An Overview of Alternative Raw Materials Used in Cement and Clinker

International Journal of Sustainable Engineering
ISSN: (Print) (Online) Journal homepage: https://www.tandfonline.com/loi/tsue20
An overview of alternative raw materials used in

cement and clinker manufacturing
Sabah Ahmed Abdul-Wahab , Hilal Al-Dhamri , Ganesh Ram & Vishnu P.

Chatterjee
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
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Published online: 29 Sep 2020.
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INTERNATIONAL JOURNAL OF SUSTAINABLE ENGINEERING
https://doi.org/10.1080/19397038.2020.1822949
An overview of alternative raw materials used in cement and clinker manufacturing

a
Sabah Ahmed Abdul-Wahab , Hilal Al-Dhamria,b, Ganesh Ramb and Vishnu P. Chatterjeec
a
Department of Mechanical and Industrial Engineering, Sultan Qaboos University, Muscat, Sultanate of Oman; bOman Cement Company S.A.O.G,
Muscat, Sultanate of Oman; cNational Council for Cement and Building Materials, Ballabgarh, India
ABSTRACT ARTICLE HISTORY

Material generated during industrial activities that do not have further use in the production process are Received 23 April 2019
often categorised as refused industrial byproducts. This paper briefly discusses the utilisation of such Accepted 4 September 2020
refused byproducts in the cement manufacturing process and evaluates their use at different stages of KEYWORDS
the cement manufacturing process. The evaluation was based on the byproducts’ physicochemical Refused industrial by-
properties without affecting the quality of the final cement product. Dealing with hazards caused by product; clinker phase;
byproduct mismanagement and storage is a tremendous task; however, such production continues to alternative raw materials; de-
rise. The worldwide diminishment of raw materials offers ample opportunities to replace these materials carbonation; mineralogy;
with refused byproducts. Many refused byproducts remain unexplored even though they might be used environmental hazard
in cement production and to develop newer types of cement. Using refused byproducts as alternatives to
more traditionally used raw materials will help maintain the world’s ecological balance while contributing
to society’s development.
Introduction (Farzanegan and Markwardt 2018). Around 50% of the total

emissions are from limestone decarbonisation, and about 40%
Portland cement underpins modern global development. As
result from the fuel used in the kiln process. The MENA
such, it is the most abundantly produced material in the world
countries are the world’s top per capita emitters for CO2 and
(Deolalkar 2016). The world has an abundance of the primary
SO2 and have had high pollution records since the 1960s,
raw materials for cement manufacturing and, compared to
exceeding the world average from 1995 onwards. This region
other construction materials, cement’s cost is low and it has
has around 57% of the world’s proven oil reserves and 41% of
good durability (Hewlett 2003).
proven natural gas reserves, and about 85% of all greenhouse
In 2017, China and India, the world’s biggest producers,
gas (GHG) emissions in this region come from energy produc
together produced 64% of the world’s cement, or 2.61 million
tion and consumption.
tons of cement out of 4.05 million tons. In 2018, these countries
The global industrial market is facing environmental and reg
together estimated production of 2.66 million tons of the total
ulatory issues regarding water disposal and usage, CO2 and sulphur
4.10 million tons, or 65% of the world’s total. In the Middle East,
oxide (SOx) emissions, depletion of reserves, and other industrial
Saudi Arabia, the region’s major cement producer, manufactured
activities. To overcome these challenges, many industries are work
0.47 and 0.45 million tons for 2017 and 2018, respectively. In
ing on alternative sources of fuel and raw materials. Considering
comparison, in the same years, the United States produced 0.86
the predicted increase in demand for cement, there is pressure on
and 0.88 million tons of cement.
the cement industry to maintain or reduce CO2 emissions.
Demand for cement in the North Africa and Middle East
Alternative fuels and raw materials are increasingly used to mini
(MENA) region is expected to grow at a compounded annual
mise cement-related CO2 emissions, and increased plant efficiency
rate of 5.5% (Uwasu, Hara, and Yabar 2014). Increasing urbanisa
is desirable from both economic and environmental perspectives.
tion has led to the steady growth of cities; hence, cement demand is
Also, there has been significant research into new, lower carbon
inevitable. Infrastructure development in the MENA region pri
cement types, including blended cements, which may contain
marily has been driven by considerable investment in the construc
industrial waste and byproducts. If these alternative cements can
tion sector. Further construction of road and rail networks across
be made economically viable, they may contribute to
major cities and infrastructure development are likely to continue
a considerable reduction in CO2 output from the cement industry.
to supplement the growth of the regional market (Abbass, Kumar,
and El-Gendy 2018). The healthy increase in construction activity
throughout the MENA region suggests that demand for cement Cement production
will continue to rise.
The process of cement making
According to the World Bank, carbon dioxide (CO2) emis
sions are generated from industrial processes such as cement Cement is produced from suitable raw materials in six stages
manufacturing and burning fossil fuels. Cement manufactur (Figure 1). Mining limestone/raw materials; grinding, homo
ing accounts for 5–6% of all anthropogenic CO2 emissions genisation, and blending various raw mix components; the
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
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
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
Table 1. Wastes used as raw material in cement production.

Waste Source Replacement for Reference
Water purification sludge Municipal water treatment plant Calcium supplementary Chen, Ma, and Dai (2010)
Marble sludge Marble industries Calcium supplementary Yen, Tseng, and Lin (2011)
Sewage sludge Municipal sludge treatment plant Silica supplementary Aranda Usón et al. (2013)
Fytili and Zabaniotou (2008)
Taruya, Okuno, and Kanaya (2002)
Sugar filter mud Sugar industry Calcium supplementary Li et al. (2014)
Red mud Aluminium industry Alumina and iron Liu and Zhang (2011)
Lime-dried sludge Sewage treatment plant Calcium supplementary Xu et al. (2014)
Spray dried sludge Drinking and wastewater treatment plant Calcium supplementary Husillos Rodríguez et al. (2011)
Ceramic waste Ceramic industry Calcium and mineraliser Puertas et al. (2008)
Oil-based mud cutting Petroleum industry Calcium supplementary Abdul-Wahab et al. (2016)
Al Dhamri et al. (2020)
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).
and fauna. Contaminants and hazardous substances are pre

sent in sewage sludge, including plasticisers, synthetic fibres,
biosolids, and various Cd-, Cu-, Pb-, Hg-, Mo-, Ni-, Se-, and
Zn-rich complex compounds. In addition, sewage sludge con
tains pathogens, micropollutants, undetected components,
and heavy metals (Donatello and Cheeseman 2013; Fytili and
Zabaniotou 2008).
In many countries, it has been discovered that huge swaths
of farmland, forests, and seawater are contaminated due to the
continuous disposal of this type of waste. As a result of such
research, many places have banned the disposal of sewage
sludge. However, if this sludge is adequately treated, it can be
used in the construction industry and, in many countries,
sewage sludge waste is used in small proportions by the con
struction industry.
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,
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.
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
O3, Fe2O3, MgO, K2O, Na2O, etc. Homogenous mixtures of
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
maintained according to standards. The requirements for

Khattab (2018)
Rice Husk Ash
the constituents like Portland cement clinker, GGBS slag,

pozzolanic materials fly ash, burnt shale, limestone, and
87.7
0.4
0.3
1.2
1.6
0.1
1.7
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
Different countries-initiated cement standards beginning in

Yan et al. (2020)
incinerated ash
the late nineties after it was observed that different cements

18.8
38.3
had different qualities, setting times, strengths and soundness.

5.8
4.1
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
variation was found in different countries’ cement composi

Mehta and
wastes
tions. Eventually, standards were based on numerous factors.

70.8
10.5
12.5
2.2
1.3
1.3
0.6
-
-
For example, standards were revised depending on the type of

construction for which the cement was being used and
whether the material was being used as concrete or mortar.
Smarzewski and Barnat-
Standards were also developed in consideration of the raw

Hunek (2016)
Cinder waste
materials available and fuels used in producing the cement,

the region’s climatic conditions, and the places the cement
51.0
21.6
8.6
2.3
1.3
-
-
-
-
would be used along with the types of use that would be

employed with the cement (Aïtcin and Flatt 2015; ASTM
C595/C595M-16. 2003. ASTM C595-03 ; ASTM Committee
C01.10, . ASTM C150/C150M-16 ; EN 197-1. 2011). In recent
Phospho-gypsum
Akin Altun and
years, the standards of various new generation cements have

Sert (2004)
Table 3. Chemical analysis of some wastes used as additives in cement grinding.
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
-
using the cement. However, standards have been developed

only for cements which meet certain mechanical, physical and
chemical requirements (ASTM, 2007 ; ASTM C595/C595M-
Ashish (2019)
16. 2003. ASTM C595-03 ; ASTM C807, 1999 ; EN 197-1.

Silica Fume
Mehta and
2011). Even today, cement is generally consumed by local

95.0
0.2
0.4
0.5
0.3
0.6
0.1
-
-
and regional markets; in very few instances, cement is exported

to other countries.
The previous discussion highlights the fact that defining
Liu, Qin, and Yu
Blast-furnace
fixed specifications for cement is an enormous task because

(2020)
of the different plants’ and different countries’ raw material

32.9
15.8
37.2
10.9
slag
0.1
0.4
0.8
-
composition, available fuels, process parameters, and climatic

conditions.
Giergiczny
(2019)
Fly Ash
46.7
19.2
7.5
9.4
1.4
1.8
1.8
2.9
5.9
Impact on the cement properties

The composition of raw materials, additives, and fuel has
Composition
a significant bearing on cement’s properties. Limestone used

Reference
for cement production by different cement plants varies con

LOI950°C
Fe2O3
Al2O3
Na2O
siderably in mineralogy, chemical composition, physical fea

MgO
SiO2
CaO
K2O
SO3
(%)
tures, and microstructure. Significant components may not

Akin Altun and Sert (2004) used weathered phosphor-

gypsum by-product as a set retarder in Portland cement.
They compared the setting and mechanical properties of phos
pho-gypsum cement that were prepared in different ratios with
Portland cement containing natural gypsum and found that
the highest 28-day compressive strength is associated with 3%
phosphor-gypsum cement. Smarzewski and Barnat-Hunek
(2016) utilised coal cinder in high-performance concrete and
studied mechanical behaviour and durability. Coal cinder,
inorganic waste produced by the combustion process in boiler
house used as cement additive with 30% showed higher com
pressive strength, increase in absorptivity and high surface free
energy. Simultaneous addition of coal cinder waste cement was
found to improve resistance to salt crystallisation of cement
concrete. Yan et al. (2020) conducted a feasibility study about
using incinerated bottom ash municipal solid waste as
a cement-stabilised macadam aggregate. The addition of the
ash showed a reduction in properties like density, water-
absorption, porosity, hydraulicity, and cementitious activity.
The increased substitution rate of the waste in cement (up to
20%) was found to be associated with a reduction in drying
shrinkage and an increase in the leaching of heavy metals.
Roslan et al. (2020) investigated experimentally the properties
of electric arc furnace steel slag waste generated from steel
industries as cement replacement (up to 20%). The properties
like workability, initial surface absorption, and heavy metals
leaching were studied along with the regular physical proper
ties. The results confirmed that the surface and water absorp
tion capacities were enhanced. The leaching tests revealed that
the results were within the limits which favoured high poten
tial for application as green concrete.
Figure 4. Rate of heat release for cement paste made of different percentages of
fly ash by isothermal calorimetry method (Pacewska and Wilińska 2013). Nazer et al. (2016) substituted copper slag up to 25% in
Portland cement mortars and studied their alkali-activation
properties by different analytical methods. The measured slag
vary considerably, but minor constituents may vary largely. reactivity was confirmed as the copper slags indicated an
Minor variations in raw materials can affect the formation interesting binding properties while used in the production
phase, so the composition of cement clinker should be ade of blended cement.
quately understood, especially because these minor constitu
ents (e.g., magnesia, barium, strontium, titanium, chromium,
Impact on cement strength and hydration
vanadium, manganese, sulphates, phosphates, fluorine, alkalis)
can directly and disproportionately impact clinker properties To achieve strength, different grades of concrete (e.g., M-25,
and the quality of the cement produced (Hewlett 2003). These M-30, M40, M-50, M-100) have been developed per require
minor constituents can affect the properties of the cement ments. These grades mainly define compressive strength and
either by changing phase relations and the reaction products meet all required physical and chemical parameters.
formed. Alternatively, they may alter the reactivity of the main Compressive strength tests are conducted at days one, three,
cementing compounds towards water by building solid solu seven and 28 to ascertain the development of the concrete’s
tions of different properties or by producing water-soluble targeted strength (ASTM, 2007 ; Kurdowski 2014). Developing
compounds. These effects may influence setting and hardening a proper concrete formulation and mix design is a must. The
processes. Because these effects may manifest singly or in water-to-cement ratio must be maintained to achieve the tar
combination, it is desirable to identify the constituents present geted parameters. After attaining the targeted concrete’s basic
in the raw materials and the proportion of their content to mechanical properties, compressive and bending strengths of
postulate their possible effect on clinker quality and the cement the concrete are measured. Short- and long-term durability
produced from them. The advantage of their presence or tests follow to ensure the concrete’s proper development.
adequate steps to safeguard against the possible harmful effects Durability tests for the concrete’s chemical resistance in dif
to control the clinker quality is required. Potentialities for ferent environments, including resistance against Na2SO4,
these naturally occurring raw materials or the potential use MgCl2, NH4Cl, HCl, and CO2 in the environment are mea
of industrial waste should be established. Most of these mate sured. The water absorption coefficient and apparent moisture
rials have been investigated in detail and are successfully used diffusivity are measured to ascertain the hygienic and thermal
by cement plants worldwide. properties of the concrete. These two tests assess the transport
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
glass powder with Portland cement with different ratios

to study its physical properties. The influence of silica
present in them as amorphous showed improvements in
compressive strengths of all mortars due to the increase in
hydration time. The pozzolanic nature of rice husk ash and
glass powder enhanced the mechanical properties of
cement mortars.
Impact on CO2 emissions

The production of cement is not only energy intensive but also
represents one of the world’s most crucial CO2 emission
sources. Based on the technology of the production, CO2
emissions range from 0.73–0.99 tons of CO2 per ton of cement
(Ali, Saidur, and Hossain 2011; Uwasu, Hara, and Yabar 2014).
More than half of this amount is produced from calcination,
which is an essential part of cement production. Therefore,
countless efforts have been made to use supplementary cemen
titious materials, which can replace at least part of the cement
in concrete with more environmentally friendly materials.
Even industrial waste with its residual energy and low chloride
and heavy metal contents can be appropriated to provide part
of the energy required to make Portland cement. Additionally,
alternative fuels that do not increase CO2 emission levels can
be used. Using alternatives should not increase production
costs; instead, they must bring profits. Waste carbons from
different industrial processes, or used oil, solvents, tar mud,
etc. can be considered as alternative fuels for Portland cement
Figure 5. Compressive strength of mortars containing cement with fly ash (FA),
high-calcium fly ash (HFCA) and granulated blast furnace slag (GBFS) (Giergiczny production.
2019). The total carbon emissions estimated from cement produc
tion in 1994 were 307 million metric tons of carbon out of
which 160 million metric tons were from process carbon
role in cement strength; therefore, the reaction between poz emissions and 147 million metric tons were from energy use.
zolanic materials and Ca(OH)2 and the resultant conversion to Overall, the top 10 cement-producing countries accounted for
a calcium silicate product will contribute to the cement’s 63% of global carbon emissions from cement production in
durability. 1994. The average intensity of CO2 emissions from total global
Liu, Qin, and Yu (2020) studied the particle size of slag cement production is 22 kg of cement. Emission mitigation
particles that present in the slag cement. The blended cement, options include improving energy efficiency, introducing new
containing 50% cement clinker and 50% slag powder, was processes, shifting to low carbon fuels, using waste fuels, and
tested for its compressive strength. The study concluded that increasing the use of additives in cement making. Eventually
the determined strength of slag cement does not only depend using alternative cement and removing CO2 from flue gases in
on glass content, but also on the particle size distribution of kilns might be approaches employed to mitigate carbon
slag present in the cement. emissions.
Mehta and Ashish (2019) investigated the effect of silica Improving energy efficiency reduces CO2 emissions from
fume and crushed waste glass as a cement substitute, due to its fuel and electricity uses and may reduce the cost of cement
high content of silicon, in concrete. The addition of silica fume production. Improvements may be attained by using more
up to 20% was found to increase the compressive, tensile and energy efficient equipment, replacing old installations with
flexural strengths of concrete due to the increase in the hydra new ones or shifting to entirely new types of cement produc
tion reaction rate. The presence of silica fume in a percentage tion. The most significant gain in reducing energy input may
above 20% was found to improve the durability properties of come from improved fuel efficiency. The main opportunities
concrete but reduce the strength due to the decrease of the for fuel efficiency in the kiln are the conversion to more energy
calcium hydroxide content in the cement concrete. The waste efficient variants, optimising the clinker cooler, improving
glass addition shows the cement vulnerable to alkali-silica preheating efficiency and burners as well as instituting process
reaction but it was reduced by the addition of silica fume controls and management systems. Introducing high-
with this cement mix. The lower specific area of glass powder efficiency classifiers or motor systems, and process control
present in cement increased the pump flow even in the lower systems are required. It has been estimated that future tech
water-cement ration. nologies will bring energy savings to almost 48%, leading to
Younes, Abdel-Rahman, and Khattab (2018) prepared CO2 emission reductions of 27% (Ali, Saidur, and Hossain
ternary blended cement using rice husk ash and waste 2011).
Research direction The carbon capture technology, a breakthrough innovation

but still requires industrial level study, shows promising influ
The cement considered as the second-highest consumer
ence in supporting to achieve commitment under the Paris
product next to the water and the consumption reaching
Agreement which calculates the reduction of annual CO2
around one ton per annum for each person. Considering the
emission by the energy sector by 60% from current levels in
level of the carbon footprint of cement concrete from the
2050. By capturing post-combusted carbon dioxide by suitable
environmental impact perspective and the life-cycle aspect
absorbers like certain amines, special capturing membranes, or
cement replacements considered vital. The prevailing usage
by calcium looping using calcium oxide and utilisation as
of successful supplementary materials like fly ash, ground-
carbon feedstock or for fuel production seen as the best option
granulated blast furnace slag, and other potential waste by-
for a significant reduction in CO2. Schneider (2019) presented
products play an important role in bringing down the
in his paper about the usage of such technology in the cement
impact. The future trend in concrete focus on self-
manufacturing more feasible due to the availability of suffi
compacting, geopolymer, demolition and recycling, and
cient heat which requires capturing the CO2. Further, the
supplementary cementitious materials. Further, focusing
separation of nitrogen from the combustion air which enters
on the production process such as belite cements, clinker
the cement kiln using oxyfuel technology results in the lesser
ization factor also of greater concern for the reduction of the
thermal requirement, and a high concentration of CO2 and
carbon footprint.
water vapour enable effective carbon capturing. Such process
The supplementary cementing materials (SCM) role in
implementation requires industrial level trails to assess the
partial replacement of cement due to their pozzolanic and/
complexities and further adjustments required in an existing
or cementitious properties beyond their ability in reducing
cement manufacturing plant.
environmental burdens also effectively improve physio-
mechanical, mobilisation, and durability properties. Panesar
(2019) studied four major SCMs effects on cement hydration,
Conclusion
fresh, mechanical, transportation, and durability. The SCMs
ability on resisting chloride ingress, alkali-silica reaction, and Because most of the world’s raw materials are quickly dimin
sulphate attacks were briefly studied by the author in different ishing, the most significant challenge that cement technolo
concretes. Giergiczny (2019) focussed in his study on gists will face in the coming years is an investigation of
improving the binder properties like long setting time, low cement’s raw materials and their optimum use. A second chal
early strengths, etc. due to the addition of SCMs. Addition of lenge is to address environmental issues related to raw material
high activated additives like silica fumes, metakaolin, etc. production. Cement plants worldwide must put more effort
minimises the negative futures of high addition of SCMs in into improving the different types of machinery used in var
the cement concrete which helps in shortening setting times ious production units. Breakthroughs can be achieved by con
and influencing high early strengths and increasing tinuous monitoring of existing units of the plant. Meticulous
durability. use of suitable fuels is necessary to limit energy conservation.
Although the utilisation of SCMs supporting the cement Optimal use of diverse kinds of fuel used during production
replacement, in some regions like the Sultanate of Oman, must be defined to avoid any underuse of fuels.
the availability is limited, or uncertain. For example, the Quality control in clinker production must be dealt with
main fuel utilised for power generation in the Gulf region, strictly to avoid problems faced by construction industries.
natural gas, phasing out coal-based power units which limit Developing new types of cement has become the need of the hour.
the fly ash availability. The availability of another major Waste generation and utilisation must be managed effec
SCM, slag, highly depends on the economy and therefore tively. More research-based efforts should be undertaken to
uncertain. In such regions degraded concrete infrastruc achieve targeted results. More scientific work is required for
tures generate as a result of ageing and infrastructure devel using the refuse generated by various industries as waste that
opment can be used as SCMs. Another conventional could be used in clinker production or to develop newer types
substitute to some degree is Belite cements. Schneider of cement go untouched.
(2019) in his study briefs that belite clinkers around 4090% Using waste generated by various production units in the
belite. It can be produced in a conventional cement kiln with concrete industry is another area warranting examination.
low process CO2 emission by lowering the lime saturation Ample scope remains for investigations of the proper utilisation
factor. The calcium sulphoaluminate cements produced of waste. One further step has to be taken up by the construction
using bauxite as one of the major raw materials which industries on the technology transfer and the adaptation of the
contain ye’elimite, belite, and gypsum show around 20 to research work done by the scientists and engineers. More stress
30% less CO2 emissions during the production process. The should be placed on testing to help in the development of quality
measures to be taken in optimising the energy demand for concrete. Proper construction fields should be identified that
cement manufacturing are also of major concern with might be able to use concrete formulated with waste.
regard to clinkerization process and finer grinding pro Undertaking such ventures will help maintain the ecological
cesses. The current electrical energy requirement of 104 to balance as well as societal development.
110 kWh/t could be bringing down to 90 to 95 kWh/t with In conclusion, cement is a critical part of concrete. As stated
efficient equipment. earlier, to initiate the hydration process, Portland cement is
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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International Journal of Sustainable Engineering

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An overview of alternative raw materials used in

Sabah Ahmed Abdul-Wahab , Hilal Al-Dhamri , Ganesh Ram & Vishnu P.

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An overview of alternative raw materials used in cement and clinker manufacturing

ABSTRACT ARTICLE HISTORY

Introduction (Farzanegan and Markwardt 2018). Around 50% of the total

Table 1. Wastes used as raw material in cement production.

and fauna. Contaminants and hazardous substances are pre­

O3, Fe2O3, MgO, K2O, Na2O, etc. Homogenous mixtures of

maintained according to standards. The requirements for

the constituents like Portland cement clinker, GGBS slag,

Different countries-initiated cement standards beginning in

the late nineties after it was observed that different cements

had different qualities, setting times, strengths and soundness.

variation was found in different countries’ cement composi­

tions. Eventually, standards were based on numerous factors.

For example, standards were revised depending on the type of

Standards were also developed in consideration of the raw

materials available and fuels used in producing the cement,

would be used along with the types of use that would be

years, the standards of various new generation cements have

using the cement. However, standards have been developed

16. 2003. ASTM C595-03 ; ASTM C807, 1999 ; EN 197-1.

2011). Even today, cement is generally consumed by local

and regional markets; in very few instances, cement is exported

fixed specifications for cement is an enormous task because

of the different plants’ and different countries’ raw material

composition, available fuels, process parameters, and climatic

Impact on the cement properties

a significant bearing on cement’s properties. Limestone used

for cement production by different cement plants varies con­

siderably in mineralogy, chemical composition, physical fea­

tures, and microstructure. Significant components may not

Akin Altun and Sert (2004) used weathered phosphor-

glass powder with Portland cement with different ratios

Impact on CO2 emissions

Research direction The carbon capture technology, a breakthrough innovation

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and fauna. Contaminants and hazardous substances are pre

variation was found in different countries’ cement composi

for cement production by different cement plants varies con

siderably in mineralogy, chemical composition, physical fea