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An Overview of Alternative Raw Materials Used in Cement and Clinker
An Overview of Alternative Raw Materials Used in Cement and Clinker
To cite this article: Sabah Ahmed Abdul-Wahab , Hilal Al-Dhamri , Ganesh Ram &
Vishnu P. Chatterjee (2020): An overview of alternative raw materials used in cement
and clinker manufacturing, International Journal of Sustainable Engineering, DOI:
10.1080/19397038.2020.1822949
Article views: 3
CONTACT Sabah Ahmed Abdul-Wahab [email protected] PC 123, Sultanate of Oman Tel +96824141360 Fax +96824141316
© 2020 Informa UK Limited, trading as Taylor & Francis Group
2 S. A. ABDUL-WAHAB ET AL.
preheater phase; processing and pyro processing in the kiln; the raw material passes and undergoes decarbonation. The
clinkerizing; and grinding, packing, and transporting materials preheating chamber utilises the hot gases emitted from the
(Hewlett 2003; Peray and Waddell 1986). kiln, thus saving energy depending on the number of stages.
In stage one, the essential raw materials-limestone, laterite, This approach makes the cement plant more environmentally
bauxite, kaolinite, clay, iron ore, sandstone, etc-are mined. friendly by reducing fuel consumption by 30–50% (Wasilewski
Limestone is a source of calcium, while bauxite and kaolinite and Duda 2012).
meet the requirement for aluminium. Laterite, red ochre, and In stage four, the pre-heated decarbonised raw mix is fed
iron ore fulfill the need for iron and, to some extent, silica. into the rotary kiln for clinkerization. The retention time of the
Quartz-phyllite and sandstone provide a source for silica. kiln feed also varies from plant to plant, taking into considera
Because the requirement for limestone greatly outweighs that tion the reactivity of the raw mix and defining the production
of other components, cement kilns are usually located close to capacity, which is generally calculated as tons per day. The kiln
plentiful limestone supplies, with other raw materials being inlet temperature is usually maintained at around 900 °C, and
transported to the plant. Erecting cement kilns near limestone the final temperature is around 1450 °C (Deolalkar 2016;
mines allows easy handling of the primary raw material, Hewlett 2003; Peray and Waddell 1986). During heating,
thereby saving energy and making cement production more a series of chemical reactions occurs between calcium, silicon,
economical. In recent years, computer-aided mining plans aluminium, iron, etc. resulting in phase formation. Kilns are
have been widely adopted to assist with quality limestone typically heated from the exit side, with fuel type depending on
production. The extracted limestone boulders are crushed in availability and suitability.
crushers for size reduction, with the advanced technology of In stage five, the clinker exiting the kiln is rapidly cooled by
modern crushers resulting in optimal crushing. Piles of various forced air. The resulting hot air is circulated back into the kiln
raw materials stacked in stockpiles also receive further proces or the pre-heater, thus reducing energy demand. The cooled
sing as part of the mining process. clinker is then ground in a suitable grinding mill with about
Stage two involves the characterisation of various raw mate 5% gypsum or another calcium sulphate source and other trace
rials. This quality control process establishes the composition components such as limestone and stannous or ferrous
of the raw materials. Then, with the help of various quality sulphate.
control tests, suitable raw mix designs are prepared. The raw In the final stage, the ground cement is conveyed to storage
materials are then ground in suitable ball mills/vertical roller silos using a suitable transport system. The silos need to pre
mills (VRMs), both of which are common grinding mills, in vent contamination and hydration, for example. Stored
order to achieve the targeted fine powder, which is stored in cement is then either packaged in waterproof bags of
pre-homogenisation silos (Aïtcin and Flatt 2015; Hewlett 20–50 kg or transported in bulk.
2003).
In stage three, the raw mix is fed into a preheating chamber.
Raw materials chemistry
This chamber consists of 5–6 vertical cyclones, through which
Cement manufacture requires a source of calcium, such as
CaCO3 or CaMg (CO3)2, which comprises almost 80–90% of
the total and the rest is iron oxide (Fe2O3, Fe3O4), quartz
(SiO2), and clay/bauxite (Al-silicates) (Aïtcin and Flatt 2015;
Hewlett 2003; Peray and Waddell 1986). Traces of Na2O, K2O,
TiO2, and MnO2 are also present in the various raw materials
used for cement making (Gineys, Aouad, and Damidot 2010;
Vollpracht and Brameshuber 2016). Some of these trace ele
ments can be beneficial to the clinkering process while others
are not.
Besides chemical composition, the dissociation of CaCO3 in
carbonate rocks depends on the rock’s textural and micro
structural features. Holocrystalline calcite (CaCO3) dissociates
at higher temperatures than fine-grained calcite (Treiman and
Essene 1984).
It is known that MgO in limestone can be present in various
forms, including magnesium silicates, dolomite, and magne
site; each has different dissociation characteristics because of
thermal stability and the break-down temperature of the lattice
structure of magnesium compounds, such as for dolomite (Ca
Mg (CO3)2), is 700–750 °C, and ankerite (Ca (Mg, Fe) (CO3)2)
is 580 °C. The presence of Al2O3, SiO2, Fe2O3, Fe3O4, etc.,
further influences these dissociation characteristics (Kääntee
et al. 2004; Madlool et al. 2011).
The mineralogical nature and dispersion characteristics of
Figure 1. Cement production process with waste utilisation areas. silica have a strong bearing on the reactivity of the cement raw
INTERNATIONAL JOURNAL OF SUSTAINABLE ENGINEERING 3
mix. Experiments have shown that a slight increase in silica helmets, goggles, masks earplugs, and protective clothing are
content in the raw mix may profoundly reduce phase forma employed by operatives to address health and safety issues.
tion in the clinker. Silicates react more readily than free silica Drilling limestone beds during mining produces large quanti
or uncombined silica such as quartz (Herfort et al. 2010; ties of dust, for example, but wet drilling, where possible,
Ludwig and Zhang 2015). minimises dust generation (Donoghue 2004; Fthenakis 2003).
Clay minerals used in cement making are essentially Other steps are also taken to minimise environmental
hydrous aluminosilicates and provide a combined source of impact. Rock blasting, which is most commonly conducted
silica and alumina (Hewlett 2003; Ludwig and Zhang 2015). in limestone mines, may lead to ground vibration, flying rock,
Clays vary incredibly in composition and hence show hugely dust generation, and high noise levels. Sequential and con
variable thermal behaviours. However, all clays show a similar trolled blasting helps minimise ground vibration, while blast
pattern of change: dehydration then dihydroxylation followed holes can be optimised to avoid excessive generation of flying
by the breakdown of crystal structures. Through this process, rock. Reducing the powder factor (i.e., the quantity of explo
the clay releases Al2O3 and SiO2 in a reactive form. The pre sive used per ton of rock broken) helps to minimise dust
sence of this reactive state is then exploited in cement generation. Similarly, detonators and explosives can be mana
production. ged so as to avoid high noise levels and control the peak
The presence of iron oxide in the ferrous state favours raw particle velocity of the entire blasting operation. During sur
material reactivity. The appearance of FeO depends upon the face mining, watering limestone can reduce dust generation
breakdown temperature of the parent phase, and the tempera (Donoghue 2004).
ture ranges of the occurrence of FeO and its oxidation are During crushing, dust generation and high noise levels are
goethite at 300 °C, glauconitic at 450–500 °C, ferriferous normal. The effects can be mitigated by watering adjacent land.
chlorite at 500 °C, siderite/biotite/hornblende at 500–900 °C, Dense shrubs, such as as Quercus ilex, Psidium guajava,
and phlogopite at 1050–1250 °C (Herfort et al. 2010; Peray and Psidium cattleianum and Mangifera indica, can be planted to
Waddell 1986). Fe3O4 may contain more iron than FeO, but it help trap dust (Rai 2016).
only becomes reactive at temperatures above 900 °C. Limonite In the preheater section of the cement plants, harmful gases
(FeO, OH.H2O) often presents in laterite, and it generally are commonly generated. Proper methodologies should be
contains amorphous silica and is more reactive (Snellings, adopted by installing modern techniques to minimise the
Salze, and Scrivener 2014). excess generation of hazardous gases, excess heat, and dust
From a chemical viewpoint, the reactivity of a raw mix is (Mikulčić et al. 2016).
strongly dependent on the availability of reactive components. In the kiln section, excess heat generation should be con
As such, it is favourable that raw mix components become trolled by adopting the waste heat recovery technique
reactive at similar temperatures to the carbonate decomposi (Khurana, Banerjee, and Gaitonde 2002; Zhang et al. 2013).
tion temperature. It is evident that highly reactive fine carbo The excess heat recovered should be appropriately used in the
nates combine poorly with low reactive clays containing silica, required sections to save energy and protect the environment.
iron, magnesium, potassium, and so on. Waste heat recovery is one of the most critical parameters to be
controlled in cement plants because doing so helps to mini
mise energy conservation and safeguard the environment.
Environmental impact Noxious gases like NOx, SO2, CO2, and CO should be
The environmental impact of the cement industry controlled properly and must be monitored on a regular
basis to avoid environmental damage to the surroundings.
Every production industry impacts the environment in both Gas emissions may impact global warming (Barcelo et al.
minor and major ways. This phenomenon is true for the 2014; Benhelal et al. 2013; Van Oss and Padovani 2002).
cement industry also (Hendriks et al. 1998; Kajaste and Dust generation in the cooler and packing plant must be
Hurme 2016). Wet process cement plants impact their sur monitored on a day-to-day basis. Proper mitigation measures
roundings by slurry disposal while dry and semi-dry plants should be adopted to avoid generation more dust than is
also create solid waste, which is an environmental concern permissible. Transport systems in every section of the plant
(Deolalkar 2016; Uwasu, Hara, and Yabar 2014). Today, how should be adequately maintained to protect the cement plant’s
ever, very few wet process plants remain. Appropriate envir surroundings.
onmental protection laws, and norms and emission limits are The cement plant’s chimneys should be appropriately mon
formulated by every country, and the adoption of a proper itored to avoid excess dust emission to the atmosphere.
environmental management plan (EMP) can minimise ecolo Installing electro static precipitators (ESP), or baghouses with
gical degradation. Most cement plants worldwide take ade filter bags, is a must for arresting the dust generated during the
quate steps to protect the environment, and assessments of cement manufacturing process (Hewlett 2003; Uwasu, Hara,
environmental norms are improved and modified annually. and Yabar 2014). Proper, regular maintenance of ESP and
baghouses is necessary to achieve environmental norms.
Mediators of the environmental impact of cement
production CO2 emissions and global warming
Several environmental impacts riddle the cement production The cement production process consumes a lot of energy.
process and, as a result, personal protective measures, such as According to some estimates, the cement industry contributes
4 S. A. ABDUL-WAHAB ET AL.
as much as 5% of total global CO2 emissions (Gartner 2004). industries like mining, petroleum refineries, thermal and
The cement industry has several sources of CO2 emissions, nuclear plants, and construction also generate a massive
including fuel combustion and calcination. The cement indus quantity of waste. However, the dump yards created by the
try’s primary energy consumption is through carbon-based electronics industry are currently the biggest in the world
fuels such as coal, pet coke, natural gas, and petroleum pro (Kiddee, Naidu, and Wong 2013; Nnorom and Osibanjo
ducts (Ali, Saidur, and Hossain 2011; Barcelo et al. 2014). 2008). The situation is alarming.
During combustion, a high percentage of CO2 emission takes
place, and the cement industry’s CO2 emissions in 2008
Waste management and an increase in waste generation
accounted for 1.8 Gt/Y worldwide (Barcelo et al. 2014). The
cement industry generates CO2 by a calcination process and With increasing quantities of waste being generated across
the consumption of natural carbon-based fuels. During the a range of industries, appropriate waste management strategies
calcination process, CO2 is emitted mainly from limestone, are a global concern. Hence, sustainable waste management has
which is the primary raw material consumed during produc been incorporated as a core principle of industries worldwide.
tion. It is estimated that about 0.5 kg CO2/kg of clinker is Many environmentally friendly waste management options
generated during the calcination process (Van Oss and have been prescribed by various international environmental
Padovani 2002). agencies. Restrictions have been put on sea-based and farmland
The primary use of fossil fuels in cement production occurs waste disposal for various environmental reasons.
during pyro-processing. CO2 emissions during this process Advanced waste management techniques are formulated
depends on the type of production process and its efficiency for suitable reuse of the waste generated by different industries.
and also on the type of fuel used in the pyro process. The role Methodologies have been developed from the viewpoint of
of the percentage of additives used and the clinker-to-cement waste disposal, improvements required in the ratio of recycled-
ratio also play significant roles. It has been observed that as the to-non-recycled resources and how to recycle waste. Hence,
clinker-to-cement ratio increases, CO2 emissions also increase. developing a waste management plan (WMP) as part of an
However, the carbon intensity of cement manufacturing is not industry’s startup is a fundamental step which is crucial to
reported uniformly by different agencies. This reality is the a venture’s success (Aranda Usón et al. 2013; Schneider et al.
subject of some variation in the literature. Total CO2 emissions 2011). The volume of waste generated, along with its quality
per ton of cement from energy and calcination also ranges and physical and chemical properties must be determined in
widely. Along with CO2, other harmful substances like NOx, advance alongside estimations of production capacity.
SOx, CO, dust, and some heavy metals in trace amounts also Accordingly, the industry’s WMP and EMP should encompass
are emitted. a minimum of two-thirds of the life of the industry.
The cement industry’s CO2 emissions can be reduced by Simultaneously, the WMP should aim to overcome adverse
improving the energy efficiency of the process, using low environmental degradation. This advance planning will not
carbon fuels or alternative fuels (e.g., waste-derived fuels, only safeguard the environment but also help generate more
maintaining a lower clinker-to-cement ratio), and removing eco-friendly products and reduce environmental degradation.
CO2 from flue gases (Valderrama et al. 2012). Many of these Developments in science and technology have opened many
techniques have already been adopted by cement plants world new fields that can utilise various industries’ waste products,
wide. However, more stringent norms should be followed to and few steps are required to adopt and implement these
control CO2 emission levels. approaches. If the gap between research and implementation
is narrowed, then ecosystem improvements will be noted
immediately.
Waste generation In the past few decades, proper WMPs have not been
developed within the cement industry. This finding is the
Industrial waste generation
main cause of today’s severe environmental issues. However,
Every process industry in the world generates some waste, if appropriate steps are taken in relation to waste dumps,
and this waste generation may be major or minor. No matter materials can be used depending on their physical and chemi
the level of waste generated, it is generally dumped in the cal properties. For example, in many instances, the quality of
plant’s surroundings. Hundreds of years ago, waste genera refuse from limestone mines will support the manufacture of
tion was not a major concern, but with increasing industria gypsum and slag and, in many cases, rejected limestone can be
lisation and a growing population, society has become more used as composite cement components (ASTM, 2013; EN 197-
aware of the need for waste management. The cement indus 1. 2011 ; Hawkins, Tennis, and Detwiler 2003; Voglis et al.
try has been no exception to this growing awareness. During 2005). Even fine materials present in these dump yards may
the wet process era, a vast quantity of waste in the form of have utility in brick and tile manufacturing (Scott et al. 2005).
slurry was generated and disposed of in plants’ surrounding Use of waste as both coarse and fine aggregates can fulfill all
open lands, rivers, ponds or lakes. These dump yards created the requisite characteristics of strength and durability in con
a nuisance in cement plants’ surroundings. Most of these crete. Certain discarded materials may also be used in manu
cement plants are closed now, but those dump yards of slurry facturing of retrofitted concrete (Gesoǧlu et al. 2012;
remain untouched. Similar situations have arisen with the Khankhaje et al. 2016; Nagaratnam et al. 2016; Neupane 2016).
paper, sugar, copper, iron, pharmaceutical, textile, leather, As stated earlier, global cement production is growing
ceramic, and marble industries, to name a few. Nowadays, yearly. While an increase in production means more waste
INTERNATIONAL JOURNAL OF SUSTAINABLE ENGINEERING 5
generated and more gas emitted, an increase in the number of However, while considerable success has been achieved in
cement plants also means an increase the CO2 emission and a few areas to safeguard the environment, human health, and
other noxious gases in the atmosphere, which is a matter of ecology from hazardous waste, the cement industry has yet to
significant environmental concern. Proper planning for the achieve widespread success in this area. Different international
gaseous waste generated must be borne in mind to avoid any healthcare and environmental agencies are putting great effort
further environmental degradation and adequately utilise all to minimise the impact of hazardous waste.
types of waste generated. Industrial waste is mainly the byproduct of manufacturing
Planning for cement plants’ waste generation should be units. One of the biggest producers of industrial waste is the
mandatory. Such planning will not only save the environment world’s building material producing industries (Huntzinger
but also reduce the amount of refuse generated. Auxiliary and Eatmon 2009; Van Oss and Padovani 2002), but other
industries which can use the generated waste must be planned sectors contribute to the waste issue as well. These sectors
to avoid waste overload. include those involved in thermal power production; metal,
metalliferous, non-metal ore, and coal mining; and paper,
sugar, and textile production. During building material pro
Waste types
duction, numerous toxic minerals in the form of fine powder
The list of waste that humans generate is endless despite are generated. These fine airborne products spread in the
environmental norms, rules, and regulations, and no perfect atmosphere carried by ambient air. These toxic fine-grained
solution has been devised to deal with waste products. By the minerals affect the vegetation cover in production units’ sur
time waste of one type is controlled, another type of waste is roundings, impacting human and animal health, soil, water
generated. Improper industrial planning, coordination, and bodies, and crops. Thermal power plants worldwide also con
cooperation are mainly responsible for this situation. It is the tribute to this issue by producing a massive quantity of fly ash.
need of the hour to think on this issue globally; otherwise This underutilised fly ash causes several diseases in humans
the day is not far off when everything will perish. Waste can and in the animal kingdom (Singh et al. 2016). The different
be classified broadly into the following three categories metal manufacturing industries also generate waste which
(Nemerow 2007): endangers the health of humans and animals and contaminates
Non-hazardous waste, both surface and sub-surface water.
Hazardous waste, and
Industrial waste.
Waste used as raw materials in clinker production
Non-hazardous waste is mostly generated as non-metal
mining byproducts and can be categorised as rejects, demol The world’s manufacturing development process started with
ished construction materials, old metal machinery, and biode the production of new materials beneficial to human beings.
gradable household waste. However, the volume of non- From the beginning of the metal age, necessary materials have
hazardous waste occupies an increasing amount of the world’s been used and unwanted materials have been rejected.
available land annually. In many locations, this waste covers However, at the beginning of the metal age, no one could
useful land, which is of great concern. Hence, proper planning have visualised the sheer volume of waste occurring both
should focus on this waste’s potential uses. Research in this before and after the manufacturing process, especially in
area has been carried out globally, and many results have been cement production. Perhaps this short-sightedness is the rea
achieved to direct the handling of non-hazardous waste. son that people involved in industrial development never
A few examples of hazardous waste generating industries thought of optimising natural resources. This pattern contin
are the pharmaceutical, automobile, paper, leather, textile, and ued for centuries, and natural resources started to diminish. At
rubber industries; nuclear and thermal power plants; nuclear the beginning of the nano-technological era, experts started
explosion tests; and petroleum refineries (Fthenakis 2003; thinking of the use of both pre- and post-production materials.
Gidarakos and Aivalioti 2012). This type of waste has the Whereas waste was previously defined as materials that do not
potential to damage the global ecosystem (Gidarakos and have further use in the industrial production, the current
Aivalioti 2012) as it disturbs the natural environment, human definition has evolved. Nothing on earth should be wasted,
and animal health, and flora and fauna. Essentially, hazardous whether natural or human made, because today’s waste is
waste causes severe damage to the microbiological environ tomorrow’s raw materials. The industrial application of waste
ment. Hazardous waste is generally dumped in barren lands, generated by process/manufacturing industries has become
forest covered areas, lakes, and the sea. These dumping sites the main thrust of technological developments worldwide.
have been used by various industrial agencies over the years Cement technologists have also come to this realisation and
and have caused severe disturbances in the world’s overall put effort into using waste materials differently (Table 1).
ecosystem. Numerous steps have already been taken to solve Definitions of what constitutes raw materials also have been
this problem. In many cases, considerable success has been modified, natural resource use is now maximised, and new
achieved but, to improve results, continuous efforts are items have been added to cement manufacturers’ lists of poten
required. tial materials for productions.
Different cement plants have identified non-hazardous and Numerous problems are faced in the process of clinker
hazardous waste products, and research has suggested their manufacturing when materials derived from fuels are used.
proper utilisation. Such waste is being used in clinker produc These problems have led to intensive focus from the cement
tion and even in some cases as post-production material. industry to understand the cause of these problems. The most
6 S. A. ABDUL-WAHAB ET AL.
frequent problems faced are related to volatile compounds crystals are relatively more substantial when compared with
such as SO3, alkalis (Na2O and K2O), chlorine (Cl), and clinker prepared with non-waste clinker.
moisture content. These oxides create a cycle in the preheater
tower in which they build until the formation that blocks the
production path, leading to lower production. In many cases, Sludge from water treatment
this stoppage in the rotary kiln requires cleaning to remove the Raw water from various sources is treated in water treatment
formation. This issue usually occurs at temperatures between plants. Impurities are removed by coagulation-flocculation,
950–1250 °C. Because alternative fuels and materials introduce sedimentation, and the filtration process, and potable water
water vapour into the preheater, when sulphur is present in the is achieved. During this process of purification, and especially
alkalis cycle, the reaction becomes more complicated. The in conventional water treatment plants, massive quantities of
presence of SO2 tends to decrease the impact of the alkalis’ sludge are generated, but discharging the sludge into rivers,
cycle while the presence of Cl and water vapour tends to lakes, sea, drains, landfills, etc. is not a disposal solution
increase it. If sulphur is present in the form of CaSO4, then because it damages the environment.
the oxygen released from the decomposition of CaSO4 at very
high temperatures (from 1200–1400 °C) leads to the formation
of more undesirable complex compounds.
Additionally, the presence of alkalis can lead to the formation
of free lime (i.e., uncombined lime) in the clinker (Figure 2,
chemical equations 6 and 7), affecting the quality of the clinker
and producing cement that has low compressive strength and
higher expansion (Chatterjee and Sui 2019). Using alternative
fuels such as polyvinyl chloride (PVC), chlorinated hydrocar
bons or sewage sludge, biomass raises the amount of chlorine in
the preheater and kiln system. Furthermore, the occurrence of
volatile chlorine in the kiln gases’ stream introduces environ
mental concerns and can cause volatilisation of metals such as
mercury, lead, and cadmium.
Some remedial measures have been successfully implemen
ted in the cement industry to counteract the problems caused
by alkalis, including preparing the kiln feed with a molar ratio
of SO3 to a total alkali oxide of 1:2.
Another effect of using waste as alternative fuel or material
in clinker preparation is that it causes changes in the clinker
phase microstructures. These changes, which can be concep
tualised as microstructure modifications, happen when trace
elements, including heavy metals, alkalis, chlorine, and
others, appear in the crystal structure of clinker phases.
Figure 3 shows clinker analysis by optical microscopy for
two types of clinker. Figure 3A and B show clinker obtained
from a cement plant that does not use any waste in their
process. The clinker phases formed in these processes are
alite and belite. However, Figure 3C and D show the micro
Figure 2. The chemical reactions happen in the preheater and kiln during the
structure for clinker prepared using 55% hazardous waste process of clinker formation at present of alkalis (Na2O and K2O), Sulphur (SO3),
obtained from the oil drilling process. The alite and belite chlorine (Cl) and moisture content (Chatterjee and Sui 2019).
INTERNATIONAL JOURNAL OF SUSTAINABLE ENGINEERING 7
Industrial waste
Several industries produce industrial waste. Like other types of
waste, industrial waste is not without its problems and, if it is
Figure 3. Clinker microstructure analysed by optical microscopy (a and b) clinker not disposed of properly, can cause land and water pollution.
obtained from cement plant that prepared with normal raw materials without High moisture content, the nature of the waste, the extent of
alternative fuel nor alternative raw materials. (c and d) clinker prepared by mixing
55% oil-based mud cutting waste. impurities present, its availability, its negligible effect on pro
duction costs and profitability, its physical properties, etc.
make the waste critical for use in cement manufacturing.
Many byproducts of chemical industries are rich in lime and
While the chemical composition of sludge may vary
enhance phase formation so are used as a minor percentage of
regionally, usually SiO2, Al2O3, Fe2O3, CaO, Na2O, K2O,
the raw material needed for cement production (Herfort et al.
and MgO are the chemical constituents present in sludge
2010; Schneider et al. 2011; Van Oss and Padovani 2002).
and TiO2, P2O5, MnO, ZnO, and PbO are present in
Numerous characteristic features of industrial waste make it
smaller percentages. Trace elements like Ba, Zr, Rb, Ce,
suitable for the manufacture of blended and special cements:
Sr, Cu, Ni, Cr, Ga, As, Nd, Nb, and Co are also present in
The source of industrial waste and its byproducts is well
sludge. As stated previously, discharging sludge is not sus
defined;
tainable as it will damage local and regional environments;
Such waste does not require any mining so only handling
however, the chemical and mineralogical composition of
costs are involved;
sludge suggests that it can be used in cement production
Industrial waste is often fine grained; hence, extensive
(Lin and Lin 2005; Taruya, Okuno, and Kanaya 2002).
grinding and crushing may not be required, which saves
More specifically, research worldwide has suggested that
energy and, consequently, cost; and
water treatment sludge could be used in lower percentages
Most industrial waste does not need much processing, (e.g.,
as a raw mix component of cement manufacturing because
drying, calcining) which reduces energy consumption and cost
its elemental composition is fine sand, silt, and clay, which
(Aïtcin and Flatt 2015; EN 197-1. 2011 ; Hewlett 2003).
is sometimes rich in lead, chromium, arsenic, barium, and
Waste used in the cement industry includes blast furnace
other metals. In fact, this sludge has been used as cementi
slag, fly ash, fertiliser slag, red mud from the aluminium
tious material, as a fine aggregate component in the con
industry, Pb-Zn slag, Cu-slag, agricultural waste, paper sludge,
struction industry, in the ceramics industry, and in
etc. (Ishak and Hashim 2015; Stefanović et al. 2010). Other
lightweight brick and aggregate manufacturing (Weng,
than this petroleum refinery sludge, sugar industry baggase,
Lin, and Chiang 2003). Research indicates that recycling
rice husks, refuse from the aluminium scrap handling industry,
sludge for use in the building and construction industries is
marble slurry, jarosite, etc. are also used to a minor extent by
safe, and its strength and durability have shown encoura
several cement industries.
ging results.
Numerous mineral and chemical constituents present in the
different waste categories mentioned above enhance the better
phases in the clinker and improve the quality of cement. These
Sewage sludge waste
minerals include dehydrated gypsum, melilite,
Sewage sludge waste is produced from municipal wastewater K-aluminosilicates, Ca-rich minerals, active quartz, etc.
coming from hospitals, nursing homes, and households. The However, if the proportion of these minerals constitutes
fresh sludge is extracted mechanically and passed to a separate more than 15% of the mixture, then the chances of poor
sludge digestion tank which operates at a high temperature. phase formation in the clinker increases. Even large size
The digested sludge is generally disposed of in landfills, which layered alite grains and free lime are formed. An optimum
causes numerous health hazards and disturbs an area’s flora proportion of minerals in the waste helps create good silicate,
8 S. A. ABDUL-WAHAB ET AL.
aluminate and ferrite phases in the clinker. In such conditions, The more basic the slag, the higher the hydraulic activity in
grain size distribution is uniform in the clinker. the presence of alkaline activators. Ordinary air-cooled slag
Fly ash, which is a fine-grained material consisting of has no or very few cementing properties. Granulated slag alone
quartz, mullite, haematite, and clay minerals as major minerals has a negligible cementing action due to activators like lime
and carbonate minerals, gypsum, and pyrite as secondary and Portland cement, and alkalies such as soda, sodium car
phases, is a byproduct of coal-based thermal power plants. bonate, or sulphate of the alkalies. An average or moderately
The quality of fly ash is ascertained by the presence of a glass high alumina content of slag enhances the quality of cement.
phase. Numerous types of glass grains (mostly spherical) are Various phases are present in the slag including glass
present in fly ash. These glass grains may be clear, solid, (supercooled liquid silicates), semi-glass, quartz, Ca-rich sili
spongy, partly crystalline, or porous. Grain sizes in fly ash cates, aluminosilicates, the presence of modified C3S and C2
can vary drastically. Technical assessment of fly ash is deter S phases, and in melilite, gehlenite, akermanite, merwinite,
mined by physical and chemical characteristics which meet rankinite, pseudo wollastonite, monticellite, oldhamite,
certain requirements. In a few cement plants, fly ash is used as anorthite, forsterite, perovskite, spinel, etc. in minor amounts
a raw mix component but, in most cases, fly ash is added to (Yildirim and Prezzi 2011).
cement to produce Portland Pozzolana cement (PPC). The various types of slag cements produced are Portland
Standards have been developed by quality assurance organisa blast furnace slag, Eisen Portland cement, Hochofen cement,
tions worldwide, which is a prerequisite for manufacturing Cimetanlaiter. et aux Cenacles, super sulphated cement, and
PPC. These standards mainly have been developed because Cimet de laiter a La Chaise.
of variation in the quality of the fly ash produced by different Cu-Zn and Pb slags are also used in cement manufacturing
thermal power plants. (Bijen 1996; Zhang, Hama, and Na 2015). In these types of
Fly ash utilisation in the cement and construction industries slags, the morphometric complexity in the glass is typical, and
can lower GHG emissions because such use offsets the emis semi-glass grains may behave as mineralisers. There is a direct
sions that result from mining activities and CO2 generation effect of this slag on the formation of belite grains. However,
during cement production. Fly ash can decrease a higher per these slags reduce the size of grains of both C3S and C2S if the
centage of the consumption of cement during construction. pyro-processing system is disturbed.
Using fly ash as a substitute for cement in roller compacted Red mud is a byproduct of the aluminium industry. It
concrete results in reductions when 15–30% of the Portland contains numerous in situ mineralisers, which help to enhance
cement is replaced with fly ash (ASTM C595/C595M-16. 2003. quick phase formation in the clinker. However, the phases’
ASTM C595-03 ; EN 197-1. 2011). This phenomenon results in forms are different in shape and size. Red mud also affects the
energy savings, and reductions in GHGs and the emission of morphology of phases, which is fragmentation of alite and
dust and noxious gases. Fly ash has also been used successfully belite, thereby increasing the granulometry of phases.
to produce bricks and in roads to save soil (Dabhade, Caution should be taken to avoid free lime formation in the
Chaudari, and Gajbhaye 2014). However, fly ash use is clinker. The primary aims when using different waste is
restricted in countries where coal-based thermal power plants To reduce energy consumption and CO2 release,
do not exist. To enhance reactivity,
Blast furnace slags are formed when iron ore, coke, and To limit the time content,
limestone or dolomite are heated at high temperatures. During To use alternative source materials,
this process, the limestone/dolomite acts as a flux and is To create cement based on sulpho alumina tests,
chemically combined with the silicates and aluminates present To characterise waste materials using different instrumental
in ore. Coke ash and the above products are mixed and pro methods, and
duce blast furnace slag. This molten product can be cooled in To emphasise the importance of grain morphology and
several ways to form various types of slag, including ground size percent distribution for motion, strength, etc.
granulated blast furnace slag (GGBS), which is rapidly cooled
with large quantities of water to produce granules (Bijen 1996).
Building waste
GGBS is mixed with Portland cement clinker to make
a blended cement known as Portland slag cement (PSC) Building waste is generally generated by the demolition of old
(ASTM Committee C01.10, . ASTM C150/C150M-16 ; Bijen buildings. These are also sometimes considered construction
1996; EN 197-1. 2011). It is preferable that MgO, SO3, and and demolition (C&D) waste. Many definitions of C&D wastes
sulphide Sulphur (S) loss on ignition and insoluble residue have been adopted (Medina et al. 2014; Wagih et al. 2013).
should not exceed 8.0%, 3.0%, 1.5%, 4.0%, and 2.5%, respec C&D waste is very complex in composition and contains
tively. GGBS with the following compositions can produce masonry materials like dirt, rock, concrete, and brick mixed
suitable PSC: SiO2 27–32%, Al2O3 17–31%, Fe2O3 0.0–1.0% with wood, roofing, drywall, and a small amount of metal.
CaO 30–40%, MgO 0.0–17% and sulphide 0.2% (Zhang, These materials are usually broken and smashed, complicating
Hama, and Na 2015). Further, the GGBS should show hydrau recovery from debris loads. Additionally, certain materials
licity, which is a function of glass content. As per practice, the have further complicating factors. Wood, for example, is typi
glass content should not be less than 85–90%. A lesser percen cally weathered, painted and in many cases attached to some
tage of glass implies the presence of slag minerals such as other material. Roofing materials and masonry materials such
melilite, and wollastonite in greater amounts (Collins and as brick, concrete, rock, and dirt within a demolition site are
Sanjayan 2000). generally mixed with other demolition materials.
INTERNATIONAL JOURNAL OF SUSTAINABLE ENGINEERING 9
Despite their special considerations, C&D waste can have significant components (ASTM C595/C595M-16. 2003. ASTM
value in cement production. Masonry materials can be used C595-03 ; EN 197-1. 2011). Additionally, limestone has been
both as coarse and fine aggregates of concrete depending on used as a component of cement. These additives were added
their physical properties. Different grades of concrete were first independently as well as in combination in permissible per
developed in laboratories, and various tests, including durabil centages in the cement mixture along with clinker. Fly ash and
ity, compressive strength, bleeding, physical properties, leach GGBS slag were added in cement grinding to produce PPC and
ing, etc. were conducted. In most cases, these materials yielded PSC cement. However, the combination of clinker, fly ash, and
promising results, with pavement concrete developed for C&D slag along with gypsum is used in cement grinding.
waste in particular showing very promising results. In many Similarly, clinker, fly ash, and limestone have been used to
instances, C&D materials are used for road construction, and produce cement. These permutations and combinations have
some masonry materials are even used to develop lightweight been decided based on the physical and chemical characteris
concrete. However, more periodic research is required for tics of the waste materials. This scientific approach to cement
more use of these waste products. manufacturing was introduced to reduce CO2 emission and
energy conservation within the cement industry. More
research is being done worldwide to find ways to conserve
Waste used as alternative addition in cement limestone deposits and use waste materials to produce new
grinding types of cement. During the development of new cement,
quality aspects are strictly monitored and, to this end, during
Various types of cement have been introduced in the recent
grinding, every possible physical and chemical parameter is
past by cement technologists the world over (Table 2). The
maintained to produce high-quality cement.
majority of these cements were developed by the addition of
Table 3 shows a list of SCMs which are used as fillers, are
alternative waste (also known as SCM, supplementary cemen
chemically active in hydrating cement, and replace clinker.
titious materials) produced by other industries. Fly ash and
Adding SCMs results in improved strength and durability in
various slags produced by metal industries are the two most
the cement composite, and they are widely used in concrete
admixtures. One advantage of cement concrete prepared with
Table 2. Wastes used as clinker replacement. fly ash is the binder’s low hydration temperature. The fly ash
Waste Source Categorised as Reference maintains a low temperature in the concrete, thus decreasing
Silica fume Silicon Supplementary Saraya (2014) the concrete’s risk of thermal impact. Likewise, fly ash
industries cementitious increases the chemical resistance of concrete and decreases
material exposure to an alkali-aggregate reaction (Czarnecki and
Granulated Steel industries Cementitious Ludwig and Zhang
blast- material with (2015) Justnes 2012; Pacewska and Wilińska 2013).
furnace self-cementing Lee and Lee (2013) Pacewska and Wilińska (2013) studied the effect of using fly
slag Bijen (1996) ash as a replacement for cement using the isothermal calori
Fine sewage Sewage plant As fine filler with Baeza-Brotons et al.
sludge some (2014) metry analytical method which measures the total heat
ash pozzolanic Chen and Poon (2017) released and the rate of heat evolution after adding water to
activities the mixture. The total heat released is measured as shown in
Bio mass ash Sugar Pozzolanic Donatello and
industries activities Cheeseman (2013) Figure 4A and B. The five stages of heat released (i.e., initial
Fly ash Coal power Pozzolanic Bijen (1996) dissolution, induction period, acceleration period, decelera
plants material Chen and Poon (2017) tion, slow period) were observed for the eight samples with
Hsu, Chi, and Huang
(2018) different ratios of fly ash. The reference sample without fly ash
Limestone Cement Filler and lesser Ishak and Hashim (2015) shows typical shapes where the total heat released was
industry density material Ishak, Hashim, and observed to decrease (Figure 4A). This influence of the delay
Ting (2016)
Kenai, Soboyejo, and ing process is due to the developing of the pozzolanic activities
Soboyejo (2004) of fly ash cement and low amount of original cement in the
Elephant Natural burnt Pozzolanic Cordeiro and Sales mix (20% cement and 80% fly ash).
grass ash material activities (2015)
Seashell Natural waste Filler and lesser Soltanzadeh et al. (2018)
powder density material
Meta-kaolin Calcined Pozzolanic Siddique and Klaus Cement standards and specifications
natural material (2009)
waste Rashad (2013) Cement is a hydraulic binder, or a fine-grained inorganic
Valipour et al. (2013) material, which forms a paste when water is mixed with its
Rice husk Agricultural Pozzolanic Sathawane, Vairagade, coarse and fine aggregates. Cement hardens into concrete or
ash and Rice material and Kene (2013)
Industry Park, Kwon, and Wang mortar over time through hydration reactions. The process of
waste (2016) hardening allows cement to retain specified strength and long-
Silico- manganese Ferro-alloy Cementitious material term stability with ageing. Common types of cement include
slag industry
Allahverdi Ahmadnezhad Portland slag cement, PPC, Portland fly ash cement, Portland
and (2014) limestone cement, Portland-burnt shale cement, composite
Zeolite Natural waste Cementitious Vejmelková et al. (2015)
material material Valdes-Vidal, Calabi- cement and others (ASTM C595/C595M-16. 2003. ASTM
Floody, and Sanchez- C595-03 ; EN 197-1. 2011). Portland cement clinker is manu
Alonso (2018) factured by defined raw materials containing CaO, SiO2, Al2
10 S. A. ABDUL-WAHAB ET AL.
Copper indus
Nazer et al.
raw materials are developed for firing in the kiln. The clinker
try waste
(2016)
39.1
30.4
13.4
7.7
2.1
1.0
1.5
0.5
2.1
thus produced should contain at least two-thirds by mass of C3
S, other phases of C3A, C4AF, and liquid.
All cements are developed by adding different compo
Steel Industry
nents in prescribed limits, and quality assurances of all these
Roslan et al.
(2020)
waste
cements are fixed according to standard norms. All these
21.9
23.1
34.9
6.6
8.2
0.2
0.2
0.0
2.2
cements should achieve set mechanical, physical, chemical
and durability requirements. Compressive strength, initial
setting time and soundness in these cements should be
Younes, Abdel-Rahman, and
2.0
-
minor constituents are defined in the standards of all the
cement producing countries of the world. Targeted limits
specified by the standards must be followed to maintain the
quality of the cement. These standards, however, have not
always existed.
Municipal solid waste
38.3
1.7
3.0
1.6
5.1
-
Initially, only a few types of cement were included in the list for
standardisation. Before standardisation, many countries devel
oped criteria for cement performance depending on the dur
ability and quality of the product. Therefore, significant
Ashish (2019)
Crushed-Glass
10.5
12.5
2.2
1.3
1.3
0.6
-
-
also been developed by countries other than the ones that are
29.1
44.2
21.0
3.3
0.8
0.2
0.1
0.1
-
37.2
10.9
slag
0.1
0.4
0.8
-
46.7
19.2
7.5
9.4
1.4
1.8
1.8
2.9
5.9
Na2O
CaO
K2O
SO3
(%)
of water through the capillary pore to determine the develop Mono sulphate is an ettringite because it contains three mole
ment of pores in the concrete. To achieve good quality con cules of anhydrite.
crete, effective fracture toughness, effective toughness, and Similarly, the mono-sulphate phase contains one molecule
specific fracture energy are also measured. The role of cement of anhydrite. Ettringite is existing as rod-like crystals in the first
in achieving the features in concrete mentioned above is very stage of the reaction or from time to time as a huge growth. In
important. Positive results of the concrete entirely depend on mature concrete or mortar, ettringite crystals develop in the
the quality of cement used in the concrete mix design. available pore spaces. Nomo sulphate have a tendency to arise
However, the coarse aggregate used in the concrete also plays in the advanced stages of hydration, a day or two days after
a crucial role. All the physical and chemical properties of the mixing. Both ettringite and mono sulphate are compounds of
coarse and fine aggregates must be appropriately cross- C3A, CaSO4, and water in various proportion.
examined to achieve the targeted quality of the concrete. The Both of ettringite and mono sulphate have a large amount
alkali-silica reaction (ASR) and alkali-carbonate reaction tests of water, particularly ettringite in the context of cement.
(ACR) are a must to ascertain the durability of the concrete However, the anions of both these hydration products can be
(Kurdowski 2014). changed by differently charged anions. The sulphate of ettrin
Four significant components-alite, belite, calcium, alumi gite can be replaced by carbonate or partly substituted by two
nate and calcium alumina ferrite-are present in the anhydrous hydroxyl ions, although practically none of these is often
state of the cement (Herfort et al. 2010; Hewlett 2003). When detected.
water is added, exothermic reactions take place. With the help In concrete that is made from cement containing only
of conduction calorimetry, the rate of heat evolution can be cement and gypsum, ettringite forms at early stage after the
monitored. Almost immediately on adding water, calcium cement and water are mixed together, but it is slowly substi
aluminate reacts to form an aluminate-rich gel. This reaction tuted by mono sulphate. This phenomenon occurs because the
is strongly exothermic, continues for a few minutes, and is available alumina-to-sulphate ratio is easily available to dis
followed by a period of a few hours of dormancy. The first part solve, but the calcium aluminate is contained inside cement
of the dormant period is when concrete can be poured and the grains without an initial access to water. Continued hydration
paste is stiff enough to be workable. At the end of the dormant progressively liberates alumina, and the proportion of ettrin
period, both the alite and belite in the cement start to react gite declines as that of mono sulphate rises. If there is a slightly
with each other. higher amount of sulphate, the cement paste will have
These reactions mainly develop calcium silicate hydrate and a mixture of mono sulphate and ettringite. With the increasing
calcium hydroxide, which is the main period of hydration availability of sulphate, there will be extra ettringite and
during which the time concrete strength increases. The grains a lesser amount of mono sulphate, and at even higher levels
react then individually from the surface inwards. Hydration of of sulphate, there will be ettringite and gypsum. If the lime
calcium aluminate stays as fresh crystals become accessible to stone is present, then carbonation becomes available owing to
water. The reaction of Ferrite also begins rapidly as water is the reaction of some of the limestone. The carbonate replaces
added. Then the reaction slows down probably due to the sulphate or hydroxyl in ettringite. Therefore, it decreases as the
formation of a layer of iron hydroxide, coating the ferrite proportion of mono carbonate increases. The displaced sul
and standing as a barrier to additional reaction (Marchon phate usually merges with the remaining mono sulphate to
and Flatt 2016; Scrivener, Juilland, and Monteiro 2015). The form ettringite. The key here is the balance between alumina
heat evolution period during concreting after mixing lasts on the one hand and carbonate and sulphate on the other
usually between 10 and 20 hours and then gradually starts to hand.
fail. In a mix containing only Portland cement, most of the The impact of using fly ash and granulated blast furnace
strength gain happens within almost a month. When Portland slag on compressive strength has been widely investigated.
cement has been partially substituted by other different mate Cement containing large amounts of such industrial waste
rials (e.g., fly ash, GGBS slag, composite cement), the strength displays improved compressive strength for an extended per
gain may happen more slowly and persist in for a longer iod, and mortar and concrete’s physical properties are also
period. improved. The initial compressive strength (within 2 and
Calcium silicate hydrate, portlandite hydroxide, calcium 7 days’ hydration) of the Ordinary Portland Cement (OPC)
hydroxide, tricalcium hydrate, and mono sulphate are the without any addition showed the highest strength. However, as
four main results of hydration. In some instances, monocar hydration progressed, as a function of time, the cement with
bonate grains also develop. Calcium silicate (C-S-H gel) is the ground granulated blast furnace slag (GGBFS) improved, but
core reaction product which is the main source of the strength the hydration was still lower than the OPC without any mix
of the concrete. No strict SiO2-to-CaO ratio is inferred. The ing. According to Giergiczny (2019), the mixture of OPC, fly
SiO2-to-CaO ratio is rather variable but typically is around ash, and HCFA showed higher compressive strength than the
0.45:0.50 in the hydrated Portland cement and up to 0.45:0.6 if OPC without any additions (Figure 5).
slag, fly ash, or micro silica is present, depending on the Fly ash is very fine dust with spherical grains that contain
proportion. Portlandite is often abbreviated as CH and forms pozzolanic properties. As soon as fly ash comes in contact with
mainly by hydration of alite which has a Ca:Si ratio 3:1. C-S-H, water, it reacts with calcium hydroxide (Ca(OH)2) to produce
on the other hand, has a Ca-to-Si ratio of nearly 2:1; hence, calcium silicate hydrates (C-S-H) and calcium aluminate
excess lime is available to produce CH. Another common (C-A) products. The calcium hydroxide is released as a result
phase developed in the hydrated cement is mono sulphate. of the cement’s hydration. Calcium hydroxide alone plays no
INTERNATIONAL JOURNAL OF SUSTAINABLE ENGINEERING 13
mixed with fine and coarse aggregates and water, and the Vishnu Chatterjee has received his PhD (1995)
hydration process becomes simple or complex depending on from Allahabad University, Earth and Planetary
the concrete mix design. Dry powder cement is anhydrous in Science, India. Dr. Chatterjee had worked as Joint
Director and Unit Head, at National Council for
nature when produced by grinding of clinker and gypsum. Cement and Building Materials, India. The main
During the process of concrete mixing, water is added to research interests are focused on raw materials for
develop concrete slurry. With the advancement of the reac cement manufacturing, petrographic studies of
tions, the products of the hydration process gradually bond various rocks, concrete, clinker, fly ash, slag, pow
together the individual components of the concrete mix. The der samples of cement, fire-damaged building
rocks, Blasting techniques and preventive mea
mix of concrete components forms a solid mass. sures, igneous petrology, experimental petrology of natural and synthetic
systems, mineralogy, and refractory materials.
Acknowledgments
The research leading to these outcomes has received Research Project ORCID
Funding from The Research Council of the Sultanate of Oman (TRC),
Sabah Ahmed Abdul-Wahab http://orcid.org/0000-0002-5250-6340
Research Agreement No. ORG/SQU/EI/15/009.
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