Journal of Cleaner Production 268 (2020) 122357

Contents lists available at ScienceDirect

Journal of Cleaner Production

journal homepage: www.elsevier.com/locate/jclepro

Review

Past practices and current trends in the recovery and purification of

first generation ethanol: A learning curve for lignocellulosic ethanol
Sonu Saini a, Anuj K. Chandel b, Krishna Kant Sharma a, *
a
Laboratory of Enzymology and Recombinant DNA Technology, Department of Microbiology, Maharshi Dayanand University, Rohtak, 124001, Haryana,
India
b ~o Paulo, 12.602.810, Saeo Paulo, Brazil
Department of Biotechnology, Engineering School of Lorena, University of Sa

a r t i c l e i n f o a b s t r a c t

Article history: Due to the negative health and environmental consequences of fossil fuels, lignocellulosic ethanol has
Received 8 February 2020 garnered a great interest as a clean and potent renewable energy resource. The presence of excess
Received in revised form amount of water hinders the application of ethanol produced, necessitating the implication of robust
10 April 2020
recovery and purification techniques. Typically, ethanol recovery starts with a conventional distillation
Accepted 16 May 2020
Available online 20 May 2020
process yielding azeotropic ethanol. Further, dehydration and purification steps are employed to achieve
fuel-grade ethanol, which consumes tremendous amount of energy and incur high operational cost;
Handling editor: Prof. Jiri Jaromir Klemes eventually limits the economic feasibility of lignocellulosic ethanol on commercial scale. Therefore, to
overcome such obstacles, the synergetic application of distillation or adsorption with membrane-
Keywords: mediated processes seems to be a promising approach in terms of energy conservation, cost-
Ethanol effectiveness, and environmental security. In this review article, we have made an appraisal of the
Distillation past and current purification and recovery technologies for first generation ethanol, which can be a
Dehydration learning trend for the recovery of lignocellulosic ethanol from the fermented broth, with desired purity.
Lignocellulosic biomass
© 2020 Elsevier Ltd. All rights reserved.
Downstream technologies
Hybrid separation process

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Bioethanol production methodologies: a brief appraisal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
3. Ethanol downstream: recovery and purification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3.1. Ethanol pre-concentration: distillation process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3.2. Ethanol dehydration: challenges and mitigation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3.2.1. Azeotropic distillation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3.2.2. Extractive distillation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.2.3. Membrane processes: genuinely effective approach . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.2.4. Adsorption process: advancing the ethanol separation and purification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
4. Current challenges and emerging technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
5. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
Declaration of competing interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

* Corresponding author.
E-mail address: [email protected] (K.K. Sharma).

https://doi.org/10.1016/j.jclepro.2020.122357
0959-6526/© 2020 Elsevier Ltd. All rights reserved.
2 S. Saini et al. / Journal of Cleaner Production 268 (2020) 122357

1. Introduction

During the last century, energy consumption has increased

steadily with the exponential rise in global population and indus-
trialization (Gebregergs et al., 2016; Nizami et al., 2017; Saini et al.,
2020). Fossil energy sources such as oil, coal, and natural gas have
been the major non-renewable resources to fulfil the increased
energy demand (Ellabban et al., 2014). The persistent diminution of
fossil fuel due to the increased energy expenditure and emissions of
greenhouse gases have led to acquire an alternative, environment-
friendly, renewable, and sustainable energy sources (de Oliveira
Ribeiro et al., 2018; Pant et al., 2016). The renewable fuel sources
are principally originated from sugars, starch, and lignocellulosic
materials (Zabed et al., 2017). Sugars (first and second generation)
are extensively used for bioethanol production (Wu et al., 2017;
Zhang et al., 2017); whereas vegetable oils and microalgae are
utilized for biodiesel production (Kinnal et al., 2018; Qari et al.,
2017). Among the renewable energy sources, bioethanol has been
widely accepted as an alternative fossil fuel (Molino et al., 2018). On
an industrial scale, bioethanol production depends upon the Fig. 1. Reports published on lignocellulose processing (lignocellulosic pretreatment,
availability of substrates such as sugarcane, corn, and lignocellu- saccharification, and bioethanol production), and dehydration of ethanol from 2010 to
losic biomass (agro-residues, dedicated energy crops, and forest- 2019.

residues) (Chandel et al., 2018).

The lignocellulosic biomass is complex in nature; therefore, the
production of bioethanol is achieved by appropriate pretreatment, required to separate, distillate, and concentrate anhydrous fuel
saccharification, and fermentation (Hsu, 2018). Pretreatment is grade second-generation ethanol.
required to alter the chemical composition and structure of the
lignocellulosic biomass that increases the accessibility of available
carbohydrate content (Saini et al., 2020). Hydrolysis of lignocellu- 2. Bioethanol production methodologies: a brief appraisal
losic polysaccharides into fermentable sugars (glucose, xylose,
arabinose, galactose, and mannose) are usually catalyzed by the Lignocellulosic biomass is the most abundant biopolymer pre-
action of mineral acids or carbohydrate degrading enzymes sent on the earth with an annual production of 1012 tons per year
(CAZymes) (Chutani and Sharma, 2015; Tian et al., 2018). Baker’s and could serve as a promising raw material for the production of
yeast or Saccharomyces cerevisiae has been frequently used to second-generation bioethanol and biochemicals (da Silva et al.,
ferment hexose sugars to bioethanol (Baeyens et al., 2015; Gupta 2018). Generally, about 60e80% of total bioethanol production
et al., 2009). Typically, lignocellulosic ethanol is produced in costs derive from the feedstock (Vohra et al., 2014). The cost of
diluted form in industries (4e10 wt % ethanol), which requires converting corn grains, sugar beets, and sugarcane into ethanol was
robust purification and concentration steps to achieve fuel-grade estimated to be approximately $1.03, $2.35 and $0.81 per gallon
ethanol (FGE) (Cesaro and Belgiorno, 2015; Kang et al., 2014). ethanol, respectively (Salassi, 2007; Haankuku et al., 2015).
Generally, ethanol concentration in the first and second-generation Recently, a biofuel research group from the USA reported the eco-
biofuel is about 17 wt % and 4 wt %, respectively (Kang et al., 2014; nomic analysis of bioethanol production from certain non-woody
Vane, 2006). Low ethanol concentration in second-generation lignocellulosic biomass ranges from $1.91 to $3.48 per gallon
biofuel is due to the low sugar content and composite nature of ethanol (Cheng et al., 2019). However, on a global scale, it is difficult
lignocellulosic hydrolysates (Lassmann et al., 2014). Therefore, the to figure out an accurate economic analysis of ethanol production,
energy investment for the recovery of second-generation ethanol is because of the disparity in feedstock price among different coun-
higher in comparison to first-generation biofuel (Dias et al., 2012). tries. The ethanol production from sugarcane, corn grain, and sugar
The quality, concentration, energy input, and production cost of beets seems to be more economically feasible in comparison to
ethanol predominantly depends upon the production conditions lignocellulosic biomass. However, some of the nations may have
and recovery process. the food and feed concerns, which limits the utilization of these
Lignocellulosic ethanol is separated using a distillation process feedstock’s for bioethanol production. Therefore, the lignocellulosic
to produce azeotropic ethanol; containing 5e10% of water biomass is a promising substitute to corn grains, sugarcane juice or
(Michaels et al., 2018). About 60e80% of total energy is required to molasses and sugar beet juice because it mitigates the issues of food
produce azeotropic ethanol from the virgin fermented broth (Galbe and energy security associated with diverting edible food for bio-
et al., 2013). Subsequently, the azeotropic ethanol is dehydrated by fuels production (Ahorsu et al., 2018). A variety of underutilized
different dehydration techniques to the desired ethanol content of lignocellulosic biomass has been explored for bioethanol produc-
99.5 wt % (Lassmann et al., 2014). tion such as rice straw and husk, corn stover, switchgrass, sugar-
In the past few years, a significant number of peer reviewed cane bagasse or straw, and paper-waste (Cho et al., 2020). The usage
papers have been published on lignocellulosic pretreatment, of non-woody lignocellulosic biomass is not only beneficial for
saccharification and fermentation processes for the production of biofuel purposes, but it also mitigates the environmental pollution
lignocellulosic ethanol; however, very few reports have been issues associated with their burning and disposal. The selection of
published on the distillation or dehydration of lignocellulosic raw material mainly depends upon the types of agricultural waste
ethanol from fermented broth (Fig. 1). Evidently, the area of produced. Therefore, the Asian countries with a huge production of
downstream and separation technologies has always been rice can utilize rice straw as feedstock; whereas countries like the
neglected both at science and technical upfront. Therefore, this USA and Brazil producing sugarcane and corn can work on their
review article is more focused on the available technologies respective residues for bioethanol production.
 S. Saini et al. / Journal of Cleaner Production 268 (2020) 122357 3

The chemical composition and recalcitrant nature of lignocel- (Mohd Azhar et al., 2017). Therefore, strategies like simultaneous
lulosic biomass develop resistance to enable cellulosic sugars saccharification and fermentation, separate hydrolysis and
accessible for microbial fermentation for ethanol production fermentation, simultaneous saccharification and co-fermentation,
(Ciolacu, 2018; De Bhowmick et al., 2018). Therefore, pretreatment on-site cellulases production, consolidated bioprocessing (Tri
methods using acids, alkali or microorganisms are required to et al., 2018), and integrated bioprocessing have been used to
reduce the recalcitrance nature of the biomass and easily convert reduce the process cost (Kumar et al., 2017). Moreover, recombi-
the polymeric sugars into monomers (Hassan et al., 2018), which nant microbial strains having pathways for both pentose and hex-
can be readily converted into biofuels, biochemicals, and bio- ose utilization have been employed to maximize ethanol yield
materials under biorefinery concept. The pretreatment process (Kobayashi et al., 2018). Unfortunately, past practices and current
helps in the delignification (Wu et al., 2019), hemicelluloses solu- research are mainly focused on the substrate pretreatment meth-
bilization (Chu et al., 2018), reduction in the cellulose crystallinity odologies, and ethanol production routes; whereas, downstream
(Williams et al., 2018), fractionation of the biomass (Cheng et al., purification strategies are comparatively overlooked. Therefore, a
2018), and increase the porosity and surface area of the carbohy- cost-competitive process to recover high-quality ethanol from
drate polymers (Chiaramonti et al., 2012). The pretreatment fermentation broth also needs due attention.
methods employed to produce lignin-free polysaccharides are
categorized under physical (Karimi and Taherzadeh, 2016), chem- 3. Ethanol downstream: recovery and purification
ical (Cheng et al., 2018), physicochemical (Kim, 2013), and biolog-
ical methods (Moreno et al., 2015; Wagner et al., 2018). A superior Lignocellulosic ethanol is produced in the diluted form; there-
pretreatment method must optimize the sugar yield and avoid fore the water and other impurities need to be removed to achieve a
inhibitors formation, i.e., furans, formic acid, and lignin derived fuel-grade ethanol product (Aditiya et al., 2016; Lassmann et al.,
phenolics which can inhibit the enzymatic hydrolysis and 2014). Recovery of bioethanol can be accomplished at different
fermentation processes (Jo € nsson and Martín, 2016). The complex temperature zones: (i) at or near fermentation temperature; (ii)
polysaccharides are further hydrolyzed into fermentable sugars slightly elevated than fermentation temperature that neither
using acid (Gupta et al., 2009) or synergetic application of hol- harms the microorganisms nor inhibits enzymes activities; (iii) a
ocellulolytic enzymes (Pino et al., 2018). Enzymatic hydrolysis is temperature deleterious to microorganisms, but safer for enzymes;
more advantageous over acid hydrolysis methods due to less en- and (iv) a temperature which is deleterious to both microorganisms
ergy requirements, low toxicity, and negligible inhibitors formation and enzymes (Vane, 2008). The temperature of recovery and sep-
(Saini et al., 2020; Verardi et al., 2012). Conversion of cellulose to aration technologies depends upon the saccharification and
glucose requires complex cellulase system (endoglucanase, exo- fermentation processes. Therefore, the optimum temperature for
glucanase, b-glucosidase, cellulosomes, xylanosomes and lytic the separation process would be the same as that of bioreactor; to
polysaccharide monooxygenases) (Chutani and Sharma, 2016; make the process more economically feasible avoiding the expen-
Khare et al., 2015), whereas the complete hydrolysis of hemi- diture to increase or decrease the temperature. Ethanol recovery
celluloses requires at least eight enzymes, such as endoxylanase, and purification strategies are categorized under the conventional
exoxylanase, b-xylosidase, a-arabinofuranosidase, a-glucuronidase, recovery system (distillation) and non-conventional system (Serra
acetyl xylanesterase, xylanosomes, and ferulic acid esterase et al., 1987). The non-conventional systems were proposed as an
(Chutani and Sharma, 2015). Thereafter, enzymatic hydrolysates alternative for ethanol recovery with energy reduction and cost
containing fermentable sugars are subsequently fermented to investments such as pervaporation, adsorption, and other alterna-
produce ethanol by the action of microorganisms (Guerrero et al., tive hybrid processes (Zentou et al., 2019). The non-conventional
2018; Saini et al., 2020). Amount of sugars, i.e., hexoses (glucose) methods were principally developed during the 70’s and are
and pentoses (xylose and arabinose) in the enzymatic hydrolysates frequently used in laboratory or pilot plants; rarely used at indus-
depend upon the lignocellulosic biomass, pretreatment, and hy- trial scale (Teye, 2009). Therefore, there is an urgent need to review
drolysis methods employed (Gandla et al., 2018). Saccharomyces and update these technologies to implement them on industrial
cerevisiae, and Zymomonas mobilis can only use C6 sugars (Wang scales and meet the expectations.
et al., 2018); whereas, Pichia stipitis (Scheffersomyces stipitis) Distillation, the initial purification step yields 37 wt % ethanol
(Demiray et al., 2018), Candida shehatae (Scheffersomyces shehatae) stream with the generation of solid residues holding most of the
(Koti et al., 2016), and Pachysolen tannophilus (Seo et al., 2009) have water content (Balat et al., 2008; Michaels et al., 2018). The solid
the ability to use both C5 and C6 sugars for the production of residues are centrifuged, and about 25% are recycled to the
ethanol, but with a slow production rate. Therefore, to increase the fermentation process (Koza, 2012; McAloon et al., 2000). Whereas,
ethanol yield; genetically modified microorganisms with genes for the pre-concentrated ethanol (37 wt %) is further purified to
xylose reductase, xylitol dehydrogenase, and xylulokinase have azeotropic ethanol using a rectifying column (Hamelinck et al.,
been used (Kwak and Jin, 2017). 2005). Subsequently, ethanol is concentrated (99.6 wt %) to form
Each step in the ethanol production and purification route has anhydrous ethanol using different dehydration techniques namely,
some limiting factors that affect the cost of the whole process (De azeotropic distillation (DiBiasio, 2015; Gomis et al., 2015), adsorp-
Bhowmick et al., 2018). Currently, research is focused on the tion (Frolkova and Raeva, 2010; Tajallipour et al., 2013), extractive
methods aiming to increase fermentable sugars recovery, decrease distillation (Huang et al., 2008), pervaporation, and membrane
inhibitory products, minimize the use of chemicals that are harmful processes (Mulder et al., 1983; Singh and Rangaiah, 2017a).
to the environment, minimize energy input and reduce the for-
mation of by-products, for overcoming the pretreatment obstacles 3.1. Ethanol pre-concentration: distillation process
(Chandel et al., 2019; Kumari and Singh, 2018). Similarly, many
efforts have been made to produce low-cost cellulases and xyla- Typically, crude fermented broth from lignocellulosic biomass
nases with high efficiency, which could minimize the production has more than 80 wt % water (Surriya et al., 2015) and lower
cost of cellulosic ethanol (Srivastava et al., 2018). The fermentation product concentration (approximately 5 wt %) (Hamelinck et al.,
process also includes some challenges, such as co-fermentation of 2005; Kang et al., 2014). The extraction of lignocellulosic ethanol
xylose and glucose, bacterial contamination during fermentation, is achieved by two modes viz., end-of-pipe removal and slip-stream
and low tolerance of yeast at a higher concentration of ethanol removal (Guidoboni, 1984). ‘End-of-pipe’ removal is generally
4 S. Saini et al. / Journal of Cleaner Production 268 (2020) 122357

employed after the completion of fermentation and the ethanol et al., 2008). Yet, it possesses several limitations, such as (i)
rich stream is subsequently purified or centrifuged in case of significantly higher energy requirement due to low ethanol con-
cellulosic ethanol (Serra et al., 1987). Whereas in ‘slip-stream’ centration (4%); (ii) unable to bring desired product dryness
removal, ethanol is recovered during the fermentation process and (Vane, 2008). Therefore, considering these obstacles, further puri-
ethanol depleted stream is then returned to the bioreactor (Wooley fication steps are required; therefore it is further discussed under
et al., 1999). Most of the ethanol producing yeasts are inhibited by dehydration processes.
ethanol concentration above 5%, and a few can produce ethanol
around 10%, but with a low productivity. Therefore, to enhance the
3.2. Ethanol dehydration: challenges and mitigation
productivity, slip-stream removal process can be employed to
extract ethanol continuously which eventually reduces the nega-
Separation of ethanol-water azeotrope cannot be accomplished
tive effect on the fermentation process (Jitesh et al., 2000; Nguyen
by conventional or modern distillation system. The extremely
et al., 2009).
strong hydrogen bonds between ethanol and water molecules
Pre-conditioning steps such as degassing, heating, and solids
hinder the separation of azeotropic mixture (Mahdi et al., 2015).
removal are mainly required prior to ethanol recovery, thus
The boiling of ethanol-water mixture results in the vapour forma-
increasing the cost and process complexity. For most of the cases,
tion, having proportionate constituents as the original mixture.
distillation is the vastly recognized industrial purification process
Therefore, azeotropic mixtures require special methods to facilitate
employed to segregate volatile fermentation products. Separation
the separation; such method utilizes the addition of entrainer to
of ethanol and water from fermentation broth is based on their
alter the relative volatilities of the components; or applies the
boiling points, i.e., ethanol with a boiling point 78.2
C is vaporized
specific membranes or molecular sieves, which allow the passage
first (Balat et al., 2008). Liquid mixture drifts continuously through
of certain constituents. In the past few decades, various entrainers,
the beer column, thus separates most of the ethanol from water;
membranes, molecular sieves, and adsorbents have been used for
producing a top ethanol stream, and a bottom stream of water
the ethanol dehydration (Fig. 3). These dehydration processes
(Karuppiah et al., 2008). To facilitate the separation of ethanol,
possesses certain pros and cons; therefore, the commercial appli-
modern distillation system is made up of three separation columns;
cation of the technology depends upon the generation of bio-
distillation column, rectifier column, and bottom stripper (Fig. 2).
ethanol produced, availability of entrainer, and the purity of
Stripping and rectification columns are availed to produce azeo-
product required (Table 1).
tropic ethanol that improves heat integration and reduces energy
expenditure as well as the capital cost of the process (Van der Ham
and Kjelstrup, 2011). 3.2.1. Azeotropic distillation
Ethanol purification is an energy-intensive process and a large Azeotropic distillation facilitates the separation of azeotropic
fraction of energy is consumed to concentrate the ethanol up to mixtures into their pure constituents. This method involves the
95.6 wt % (Nagy et al., 2015). The amount of energy required for the addition of a volatile component called entrainer, which forms a
distillation process depends upon the final quality of the ethanol ternary azeotrope to accelerate the separation of the desired
product. Moreover, energy requirement also increases with a component (s). Modification in the volatilities of component and
decrease in the concentration of the ethanol in the feed stream the distillation equilibrium must be achieved by the addition of
(Madson and Lococo, 2000). Conventional distillation method re- entrainer to extract anhydrous ethanol. Azeotropic distillation
quires around 8.0 MJ-fuel/kg-ethanol heat energy to produce system typically consists of two distillation columns; (i) modern
azeotropic ethanol (Serra et al., 1987); whereas, an advanced distillation column, and (ii) azeotropic column (Fig. 4). Basically,
distillation system consumes only 4.5 MJ-fuel/kg-ethanol heat en- ethanol is concentrated up to 92.4 wt % in a modern distillation
ergy (Lynd et al., 1996). Further reduction in energy consumption to column and sent to an azeotropic column for further purification. In
about 3.4 MJ-fuel/kg-ethanol has been achieved using a modern an azeotropic column, purified ethanol (>99 wt %) exits as a bottom
distillation system (Díaz and Tost, 2017). Though, distillation is a stream, while the top stream is rich in water vapour, solvent, and
well-known recovery technique in the ethanol industries (Onuki small amounts of ethanol. Further, the top stream is divided into an
organic phase (rich in ethanol-entrainer), and the aqueous phase

Fig. 2. Modern distillation system producing azeotropic ethanol from crude fermented broth.
 S. Saini et al. / Journal of Cleaner Production 268 (2020) 122357 5

Fig. 3. Historical timelines of ethanol dehydration technologies evolved from 1985 to 2019.

Table 1
Advantages, disadvantages, and commercial applications of different ethanol dehydration technologies.

Separation Principle Advantages Disadvantages Author’s view Commercial applications

process (Country)

Azeotropic Addition of a volatile Low ethanol stream (2e10 wt Requires a higher amount of Suitable process for the purification Around 60% of Brazilian
distillation entrainer to form a ternary % ethanol) can be purified to entrainer and high energy of lignocellulosic ethanol and some industries of
azeotrope fuel grade ethanol investment USA using cyclohexane
Extractive Addition of a high boiling Offers a number of entrainer High price of ILs and hyper- Need to develop a better extractant More than 100 industrial
distillation point entrainer to modify viz., solvents, salts, ionic branched polymers and high using combination of various salts towers in China and few
the volatility of ethanol- liquids, and hyper-branched energy requirements and liquids solvents for higher of USA using ethylene
water polymers efficiency. glycol
Membrane Separation is based on the Cost-effective, energy saving, Membrane blockage due to Need to develop advance 62 plants in Europe, South
separation permeability of and environmental benign bio-macro-molecules membranes that are resistant to high East Asia, Canada, and
membranes process. pollution and short life span. temperature with Germany
Adsorption Molecular sieves with a Starch and cellulose based High price of the available Novel adsorbents can be made using Most of the USA
process specific pore size adsorbent from renewable adsorbent and low capacity to lignocellulosic or other waste industries using
source. stand over a high ethanol product molecular sieves
stream.

(rich in water-entrainer) (Luyben, 2006). The organic phase is ethylene glycol (Kiss et al., 2012). Previously, benzene and cyclo-
subsequently processed in a decanter to recover ethanol, while the hexane have been extensively exploited; of these benzene has been
aqueous phase is sorted out in the entrainer mixing column to discontinued due to its carcinogenic nature (Pla-Franco et al., 2014).
reuse entrainer (Huang et al., 2008). However, a considerable Azeotropic distillation is a less applied method due to the disad-
amount of entrainer is required to achieve the desired purity level vantages of high energy investment and capital cost along with
of ethanol, therefore, increases the energy expenditure and capital health and safety issues while working with carcinogenic (ben-
cost (Chen, 2015). zene) and flammable (cyclohexane) solvents. Therefore, to alleviate
Previously, cyclohexane has been exploited as an entrainer to these drawbacks, several scientific groups have switched the path
obtain anhydrous ethanol from a starting feed of 2.69 wt % ethanol towards the usage of less toxic and high boiling point entrainers;
(Zhang et al., 2009). The energy requirements for the dehydration consequently, evolved the extractive distillation.
of ethanol were found as 4.2 and 5.4 MJ-fuel/kg-ethanol for the
starting feed of 10 wt % and 6 wt % ethanol, respectively (Vane,
3.2.2. Extractive distillation
2008). Earlier, studies revealed that energy requirements for
In extractive distillation, the relative volatility of ethanol-water
ethanol dehydration were about 8.5 MJ-fuel/kg-ethanol using
mixture is modified by adding some high boiling point solvent,
benzene as an azeotropic agent (Hutahaean et al., 1995). A superior
which facilitates the separation of an azeotropic mixture
azeotropic agent has several advantageous properties such as;
(Meindersma et al., 2016). The low amount and partial evaporation
inexpensive, non-toxic, chemically stable, non-corrosive, low vis-
of entrainer in contrast to azeotropic distillation make extractive
cosity and ease to recover from the liquid stream (Rodriguez
distillation a more feasible process in terms of both energy
Rodriguez, 2016). Therefore, many azeotropic agents have been
expenditure and capital cost (Lei et al., 2005). High boiling solvents
used in azeotropic distillation such as acetone, ethyl acetate,
have been always considered to be more propitious for ethanol
toluene (Waldron, 2010), isooctane (Gomis et al., 2007), diethyl
dehydration (Lei et al., 2014). The cost of the process depends upon
ether (Oliveira et al., 2016), hexane (Gomis et al., 2015), n-heptane
the type of solvent used such as volatile liquid solvents (Dai et al.,
(Udeye et al., 2009), n-pentane, cyclopentane (Berg, 1998), ben-
2014), solid salts (or dissolved salts), hyperbranched polymers
zene, cyclohexane (Gomis et al., 2007; Sun et al., 2011), and
(Seiler et al., 2003), a mixture of liquid solvents and solid salts (Lei
6 S. Saini et al. / Journal of Cleaner Production 268 (2020) 122357

Fig. 4. Schematic presentation of the azeotropic distillation process to produce anhydrous ethanol along with entrainer recovery system.

et al., 2003), and ionic liquids (Lei et al., 2014). Irrespective of en- hyperbranched polymers as extractants for ethanol dehydration
trainers, the extractive distillation system works on the similar (Al-Amer, 2000; Seiler et al., 2004; Peleteiro et al., 2015). Specific
principle; where fermented broth is concentrated in the modern properties of hyperbranched polymers such as low viscosity and
distillation column; ethanol dehydration and recovery of entrainer thermal stability make them feasible for separating azeotropic
is carried out using extractive column and solvent recovery column, mixture; therefore, poly-ethylene-glycol and poly-acrylic acid have
respectively (Fig. 5). been adapted as extractants (Al-Amer, 2000). However, on an in-
Previously, extractive distillation using volatile or semi-volatile dustrial scale, hyperbranched polymers are rarely used due to their
liquid solvent as an entrainer has been experimented for ethanol high prices (Seiler et al., 2004). Like hyperbranched polymer, ionic
dehydration (Zhao et al., 2017). Different liquid solvents have been liquids (ILs) are the novel separating agents used for ethanol
evaluated in extractive distillation viz., ethylene glycol (Gil et al., dehydration (Dai et al., 2014). ILs offers significant advantages; high
2014; Ravagnani et al., 2010), diethyl ether, toluene (Amarasekara, separation ability, high thermal and chemical stability, less corro-
2013; Soccol et al., 2016), and furfural (Berg and Yeh, 1985). siveness, low melting points, and superior solvent capacity for both
Among all, ethylene glycol was found to be the most frequently polar and non-polar components (Gutierrez Hernandez, 2013).
used liquid solvent, which possess the characteristics of extracting Several scientific groups from different countries have studied the
highly pure ethanol (Benyahia et al., 2014). However, there are few energy investment and performance of various ILs as separating
drawbacks of extractive distillation; (i) high liquid solvent to feed agents (Dai et al., 2014; Meindersma et al., 2012; Orchille s et al.,
ratio (5:1) (ii) high energy consumption and capital cost. To over- 2009; Tian and Row, 2013; Wasserscheid et al., 2002). A compar-
come the limitations, different salts have been exploited as an ative study of energy investment for liquid solvent (ethylene glycol)
entrainer in extractive distillation (Mahdi et al., 2015). A minimal and IL (1-ethyl-3-methylimidazolium dicyanamide) revealed that
amount of salt has the potential of enhancing the volatility of some IL is 16% more energy-efficient (Meindersma et al., 2012). Although,
volatile components, thus facilitates the separation (Aditiya et al., extractive distillation using various entrainer has specific advan-
2016). The characteristic features of salt used for separation tages but also possesses certain disadvantages such as complexity
include low toxicity, recyclability from the mixture, non-corrosive, and cost of entrainer. Therefore, future research should be focused
and safe in handling and transportation. The frequently used salts on experimenting combination of different salts and solvents to
for ethanol dehydration include potassium acetate (Ligero and make the process efficient at the industrial scale.
Ravagnani, 2003), sodium acetate (Furter, 1993), calcium chloride
(Gil et al., 2008), sodium chloride (Llano-Restrepo and Aguilar- 3.2.3. Membrane processes: genuinely effective approach
Arias, 2003), calcium nitrate (Ligero and Ravagnani, 2002), so- Membrane technology has semi-permeable barriers that apply
dium nitrate (Frolkova and Raeva, 2010), cobalt (II) chloride (Pena the principle of specific permeability; which is extensively used for
et al., 1994), strontium bromide (Vercher et al., 1994), and barium the purification of bio-based products (Meireles et al., 2016). Per-
nitrate. Similar to the liquid solvent and dissolved salt, a combi- vaporation is a membrane-based separation technology that em-
nation of both can be used as an extractant. A mixture of ethylene ploys the practice of sweep gas and vacuum to obtain anhydrous
glycol and calcium chloride has been experimented to extract ethanol (Dorraji and Vatanpour, 2016). In pervaporation processes,
99.5 wt % of ethanol (Gil et al., 2008). Earlier, a scientific group from fermented broth contacts the semipermeable membrane at the
Beijing compared the efficiency of ethylene glycol and a mixture of feed side, and a vacuum is applied on the opposite side, splitting the
ethylene glycol with potassium chloride to obtain 99.5 wt % ethanol stream into two components; a gaseous permeate and liquid
and reducing one-fourth amount of solvent (Zhou and Duan, 1999). retentate (Fig. 6). Further, a vacuum pump is used to lower the
Several scientific groups have explored non-volatile partial pressure of pervaporated gaseous permeate, which extract
 S. Saini et al. / Journal of Cleaner Production 268 (2020) 122357 7

Fig. 5. Schematic presentation of the extractive distillation process for ethanol dehydration along with solvent recovery system.

anhydrous ethanol, while liquid retentate passes through the unit. dehydrate various alcoholic solvents (Morigami et al., 2001).
Pervaporation membranes are nonporous; hence, separation of However, the uses of LTA zeolite membranes are limited due to the
the molecules is based on the affinity with the membranes. The high cost of membrane materials and complexity in membrane
molecules possessing low affinity with membrane are retained, formulations. The currently available LTA membranes are appro-
while molecules with high affinity are absorbed and diffused priate to separate a small amount of water from aqueous mixture.
through the membrane (Thomas et al., 2017). Broadly, there are two Therefore, to overcome this obstacle, hydrophilic Faujasite (FAU)
types of membranes based on the permeability; hydrophilic (water type zeolite membrane with a larger pore size was practised
permselective) or hydrophobic (ethanol permselective) (Ryu, (Sawamura et al., 2015). Recently, several challenges and mitigation
2008). Furthermore, membranes can be categorized as; inorganic, associated with the use of LTA zeolite membrane have been
polymeric and composite membrane, based on materials used for reviewed (Wenten et al., 2017). Moreover, researchers have devel-
membrane production (Manshad et al., 2016). Zeolites, the inor- oped hybrid membranes for ethanol dehydration. Chitosan/tita-
ganic membrane are made up of hydrated alumina silicates of so- nium dioxide (CS/TiO2) nanocomposite membranes made up of
dium, potassium, calcium, and barium, possess high potential in tetrabutyl titanate and acetyl acetone has been studied for perva-
pervaporation process to produce FGE (Makertihartha et al., 2017). poration. Among different compositions, CS/TiO2 nanocomposite
Depending upon the zeolite framework, the organic (ethanol) or membrane with 6 wt % TiO2 showed the best results (Yang et al.,
inorganic (water) components can be segregated from the aqueous 2009). Recently, the use of cross-linked polyimide membranes in
solution. Furthermore, zeolite membranes can be either hydro- ethanol dehydration has been reported. Carboxyl-containing cross-
philic [Linde Type A (LTA)] or hydrophobic (silicate-1) (Wenten linked polyimide membrane was synthesized via chemical and
et al., 2017). A Japanese scientific group exploited a strong hydro- thermal cross-linking for ethanol dehydration (Xu and Wang,
philic LTA membrane for large scale commercial applications to 2015). Other cross-linked polyimide membranes have been syn-
thesized via thermal, diamino, and diol cross-linking to study the
membrane morphology and performance (Le et al., 2012). The cost-
effectiveness of azeotropic distillation (cyclohexane) and perva-
poration to obtain anhydrous ethanol has been compared, which
revealed that azeotropic distillation was 2-fold costlier than per-
vaporation process (Kaminski et al., 2008). In spite of owning
several disadvantages such as membrane complexity, high cost and
short membrane lifetime; pervaporation is the promising tech-
nology offering the advantages of energy-saving, environmentally
benign, and cost-effective process. Therefore, upcoming research
should be oriented towards developing a cost-effective pervapo-
ration membrane with higher ethanol selectivity and having long
lifetime as compared to commercially available membranes.

3.2.4. Adsorption process: advancing the ethanol separation and

purification
Ethanol dehydration can be accomplished by the combination of
distillation and adsorption processes (Szitkai et al., 2002). Molec-
ular sieves used in the adsorption process can separate ethanol by
adsorbing water from the fermented broth. In order to avoid
contamination with microbial cells, the fermentation broth can be
Fig. 6. Pervaporation membrane process showing the recovery of dehydrated ethanol filtered or centrifuged prior to adsorption. The efficiency of water
from aqueous solution. absorption depends upon the pore size of molecular sieves (Chen
8 S. Saini et al. / Journal of Cleaner Production 268 (2020) 122357

Fig. 7. Schematic presentation of adsorption process using molecular sieves for the dehydration of ethanol from the fermented broth.

et al., 2014). Therefore, molecular sieve with a pore size of 3 Å can ethanol from fermented broth arise due to the complexity of the
adsorb water molecules of 2.5 Å in diameter, excluding the ethanol lignocellulose hydrolysates (Cuellar and Straathof, 2020). Ethanol
molecules which are typically of 4 Å in diameter from the aqueous separation is the cost-intensive and energy-consuming step in
solution (Fig. 7). ethanol production plant (Zentou et al., 2019). The energy
Broadly, two techniques are implanted in adsorption processes; requirement for the recovery and purification of ethanol depends
liquid-phase adsorption and vapour-phase adsorption (Carmo and upon the ethanol concentration in the feed stream. The energy
Gubulin, 1997). Earlier, vapour phase adsorption using different requirement for ethanol separation has been estimated to be about
types of adsorbents including lithium chloride, molecular sieves, 12e15% and 35% of combustion energy for feed stream having
activated alumina, silica gel, and some bio-based adsorbent have 12 wt % and 4 wt % ethanol, respectively (Granjo et al., 2020).
been reviewed (Huang et al., 2008). Plant-derived bio-based ad- Therefore, it is necessary to have cost-effective separation tech-
sorbents are mainly classified as: starch-based (cornmeal and corn nology to make lignocellulosic ethanol production economically
cobs) (Karimi et al., 2016; Sun et al., 2015) and lignocellulosic res- viable. Recovery of by-products such as fusel oil and vinasse from
idues (sawdust, rice straw, and bagasse) (Augier et al., 2016; Kim the fermented mash can provide a better trade-off the cost incurred
et al., 2015; Okewale et al., 2015). However, for liquid-phase during ethanol distillation. Fusel oil which contains higher alcohols
adsorption, zeolites molecular sieves (3 Å and 4 Å) are most is recovered from the bottom of the rectifier column and is
preferred. Additionally, several bio-based adsorbents such as concentrated at the end of the distillation process. It can be used as
polysaccharide-based synthesized adsorbent and a-amylase- a solvent or as a platform material for the extraction of amyl acetate
modified yellow corn grits have been applied for this purpose esters and other chemical compounds. Another by-product is
(Dehabadi and Wilson, 2014). Researchers from Laboratory of vinasse, which is recovered from the bottom of stripper column and
Renewable Resources Engineering, Purdue University were first to then fed to evaporation column for concentration. Vinasse is a good
report the application of starch and cellulose-based adsorbent for source of fertilizer or used in thermophilic digesters to produce
achieving anhydrous ethanol (Ladisch and Dyck, 1979). Thereafter, methane (Chandel et al., 2014).
bleached wood pulp, oak sawdust, and kenaf core were also The membrane separation process requires less energy for
experimented as an adsorbent (Benson and George, 2005). A potent ethanol separation; however it is not employed on an industrial
adsorbent must possess advantageous properties such as: high scale due to the short lifetime of the membranes (Hajilary et al.,
adsorption capacity, environmentally friendly, economical avail- 2018). Therefore, to overcome these limitations, next-generation
ability, regeneration, durability, and no aggregation with fermen- technologies should include a combination of distillation and
tation by-products. Novel adsorbents can be made through the membrane processes that could serve as an energy-efficient pro-
usage of lignocellulosic or other waste product to reduce the ad- cess than operating these processes alone. The synergistic appli-
sorbents and operational cost. The energy investment for the cation of distillation and membrane separation is not yet applied at
adsorption processes is calculated to about 1e2 MJ-fuel/kg-ethanol industrial scale due to a concern with membrane lifetime, pollu-
(Vane, 2008); which was reported to be the same for azeotropic tion, and separation factor (Khalid et al., 2019). However, these
distillation but with different purity levels, i.e., 99 wt % and 94 wt % technologies are likely to be accepted at the industrial level with
ethanol, respectively (Madson, 2005). To make this process more the advancement in membranes technologies. Notably, develop-
efficient in terms of both energy investment and cost reduction, ment of cross-linked hydrophilic polymers membranes (e.g. cellu-
future research should be focused on advantageous properties of lose esters and polyvinyl alcohol), and hydrophobic
adsorbent. Recently, several pros and cons of the adsorption pro- perfluoropolymers (e.g. Teflon AF and Hyflon AD), that resists high
cess have been discussed (Zentou et al., 2019). Yet, adsorption temperature and possess high separation factor, which can be used
process can be preferred for producing anhydrous ethanol from for the recovery of ethanol in near future. Consequently, emerging
lignocellulosic fermented broth containing low ethanol content processes employing simultaneous application of distillation and
(4e7 wt %). membrane separation could serve as a promising technology for
the recovery and purification of ethanol.
4. Current challenges and emerging technologies Azeotropic nature of ethanol-water mixture is the second key
challenge in the ethanol purification (Laksmono et al., 2018). In the
The difficulties in developing an efficient process to separate last few years, different types of methods have been developed for
 S. Saini et al. / Journal of Cleaner Production 268 (2020) 122357 9

Fig. 8. Hybrid separation process of reverse osmosis and pervaporation module proposed for ethanol dehydration.

ethanol dehydration from the azeotropic mixture, but the capital for the recovery and purification of ethanol could be a promising
and operational cost are the major challenges. Currently, extractive technology in terms of energy, capital cost, and environmental
distillation with an ionic liquid and hyperbranched polymers safety. Here, we conclude that there is an urgent need for further
drafted molecular sieves represent the promising technologies for research to develop both product and process, using the synergetic
ethanol-water azeotropic separation with low energy investment application of multiple separation technologies.
(Cai et al., 2018). Further, the current research methods are mainly
oriented towards adsorption processes by developing new adsor- 5. Conclusion
bents for commercial-scale purposes. Properties of adsorbent, such
as adsorption capacity and pore size of adsorbent influence the In this review, a comprehensive study of the scientific literature
efficiency of the process. An adsorbent with smaller size and has been summarised to collate an update the various high-
highest adsorption capacity will minimize the energy requirements throughput techniques used in the recovery and purification of
of the process and eventually lower the overall cost of the process. fuel-grade ethanol. Conventional distillation continues to be the
Therefore, the newer technologies should be evolved and applied in most dominant technology for the recovery and concentration of
the advancement of adsorbent properties, which can make the ethanol from the fermented broth. However, at lower ethanol
ethanol recovery process more feasible at industrial scale. concentrations, it possesses several disadvantages, such as high
The key challenge in ethanol purification is to optimize both the energy consumption and operational input cost. High energy con-
design and operation variables of the purification process to reduce sumption, processing costs, and environmental sustainability limit
the time and cost of the process (Maleta et al., 2019). However, any the use of extractive and azeotropic distillation process. Therefore,
single process mentioned earlier is not efficient to approach the to overcome these limitations; membrane and adsorption pro-
required product purity. Therefore, a process needs to be integrated cesses having the advantages of low energy investment and envi-
with other established methods to achieve the requirements of ronmentally friendly are implemented. Short membrane lifetime,
separation. Hybrid separation processes have been studied for the intense carbon footprints, cost of membrane and adsorbents makes
purification of ethanol, biodiesel, furfural, acetic acid, butanol, these processes unfeasible for industrial purposes. To mitigate
pyridine, and propanol (Harvianto et al., 2018). Hybrid separation these obstacles, combinatorial approaches of adsorption or mem-
processes involving adsorption or membrane processes coupled brane based processes coupled with distillation has been imple-
with traditional distillation has shown greater research interest. mented. Moreover, a proposed hybrid model of pervaporation and
Earlier, economic evaluation of hybrid configurations such as reverse osmosis could serve as an efficient technology in the near
distillation-adsorption, distillation-vapour permeation, vapour- future. It can be concluded that the hybrid system is an alternative
permeation adsorption, distillation-vapour permeation-adsorp- approach due toconsiderable savings in both energy and cost for
tion, and stripper-membrane have been reviewed (Singh and the recovery and purification of second-generation lignocellulosic
Rangaiah, 2017b). Other successful and potential hybrid processes ethanol.
include distillation-membrane separation, distillation-extractive
distillation, and liquid-liquid extraction-extractive distillation
Declaration of competing interest
(Conde-Mejía et al., 2016; Granjo et al., 2020).
Further, reverse osmosis in place of distillation process is a novel
The authors declare that they have no known competing
approach that leads to the reduction in the overall energy con-
financial interests or personal relationships that could have
sumption of the process (Khalid et al., 2019). Drawbacks such as the
appeared to influence the work reported in this paper.
short lifetime of reverse osmosis membrane with higher ethanol
concentration need to be addressed. Therefore, new processes
should focus on applying membrane technology and hybrid Acknowledgments
membrane processes. Nevertheless, the application of reverse
osmosis can be applied at an industrial level with the advancement The authors acknowledge Maharshi Dayanand University for the
in the reverse osmosis membranes. A hybrid system of reverse infrastructure facilities. KKS also acknowledges FIST-DST New
osmosis and pervaporation membrane separation (Fig. 8) proposed Delhi, India (Grant No. 1196 SR/FST/LS-I/2017/4) for the financial
support to the Department of Microbiology. AKC is grateful to the
10 S. Saini et al. / Journal of Cleaner Production 268 (2020) 122357

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