and problems, 146–147 natural forest protection project, 155
prepared from steam explosion, 147f thermocuring, 155–156
sugar-based building blocks, 146 xylose extraction, 156f
258 Index
Lignocellulose recalcitrance Mechanical combing classification devices,

cell wall level, 22 57–58
description, 20–21 Mercury intrusion method, porous structure
structural analysis, 21–22 determination, 31–32
terminology, 20–21 Methane, SRI 8610C gas chromatography
Lignocellulose transfer structure system, 34
apoplastic pathway, 25–26 3-Methoxy-4-hydroxybenzaldehyde.
bulk flow, 26 See Vanillin
diffusion, 26 Methyl-tetrahydrofuran (MTHF), 146
leaf transpiration, 25–26 Microbial basic nutritional elements, 88
symplast pathway, 25–26 Milling wood lignin, 78
volume flow rate of water, 26–27 Minerals crisis, 2
Lignocellulosic resources Moderate liquefaction, 118–121
agricultural straw applications, 10, 11f Moisture stratification, 174
characteristics, 6–7 Molecular diffusion, 169
classification, 6 Molecular level selective fractionation
energy utilization, 7–8 technology, 38–39
material utilization, 8–10 Monitor and control generated system
Lignosulfonate, 79–80 (MCGS)
Liquefaction technology automatic control interface, 203, 204f
definition, 116 controlling program script, 203
direct, 116–118 definition, 202
indirect, 116 operation records and process analysis,
moderate, 118–121 203, 204f
phenol, 119 real-time database, 202–203
polyhydric alcohol, 119–121 user window, 202–203
usage, 121 Monosaccharides, 34
Liquid fermentation, solid phase
enzymolysis, 95–96 N
Liquid hot water method. See Autohydrolysis
Natural bamboo fiber, 228–229
method
Natural resources
5-L laboratory steam explosion device,
definition, 1
188, 189f
nonrenewable, 1
Long fibers, 9, 15, 16
renewable, 1, 2f
Low-carbon economy, 247–248
Needlebush, 235
Low-carbon lignocellulose refining project,
Nitrogen adsorption method, porous
248
structure determination, 31–32
Low-pressure and pollution-free steam
Nonfood lignocellulosic material resources, 7
explosion technology, 58–61
NSSSFS system, 93–95, 94f
M Nutrition, 88
Marsh gas, 135–136
Mass balance, 227 O
Mass transfer Oligosaccharides, 233
parameters, biorefinery process, 32 Organic acids, 143f
porous media, 27, 169 Osmosis, 26
Material utilization, lignocellulose, 8–10 Oxalic acid
MCGS. See Monitor and control generated carbohydrate oxidation method, 144
system (MCGS) carbon monoxide coupling method, 144
Index 259
ester compounds, 144 Pyrolysis

glyoxylic acid, 144 bio-oil characteristics, 107–109
novel technology, 144–145 cellulose, 105–106
potassium oxalate, 143–144 definition, 101
sodium formate method, 144 fast pyrolysis, 101–102
steam-explosion pretreatment, 145f heating rate, 103–104
hemicelluloses, 106–107
lignin, 107
P lignocellulose and coal co-firing, 102
Papermaking raw materials, 9 lignocellulose pyrolysis reactor, 103
Paul screening instrument, 188–189, 190f performance, 105–107
Penicillium decumbens, 208 pressure, 104
Pennisetum hydridum, 212–215 products, 102–103, 107–109
Perennial plants, 9 temperature, 104–105
Petroleum refining
vs. biorefinery, 125–126 Q
description, 125 Quercetin-3-O-rhamnoside, 242
schematic illustration, 126f
Phase change, 173 R
Phenol liquefaction, 119
Physical conversion technologies Refinery, 11
building materials, 99 Refining lignocellulosic feedstock, 13
ecological plank, 100–101 Renewable fuels, 248
man-made board, 98–99 Renewable resources, 1, 10
mechanisms, 98 Resources
solid fuel, 98 classification, 1
wood-plastic composites, 99–100 crisis, 2–3
Pilot plant, 206–207 definition, 1
completeness, 207 issues, 1–2
pilot scale, 206 recycling, 3
Piping and instrument diagram (PID), 209 Rhus chinensis, 241
Plant biomass, 221
Plant lignocellulose, 21 S
Pollution-free steam explosion technology, Sachs’s convenient classification, 40
152 Scanning electron microscope (SEM), 31–32
Polyethylene plastic film, 81–82 Seepage recalcitrance, 27–28
Polyhydric alcohol liquefaction, 119–121 vs. biomass recalcitrance, 27, 28t
Porous media, 167 lignocellulose interfacial properties, 28
heat transfer process, 169 Selective structure deconstruction
mass transfer process, 169 technologies
Porous structure complete conversion of functionality, 43
cell level, 23 description, 42
cell wall level, 23–24 development trends, 45–47
tissue level, 22–23 hemp material, partial structure
Primary lignocellulosic material refining, deconstruction, 44
development stages, 38 history, 42–44
Process engineering, 14–15, 14f, 167, 168f overall conversion of functionality,
Product engineering, 14 42–43
Pueraria lobata, 239–240 partial functionality, 43–44
260 Index
Selective structure deconstruction hydrothermal pretreatment process, 176t

technologies (Continued) intensity factor, 185–186
strawboard making method, 44–45 physical tearing, 177
straw, partial structure deconstruction, 45 pretreatment and equipment, 186–188
Separate hydrolysis fermentation (SHF), significance of multistage model, 182–185
90–91 Steam explosion treatment technology, 49–50
Short-and long-fiber dry classification capital costs, 70, 70f
equipment, 58f cellular level, 48, 48f
Short cellulose fibers, 16 equipments, 50–58
Short fibers, 15, 16 features, 59
Simultaneous saccharification and hemicellulose hydrolysis, 49
fermentation, 90–91, 93–95 history, 47
Slender fiber, 9 impact factors, 50
Sodium carboxymethyl cellulose (CMC), lignocellulose refining advantages, 68
151–152 low-pressure and pollution-free, 58–61
Sodium formate method, 144 mixed medium, gas phase, 61–62
Softwood physical/chemical structure breakage,
biomass refining, 234 48–49
biorefinery industrial chain mode, 236 pretreatment methods, advantages vs.
characteristics, 235–236 disadvantages, 68–70, 69t
chlorine bleach effluent, 235 principles, 48–50
refining, 234 raw material utilization, 70–71, 71f
traditional application, 234–235 technical evaluation, 67–71
waste liquid in cooking process, 235 two-phase, 63–67
Solid matrix, 175 Stoma, 23
Solid-state fermentation (SSF) process, 88 Stomatal transpiration, 25–26
bacterial cellulose production, 96 Straw and nonwood fiber raw material
biopesticide production, 97 processing equipment, 55f
definition, 191–192 acid-or alkali-leaching process, 56
enzyme production, 97 airflow classified equipment, 57–58
GDSSF, 191–196 knife discs, 55
heat and moisture transfer theory, 173–174 knife rolls, 55
heat transfer mechanism, 173 mechanical combing classification
moisture stratification, 174 devices, 57–58
solid matrix, 175 Paul fiber screening instrument, 57–58
solute transport, 175 press type dryer, 57
vertical distribution maps, matrix roller dehydration unit, 57
water, 171f screw conveyors, 56
water vapor transfer mechanism, 170–173 straw baler, 55–56
xanthan production, 96–97 twin wire extrusion machine, 57
Solute transport matrix, 175 Straw cellulosic ethanol system, 250
SSF. See Solid-state fermentation (SSF) Straw refining industry production line
process cellulose and lignin, 227
Stalk fibers, 9 hydrolysis liquid, 224
Steam exploded lignin, 80 pretreatment process, 224
Steam explosion production route, 224, 225f
based on energy conservation, 177–181 products type, 224, 225f
cellular-level, 177, 178f Submerged fermentation (SMF), 191–192
explosion intensity, 176 Substrate water, 88–89
Index 261
Sugar platform establishment Transition zone diffusion, 172

cellulose, 73–75 Two-phase steam explosion technology,
description, 71 63–67
hemicellulose, 71–73
Sumac, 241–242, 243f U
Sweet sorghum, 129–130 Unbound water, 88–89
Swelling, 88–89
Symplast pathway, 25–26 V
Systemic engineering, biorefinery process
Vanillin, 158–159
basic design, 207–209
Vascular tissue system, 21–23, 40
bioprocess design, 204
concept design, 205
W
ecoindustry, 210
enzymatic hydrolysis and fermentation Waste reuse, 3
fuel, 211 Water binding capacity, 88–89
P. hydridum, 212–215 Water crisis, 2
pilot test, 206–207 Water vapor transfer mechanism, SSF
preliminary evaluation, 205 process, 170–173
technical and economic evaluation, 209 Wheat straw separation process, 59, 60f
Wooden architecture, 8–9
T Wood tar, 141
Thermochemical conversion technology, Woody fiber, 9
101–122. See also Pyrolysis
X
Thermocuring technology, 100
Traditional medicine Xanthan production, 96–97
kudzu, 239–240 Xanthomonas campeseris fermentation,
medicinal plant resources, 242–244 96–97
Rhus resource, 241–242 Xylan, 233–234
Transfer mechanism of water, SSF Xylitol, 73, 156–158
process, 170 Xylooligosaccharide, 157
Transfer principles, 168 Xylose, 156–158
heat transfer process, 169
mass transfer process, 169 Z
solid-state fermentation, 170–175 ZT10-00 Paul screening instrument,
steam explosion process, 176–186 188–189, 190f

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Lignocellulose Biorefinery Engineering

Biodiesel science and technology

AMSTERDAM • BOSTON • CAMBRIDGE • HEIDELBERG

Copyright © 2015 Elsevier Ltd. All rights reserved

No part of this publication may be reproduced, stored in a retrieval system or transmitted in

British Library Cataloguing in Publication Data

Library of Congress Control Number: 2014952430

ISBN 978-0-08-100135-6 (print)

For information on all Woodhead Publishing publications

Typeset by SPi Global

40 Biomass combustion science, technology and engineering

59 Fluidized bed technologies for near-zero emission combustion and gasification

1.1.2 Resource issues and resource crises

Recyclable resources (such as metal deposits)

Natural Geophysical processes (such as wind energy,

Long-term (such as wood)

1.1.2.2 Resource crises

1.2 Resource recycling and waste reuse

Recycling of resources is the comprehensive development of natural resources, full utili-

1.2.2 Waste reuse

1.2.3 Biomass recycling

1.2.4 Eco-industrial systems and eco-industrial parks

Figure 1.2 Energy recycling model for the agricultural industry.

1.3 Lignocellulosic resources

1.3.2 Characteristics of lignocellulosic resources

1.3.3 Utilization history of lignocellulosic resources

1.3.3.1 History of lignocellulose utilization for energy

1.3.3.2 History of lignocellulose utilization for materials

(1) Accessibility; easy processing.

1.3.4 Current situation of lignocellulose utilization

1.4 Lignocellulose biorefinery engineering

Lignin modified phenolic resin adhesive, lignin

Fertilizer Cellulose based Paper, cardboard, viscose fiber, carboxymethyl

Coumaric acid, ferulic acid, vanillin,

Industrial raw Bio-based Cellulose Glucose fermentation products, oxalic

Hemicellulose fermentation products,

Mushroom Pyrolyzation Bio-oil

Fermentation Methane, bioethanol, biobutanol

Figure 1.3 Applications of agricultural straw lignocellulose.

lignocellulose were inefficient and uneconomical, but it is undeniable that lignocel-

development of lignocellulosic resources, forming the new biorefining concept. The

1.4.2 Key points of lignocellulose biorefinery engineering

1.4.2.2 Feedstock engineering for lignocellulose biorefining

1.4.2.3 Conversion engineering for lignocellulose biorefining

Ecological industry and circular economy

Intermediate Conversion Products

Figure 1.4 Lignocellulose biorefinery process engineering.

the end-product, the appropriate component or structure can be selected by using

1.4.2.4 Product engineering for lignocellulose biorefining

1.4.2.5 Process engineering for lignocellulose biorefining

1.4.2.6 Modes of integrated industrial lignocellulose

Straw Chop Rehydration Steam explosion Water extraction

Enzymatic Extract Coarse

Fermentation Ethanol Digested Filter

Lignocellulosic biomass is often described as “recalcitrant.” This term is used

The term recalcitrance also describes the resistance properties of lignocellulosic

2.1.2 Structural analysis of lignocellulose recalcitrance

2.2 Lignocellulose porous medium

2.2.1 Porous structure at the tissue level

2.2.2 Porous structure at the cell level

2.2.3 Porous structure at the cell wall level

Figure 2.1 Cell wall surface of the

Tissue Rectangular 20–35 Cell Pit 0.5–50.0

6¢¢(Ф150) 0.75 0.45 35–90 45

12¢¢(Ф150) 0.75 0.45 45 233