Cement Industry - Sustainability, Challenges and Perspectives - SUB

Environ Chem Lett (2011) 9:151–166
DOI 10.1007/s10311-010-0302-2
REVIEW
Cement industry: sustainability, challenges and perspectives

F. A. Rodrigues • I. Joekes
Received: 26 April 2010 / Accepted: 6 October 2010 / Published online: 23 October 2010
Ó Springer-Verlag 2010
Abstract Cement-based materials, such as concrete and its properties are also presented. Special attention is given to
mortars, are used in extremely large amounts. For instance, the role that cement chemistry can play in terms of sus-
in 2009 concrete production was superior to 10 billion tons. tainability. The most relevant aspects are outlined, such as
Cement plays an important role in terms of economic and the use of alternative materials, new possibilities and also
social relevance since it is fundamental to build and improve the recycling of materials. It is also argued that an important
infrastructure. On the other hand, this industry is also a aspect is the role of research and development necessary to
heavy polluter. Cement production releases 5–6% of all improve cement sustainability.
carbon dioxide generated by human activities, accounting
for about 4% of global warming. It can release huge amounts Keywords Cement Sustainability Green chemistry
of persistent organic pollutants, such as dioxins and heavy Carbon dioxide Pollutants
metals and particles. Energy consumption is also consider-
able. Cement production use approximately 0.6% of all
Abbreviations
energy produced in the United States. On the other hand, the
CKD Cement kiln dust
chemistry underlying cement production and its applica-
c/s Cement to sand ratio
tions can be very helpful to overcome these environmental
ITZ Interfacial transition zone
issues. In terms of manufacture, there are many alternative
MDF Macro-defect-free cement
materials that can be used to minimize carbon dioxide
NOx Nitrogen oxides
production and reduce energy consumption, such as calcium
PCDDs Polychlorinated dibenzodioxins
sulfoaluminates and b-Ca2SiO4—rich cements. Using resi-
PCDFs Polychlorinated dibenzofurans
dues from other industrial sectors can also improve the
PCBs Polychlorinated biphenyls
sustainability of cement industry. Under adequate condi-
PAHs Polycyclic aromatic hydrocarbons
tions, waste materials such as tyres, oils, municipal solid
PCDDs Polychlorinated dibenzo-p-dioxins
waste and solvents can be used as supplementary fuel in
w/c Water to cement ratio
cement plants. Concrete can be used for encapsulation of
waste materials such as tyres, plastics and glasses. In this
review, we discuss some aspects of the cement industry Introduction
associated with environmental science. Other issues such as
economic aspects, the chemistry of cement manufacture and Construction industry is an important and dynamic sector in
the world economy. It is responsible for the creation of jobs,
the modernization of infrastructure and the improvement of
F. A. Rodrigues (&) life standards, among others. Also, this industrial sector is
Universidade de Mogi das Cruzes, Mogi da Cruzes, Brazil directly related to many other areas, such as financing,
e-mail: [email protected]
energy, mining and transportation, just to mention a few.
I. Joekes Cement, the most important component of construction,
Universidade Estadual de Campinas, Campinas, Brazil plays a fundamental role in modern world. This material is
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152 Environ Chem Lett (2011) 9:151–166
produced in almost every country and region and presents imagine a world without cement-based materials. The
many interesting aspects, such as physical, chemical and availability of basic raw-materials, the simple manufacture
mechanical stability. Cement, when compared to other process and its endless applications make cement a very
materials, can be considered inexpensive and abundant. On popular and widespread material. According to Meyer
the other hand, in many aspects, the chemistry of cements is (2009), the world production of concrete is superior to 10
not so familiar or well established. Additionally, the pro- billion tons yearly.
duction of cement is not an environmentally friendly process. A comparative analysis may be useful to introduce
It requires very high temperatures (usually above 1,500°C) cement industry. For instance, let us consider data from
and the consumption of large amounts of non-renewable world mining production in 2007. Combined, the extrac-
raw-materials. It is estimated that 5–6% of all carbon dioxide tion of aluminum, alumina and bauxite, cadmium, cobalt,
generated by human activities is derived from cement fab- cooper, garnet (industrial), gypsum, kaolin, lead, lime,
rication. Also many important pollutants are usually gener- manganese, phosphate rocks, soda ash and zinc rendered
ated, such as dioxins and heavy metals, among others. about 1,398,000 thousand metric ton. Therefore, the pro-
Numbers related to cement-based materials and construc- duction of all these materials together corresponds to
tions are very impressive. Engineers use to say that concrete is approximately half of cement production for the same year
the second component mostly used by man, just after water. (US Department of Interior 2007).
Cement, as a technological material, is very successful, as Table 1 shows the top-10 producers of cement among
everyone knows. Many characteristics can be easily cited. countries (US Department of Interior 2005–2009). There
First of all, it works very well at room temperature. It is simple are many interesting features worthy to mention. In 2007,
to use, easy to shape, and within few hours, renders an China produced about half of the cement in the world. It
‘‘artificial’’ rock, having numberless applications. Cement is reflects not only the extraordinary growth of Chinese
used to build simple houses, highways, bridges and more economy but also, in some sense, the changes occurring in
complex systems as dams or nuclear power plants. In fact, it is that country (Shen et al. 2005; Zhang and Zhao, 2000). In
almost impossible to imagine the world without cement or the last 20 years or so, China experienced many important
concrete. Despite such popularity, cement industry faces changes: the raising income of foreign investment, unem-
many challenges due to environmental concerns. As will be ployment in rural areas, reorganization of state-owned
discussed in this review, cement industry is an important facilities and business and the liberalization of private
polluter, releasing huge amounts of carbon dioxide, NOx, business. Probably, the most visible result of these modi-
dibenzo-p-dioxins (PCDD), dibenzofurans (PCDF), heavy fications was the urbanization and the growth of cities.
metals and particles, among other pollutants. Also energy Urbanization is an important issue regarding cement con-
consumption is considerable. It is estimated that about 0.6% sumption. In only 22 years (from 1978 to 2000), the urban
of the energy consumed in the United States is used to produce Chinese population changed from 170 million to 456 mil-
cement. Moreover, large amounts of non-renewable materials lion or from 17.9 to 36.1% of total population. In 2003,
are consumed in the process. Many efforts have been made to urbanization in China reached 41% while world average is
minimize the impact of these issues. Governments, industrial around 46% (Shen et al. 2005). India, the second major
sector, researches and other organizations are dealing seri-
ously to improve the sustainability of cement industry.
On the other hand, construction materials can be very Table 1 Cement production for major countries in the period
2004–2007 (thousand metric tons)
useful to minimize hazardous effects from other economic
activities. The industry is using and/or testing alternative Country 2004 2005 2006 2007
materials to generate energy in cement production, such as China 934,000 1,040,000 1,200,000 1,350,000
used tires and other solid wastes. In this review, the role of
India 125,000a 145,000a 155,000a 170,000a
cement industry in a challenging perspective is presented.
USA 99,000 101,000 99,700 96,500
Many important aspects are discussed, such as the recent
Japan 67,400 69,600 69,900 67,700
improvements in cement industry, new technologies in a
Russia 43,000 48,700 54,700 59,900
materials, new remediation methods, the recycling of waste
Korea 53,900 51,400 55,000 57,000
materials, among others.
Spain 46,800 50,300 54,000a 54,500
Turkey 38,000 42,800 47,500 49,500
Italy 38,000a 46,400 43,200 47,500
Cement and the economy
Brazil 38,000a 36,700 39,500 46,400
World 2,130,000a 2,310,000a 2,550,000a 2,770,000a
Probably, the most remarkable aspect of cement industry is
a
the large-scale numbers. It would be very difficult to Estimative
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Environ Chem Lett (2011) 9:151–166 153
cement producer, shows a different but similar pattern, and a fundamental role in modern world, since it is responsible
urbanization is also an important driving force in cement for sustaining population growth and economic
industry. development.
Cement is used to build better houses (especially in poor The economic importance of the construction industry is
countries and regions) and to improve infrastructure, such doubtless considerable. It is indeed difficult to measure its
as dams, airports, roads and sanitation. In many countries, economic impact. Cement is a produced and consumed at
the consumption of cement is a consequence of the lack of extraordinary rates and amounts. However, cement is never
infrastructure. In countries like China and India (and cer- used alone. For instance, in order to make an ordinary
tainly many others), part of population does not have building, many other materials and economic sectors are
adequate housing or simple services, such as electricity and involved. Before a construction starts, the planning may
treated water. Also they lack satisfactory roads, power involve engineers and architectural companies. Many
supply and jobs. To attend this demand, in most cases, materials are needed such as sand, rocks, steel, aluminum,
public investments are necessary to build infrastructure and gypsum, glasses and polymers, just to mention a few. Con-
so, to consume cement. Moreover, especially in Asia, the tractors and construction firms are responsible by personnel
transition to ‘‘modern’’ societies has many implications in and services. Also other services are fundamental in building
terms of political and sustainable production (Rock et al. sector: hydraulics, electricity and gas. Electric and elec-
2009). The continuous urbanization of these countries also tronic components, heating and/or air conditioning systems
demands construction materials due to growth of cities and are also present (Horvath 2004; Pulselli et al. 2008). Finally,
migration of population. Furthermore, the mobility of it should be mentioned that individuals are also cement
population requires the construction of many kinds of new consumers, since it is very usual that people buy cement to
buildings (Shen et al. 2005). make small reforms or home improvements.
It should be pointed out, though, that unlike other It is clear that cement is an important material in everyday
materials, increasing cement consumption is not a good life; in fact, few other materials could claim to be as uni-
parameter to measure economic growth. In countries like versal as cement. Its importance is not restricted to con-
USA and Japan, where population has attained excellent struction and repair but is an important part of world
life standards, the cement production has not changed very economy and life standard. From the historic viewpoint,
much in recent years. It is used to maintain existing cement was studied mainly by civil engineers, interested in
infrastructure and, of course, to reform old facilities and the development of mechanical properties. As any other
build new ones (Horvath 2004). In 1997, European Union material, there is an increasingly interest in the compre-
(15) produced and consumed about 11% of world cement, hension of fundamental aspects and properties of cement-
being Italy the major producer. On the other hand, for based materials, in order to improve their performance. In
obvious reasons, Africa shows the lowest production and this sense, the chemistry of cement is fundamental to
consumption of cement among continents (Szabó et al. improve sustainability. Innovation seems to be the keyword
2006). to face the many challenges in this sector. ‘‘Greener’’ pro-
In some way, the use of cement materials is a general cesses can be achieved in many different ways, and some
claim in modern societies. In the last one hundred years, important issues are discussed in the following sections.
world has changed enormously in terms of life standards
and infrastructure, due in part to cement-based materials.
There is no signal that this trend will change in the forth- Terminology, chemical aspects and hydration
coming future. At the end of XIX century, United States
and Europe accounted for approximately 91% of world The term cement is widely used in many different areas as
cement production (Tafunell 2007). Table 2 shows that this dentistry (Zhao et al. 2009; Nakajo et al. 2009), medicine
situation has changed dramatically. Cement industry plays (Gupta et al. 2004; Dorozhkin 2008; Boesel and Reis,
2008) and civil construction (Brandt 2008; Millard and
Kurtis 2008). It may be applied to polymeric, metallic,
Table 2 Major components of ordinary Portland cement type I
ceramic and composite materials. In common, all these
Component Formula Notation % (average) cements present the capability of hardening under specific
Tricalcium silicate Ca3SiO5 C3S 45–60
conditions and to maintain its structural stability for an
Dicalcium silicate b-Ca2SiO4 b-C2S 15–30
extended period of time. In this sense, cement-based
materials can be thought as a solid, whose binder is any
Calcium aluminate Ca3Al2O6 C3A 2–15
kind of cement. However, in the present context, the term
Calcium ferroaluminate 4CaOAl2O3Fe2O3 C4AF 5–15
binder is limited to Portland cement and related materials,
Gypsum CaSO41/2H2O CS 5
used for construction purposes.
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Historically, cementitious materials were used for a long There are many interesting papers and books available
time. The Egyptians used gypsum and lime for the con- (Malhotra 1983; Houst et al. 2008; Hale et al. 2009; Brooks
struction of Pyramid of Cheops, approximately 3,000 BC. et al. 2000).
Romans built many concrete structures, such as the Coli- Many types of cements are available for use in civil
seum in Rome. In fact, the word concrete comes from the construction. Standard ASTM (American Society for
Latin ‘‘concretus,’’ or in modern terminology ‘‘grow Testing and Materials) C150/150 M covers 10 types of
together’’ (Young and Mindess 1981). Portland cement. The distinction between these cements is
In many situations, the words cement and concrete are based on chemical composition and specific needs and
used as synonymous although this is incorrect. In order to requirements, such as the development of mechanical
clarify some terminological aspects, it is useful to keep in resistance or durability. The discussion presented here is
mind some definitions. Concrete can be defined as a mostly based on cement type I; Table 1 displays the major
composite formed by cement, water, coarse aggregates components of commercial cement.
(usually crushed rocks and stones) and fine aggregates It is common in cement chemistry to express chemical
(mostly sand). Mortars are similar to concrete but lack formulas in abbreviated terms. The notation C3S means
coarse aggregates (Lea 1971; Taylor 1997). To guarantee that this component presents three molecules of CaO (=C)
satisfactory mechanical and durability properties, the rel- and one molecule of SiO2 (=S). In terms of oxide com-
ative proportion of each component should be within a position, this compound can be described as 3CaOSiO2.
limited range. For instance, if we think about mortars, the Here, we will preferentially use the familiar chemical
proportion between solids is expressed as cement to sand formulas.
ratio (c/s). This ratio is dependent on the kind of applica- It can be seen that tricalcium and dicalcium silicates are
tion, but a ratio of 1:3 is usual. It can be observed that the major components of ordinary cement. Many properties
‘‘aggregates concentration’’ is much higher than ‘‘cement of concrete that we recognize on a daily basis are conse-
concentration’’. Aggregates are used to fill up higher vol- quence of these calcium silicates. Probably, the key aspects
umes in construction. ‘‘Water concentration’’ is expressed for cement popularity are the many interesting (and chal-
as water to cement ratio (w/c); the w/c ratio in mortars is lenging) characteristics of the reactions between these sil-
typically in the range 0.3–0.6. icates and water (Manzano et al. 2007; Richardson 2000).
There are many other composites prepared with Portland Probably, chemists and other scientists do not realize how
cement, besides plain concrete. Probably, the best known is difficult would be to explain the ‘‘upcoming’’ events, the
reinforced concrete, where steel is introduced to improve hydration of cement (Hadley et al. 2000; Faure and Rodts
stability (Belmouden and Lestuzzi 2007). In fiber-rein- 2008; Hartman and Berliner 2005). First of all, cement
forced concrete, many materials are actually used to pre- hydration takes place at room temperature. It should be
pare specific composites, although metals, polymers and pointed out that cement hydration is an exothermic process
ceramics are more frequent (Buchan and Chen 2007; (Azenha et al. 2009; Trtnik et al. 2008); after addition of
Ahmed and Mihashi 2007). A very interesting composite water, a ‘‘paste’’ is produced. This paste presents very
made from Portland cement is called MDF, macro-defect- attractive rheological properties (Wallevik 2009; Nachbaur
free cement (Kendall et al. 1983). MDFs combine cement et al. 2001) since it can be easily casted and shaped. Within
properties and water-soluble polymer, such as poly acryl- minutes, many coupled chemical reactions are occurring,
amide or poly(vinyl) alcohol. MDFs are processed as and interesting enough, far from thermodynamic equilib-
polymers, through calandering, pressing and machining. In rium (Lothenbach et al. 2008). Moreover after few hours, a
many aspects, MDF’s properties are very superior when solid is formed, and it is ready to support relatively high
compared to traditional cement-based materials (Rodrigues loads without significant volume variation.
and Joekes 1998; Santos et al. 1999). Unfortunately, MDFs These changes, from a gray powder to a stable solid, can
present an important limitation; their mechanical properties be attributed mainly to the hydration kinetic of calcium
are severely damage when exposed to water. This behavior silicates, especially tricalcium silicate. This chemical
is exactly opposed to the idea of hydraulic cements. To the hydrates faster than dicalcium silicate (Young and Mindess
best of our knowledge, commercial use of MDF is limited 1981; Garrault and Nonat 2001). In the initial ‘‘curing’’
(Scrivener and Kirkpatrick 2008). stage and even after months, tricalcium silicate dominates
Nowadays, most of the commercial concretes or mortars the characteristics of concrete. After about 1 year, both
contain also admixtures. These components are usually silicates show the same chemical characteristics and
added to concrete to modify certain properties and to attain hydration degree. In addition, the hydration products are
specific needs and performance (Aitcin 2000; Idorn 2005). about the same for both components (Young and Mindess
Admixtures play an important role in cement chemistry and 1981). However due to complexity of the final product, the
sustainability, but this subject will not be treated here. hydrated phase, it is usual to denote this material as C–S–H
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(hydrated calcium silicate). Literature reports many dif-

a b
ferent viewpoints on the structure and nanostructure of
C–S–H (Matschei et al. 2007a; Kalinichev et al. 2007;
Chen et al. 2004). Also, hydration of calcium silicates is
affected by many variables (Peterson and Juenger 2006;
Ridi et al. 2005).
Calcium aluminates are also important in cement
chemistry and concrete properties. The phase diagram for
the system calcium oxide–calcium aluminate shows that
many compounds can be formed. The presence of con- c d
taminants may influence the final chemical composition
and phase formation for this system (Dı́az et al. 2005;
Matschei et al. 2007b). The presence of iron leads to the
formation of solid solutions. Usually, this complex system
is referred as C4AF. The hydration and the products formed
during aluminate hydration are also very complex (Ghorab
et al. 1998a, b). If pure, calcium aluminates react imme-
diately with water, forming hydroaluminates (Minard et al.
2007). The presence of hydroaluminates is very undesir-
Fig. 1 Simplified version of the topochemical hydration of cement
able since it would make the paste unsuitable for casting,
due to very fast stiffening (Clark and Brown 1999, 2000).
This reaction would be faster than the corresponding for several variables. The above representation is a very simple
calcium silicates. During the cement preparation, gypsum illustration; however, it is helpful to present a chemical
is added to avoid this behavior. The hydration of calcium reaction between common solid and liquid water, rendering
aluminates in the presence of gypsum leads to the forma- a hydrated phase.
tion of a thermodynamic unstable phase called ettringite
(Ca6Al3(SO4)3(OH)1226H2O). The mechanism involved in
the delay of calcium aluminate hydration is still a matter of Cement production and the environment
discussion (Collepardi 2003; Tian and Cohen 2000).
On the other hand, since Portland cement is a material Cement can be considered an inexpensive material. In
produced worldwide, it should be clear that for each order to be competitive, manufacture plants tend to be
country or region, it will present specific characteristics. close to raw-material sources to minimize the costs of
For instance, actual chemical composition is dependent on production (Kendall et al. 2008). In fact, the costs of
many variables, such as the nature of raw-material and transportation are very important and may determine the
impurities, among others (Mechling et al. 2009; Papadakis final cement price (Newmark 1998). Figure 2 presents a
and Tsimas 2005; Sahu and Thaulow 2004; Heikal 2000). simplified diagram for the production of commercial
The use of supplementary material, intentionally added to Portland cement.
cement, will be discussed later. To prepare cement, sources of calcium and silica are
The mechanism of cement hydration can be described needed. The major raw-materials used are limestone and
as a topochemical process (Mehta and Monteiro 1993). dolomite as the sources of calcium; usually quartz, clays
Figure 1 is a simplified description of hydration. When and shale are used to provide silica. Many other minerals
water reaches anhydrous grains (a) it reacts rapidly on the can be used as bauxite, iron ore and slag, among others
surface, in an exothermic process. For tricalcium silicate, it (Türkmenoğlu and Yavuz-Işıkli 2008; Ewais et al. 2009).
takes about 15 min. As consequence, an external core is Also a large number of raw-materials are used or under
formed (b); the presence of hydrate cement particles will test (Erdem et al. 2006; Carrasco et al. 2005; Konsta-
retard internal hydration of cement grains. This is some- Gdoutos and Shah 2003). It should be considered that in the
times referred as the dormant period (Mindess and Young forthcoming future, may be experienced a shortage of raw-
1983), and it takes about 2 h. After this period, by diffu- materials in certain regions (Shih 1999; Shen et al. 2005). A
sion, water penetrates into the interior of particles, pro- more detailed and interesting analysis about materials con-
moting the set of cement (c). Finally, after many months sumption in the world, in the last 100 years, indicates the
the hydration will be almost complete (d). need of more efficient processes (Krausmann et al. 2009).
As pointed out before, however, the actual cement After mining of raw-materials and initial crushing, the
hydration is a very complex phenomenon, determined by chemical composition is adjusted using several possible
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1. Quarrying raw
-material
2. Intial processing (crushing)
3. Blending, mixing, adjusting composition
4. Initial heating
5. Secondary heating
6. Clinker cooling
7. Gypsum addition (cement) Fig. 3 Environmental map for cement production: the release of
pollutants into atmosphere
8. Final grinding
production, taking into account the potential generation of

9. Packing, distribution
hazardous substances. This ‘‘environmental map of cement
production’’ is not definitive since there is a great vari-
Fig. 2 Major steps of commercial production of cement ability of processes, raw-materials and plant design; how-
ever, it can be useful to better understand the impact of
mineral sources. The solid mixture is heated at very high cement fabrication on environmental issues.
temperatures, usually above 1,500°C. This solid product is Figure 3 shows a schematic diagram (environmental
called clinker. Commercial cement is obtained after addi- map) describing the preparation of cement. It can be dis-
tion of gypsum to clinker and final grinding. tinguished three major regions inside the rotary kiln,
A curious aspect is that cement productions has not according to temperature and released substances: (1)
changed significantly over the last 150 years or so. It does dehydration, (2) calcination and (3) clinkering zones. Here,
not mean, however, that many improvements were not we will describe three major sources of environmental
added to production. Thomas A. Edison, for example, concerns: generation of particles, generation of organic
received 49 patents related to cement production (Thomas pollutants and the release of carbon dioxide.
Edison Papers).
The fabrication of commercial Portland cement is a Generation of particles
typical solid-state reaction, mostly based on the use of high
temperatures (Suresh and Ghoroi 2009). Many other cera- In all three stages, solid particles can be spread into
mic materials are produced in a similar way (Schackelford atmosphere and cause several problems (Spoo and Elsner
and Doremus 2008). Usually, the reaction between solids is 2001; Xiao and Cai 1995). As a matter of fact, the gener-
limited by the very low mobility of individual species, in ation of particulate material starts with mining and may
contrast to reactions in gaseous or liquid environments. The continue until cement is used by final consumer. For
use of elevated temperatures enhances diffusion in solids instance, the great majority of cement particles shows
favoring the reaction between them. The mechanism and diameter much inferior to 100 lm (Chindaprasirt et al.
kinetic of solid-state reactions are also relatively more 2005) favoring their dispersion. It is well known that small
complex (Khawam and Flanagan 2006). particles, presenting high surface area, can be easily
An important aspect should be presented at this point. transported by air (Sun et al. 2004).
Cement plants can be very different. New facilities tend to Nevertheless, here we are concerned only with particles
be more efficient and better prepared to avoid environ- that are produced in cement facilities. In the three stages
mental risks (Huntzinger and Eatmon 2009). These dif- presented here, the particulate material will collectively be
ferences arise even in developed countries; however, in named cement kiln dust (CKD), as it is usual in cement
underdeveloped countries it can be dramatic, due to the industry. CKD is also a complex solid with variable com-
lack of legislation and poverty. In many situations, working position. It can be assumed that major components are
conditions are really unsatisfactory (Mwaiselage et al. sulfates, chlorides, aluminates, oxides and salts (Duchesne
2005). and Reardon 1998). Due to high calcium oxide concen-
On the other hand, from the environmental viewpoint, tration, it is a very basic material. An interesting study
perhaps it should be more appropriate to visualize cement (Massicotte et al. 2004) on the effect of CKD on earthworm
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(Lumbricus terrestris) suggested the inhibition of immune Karstensen 2008; Carrasco et al. 2002). Since cement kilns
system of this invertebrate, although more detailed inves- reach very high temperatures, the initial idea is that these
tigation is still needed. residues could be used together with traditional fuels,
According to van Oss and Padovani (2002), up to 20% generate specific heat and after all, they could be com-
of clinker mass can be lost as CKD, even though modern pletely destroyed.
plants can reduce this number significantly. Once particles Previous experience showed that PCDD/F and PCBs can
are released, their dispersion is dependent on many factors, be formed during the burning of municipal solid waste
such as topography and atmospheric conditions (Polat et al. incinerators. The mechanisms involved in the formation of
2004; Abdul-Wahab 2006). Humans and animals can be these organic pollutants are sometimes very complex
contaminated by inhalation and contact with skin and eyes. (Dickson et al. 1992). It is a good assumption that engi-
Also these particles can be carried to large distances and neering aspects such as feeding rate and type of incinera-
accumulate in soils, rivers, etc. More important, this dust tor may inhibit or minimize the formation of pollutants
may have relatively high concentrations of heavy and toxic (Prisciandaro et al. 2003).
metals (Zaki et al. 2007; Eckert and Guo 1998). For On the other hand, in the second stage (calcination zone)
instance, Isikli et al. (2006) showed that in vicinity of a it was confirmed the formation of PCDD/Fs, associated
cement plane in rural Turkey, the concentration of cad- with the lower temperatures. In this case, the burning
mium in plants and soil was much above control sites. conditions seem to be of fundamental importance on the
A similar study (Morales et al. 1996) suggested that concentration of these pollutants (Lohman and Seigneur
atmospheric concentration of zinc and cadmium was higher 2001).
in western Venezuelan savannah than expected, also due to In dehydration zone (roughly up to 600°C), free or
emissions from a cement factory. A more dramatic situa- unbounded water is lost, and most of clays start to
tion was described in Nigeria (Abimbola et al. 2007) where decompose. Also depending on fuels used or available to
the high concentration of heavy metals was associated with cement production, many organic pollutants can be gen-
human diseases. On the other hand, negligible effect of erated such as dioxins, furans, polycyclic aromatic hydro-
cement and cement dust was observed in rats (van Berlo carbons (PAHs), polychlorinated dibenzofurans (PCDFs),
et al. 2009). polychlorinated dibenzo-p-dioxins (PCDDs) among others.
The emission of CKD can be reduced by the use of Also gases like NOx and sulfur compounds, just to mention
modern technologies. Also, there is a continuous interest in a few, can be expelled from industrial kilns if the process is
the utilization of CKD. It has been used in soil adjustment not well controlled (Lemieux et al. 2004; Börjesson and
(Peethamparan et al. 2008) or sewage treatment or even in Gustavsson 2000).
concrete manufacture (Maslehuddin et al. 2009). In the third stage of cement manufacture (clinkering
zone), the addition of liquid wastes as partial substitution
Organic pollutant of traditional fuels leads to almost no generation of organic
pollutants (Benestad 1989).
The term dioxin encompasses a large number of com-
pounds. It can be applied to a class of substances related to Carbon dioxide
halogenated aromatic hydrocarbons. Basically, three clas-
ses are usually considered (Srogi 2008): polychlorinated In the calcination zone, there is an additional source for
dibenzodioxins (PCDDs), polychlorinated dibenzofurans environmental concern: the release of carbon dioxide.
(PCDFs) and the ‘‘dioxin-like’’ polychlorinated biphenyls Numbers are somewhat controversial, but it is estimated
(PCBs). All these compounds are extremely toxic, even in that cement production accounts for about 5–6% of all
very small concentrations (Schecter et al. 2006; Jin et al. carbon dioxide emissions caused by human activities
2009). Dioxins are generated in many industrial processes (Morsli et al. 2007; Gartner 2004; Pulselli et al. 2008). For
such as incineration (Reis et al. 2007; Yasuhara and instance, as result of Kyoto Protocol, in 2003, European
Katami 2007), paper industry (Charlestra et al. 2008), Union set through the Emissions Trading Directive (ETD)
preparation of pesticides (Götz et al. 2007) among others. specific target for the reduction of green house gases. Some
The formation of PCDDs, PCDFs and PCBs may occur industrial sectors were selected, such as oil refining, pulp
during cement fabrication, especially due to the co pro- and paper, steel and cement (Lund 2007).
cessing of hazardous materials in cement kilns (van Loo The production of CO2 in cement plants does not occur
2008). Many residues can be used as supplementary fuels only in the calcination zone, inside the kiln. In fact, there
in cement industry. In fact, it seems to be a very good are four major sources of CO2 formation during the pro-
approach to the disposal of materials as used tyres, carpets, cess: the burning of fossil fuels, chemical reactions,
oils from industrial activities etc. (Prisciandaro et al. 2003; transport and electricity, as presented in Fig. 4.
123
fossil
40%fuels
80
40%
CO2 released (103 tons)

75
5% electricity
50% 5% 5% 70
transport
5%
65
50%
chemical reactions
Fig. 4 Distribution of carbon dioxide release during cement 60

preparation
55
1990 1992 1994 1996 1998 2000 2002
About 50% of carbon dioxide produced during cement year
fabrication is due to thermal decomposition of calcium
carbonates (Rehan and Nehdi 2005). Although the com- Fig. 5 Carbon dioxide released in United States of America from
cement industry
plexity of raw-materials used in the process, a simplified
equation can be used to represent the release of carbon
dioxide: sustainability. Clearly, cement manufacture is an energy-
D intensive process. When the burning of fossil fuels and
CaCO3 ! CaO þ CO2
other energy sources are considered, the total balance is
After calcium carbonate decomposition (and many other quite impressive: 1 ton of cement generates approximately
possible carbonates), the calcium oxide will be able to react 1 ton of carbon dioxide (Worrell et al. 2001). Also it
with other components to render the silicate. consumes about 60–130 kg of fossil fuel and 110 kWh
The syntheses of tricalcium and dicalcium silicates can (Morsli et al. 2007). Interesting enough, in United States of
be presented as follows: America, cement industry consumes 0.6% of total energy
D produced in the country. In terms of natural resources, the
SiO2 þ 3CaO ! Ca3 SiO5 production of 1 ton of cement demands about 1.4–1.6 ton
D of raw-materials (Horvath 2004).
SiO2 þ 2CaO ! Ca2 SiO4 :
Figure 5 shows the variation in carbon dioxide released
Disregarding other sources of calcium, calcium silicates by cement industry in USA, from 1990 to 2001 (Jacott
will demand the release of carbon dioxide; each molecule et al. 2003). It can be seen that there is a continuous growth
of Ca3SiO5 requires 3 molecules of CO2, and b-Ca2SiO4 in CO2 emissions since 1991. In this period, the total
needs two molecules of CO2. As it will be presented latter, variation amounted 32%.
the preparation of cements containing higher concentration In relation to carbon dioxide release, many other aspects
of b-Ca2SiO4 can be an effective way to minimize the could be presented. Engineering aspects are out of the
release of carbon dioxide. scope of this work; briefly, for instance, industry works to
Clinkering zone is the final stage for cement manufac- improve the efficiency of cement preparation in many
ture. Under these conditions, as pointed before, particles aspects; the use of chemical admixtures allows reduction in
can be release to atmosphere, being a potential cause of cement dosage, saving raw-materials and limiting carbon
many healthy problems. dioxide release; the utilization of alternative materials to
It is clear that chemical reactions and the burning of produce concrete; better designed buildings and others
fossil fuels are the major contributors in the process. It (Damtoft et al. 2008; Jegatheesan et al. 2009; Gartner
means that an efficient way to reduce CO2 release is the use 2004). Recycling in cement production will be discussed
of lower temperatures. In practice, however, this is a very later, as a separate topic, although in many circumstances
ambitious task, since the preparation of Ca3SiO5 requires carbon dioxide reduction is also obtained.
huge amounts of energy. Considering only environmental and sustainability
The whole process of cement production presents many aspects, it is clear that cement industry faces many chal-
environmental risks and may be harmful to people and lenges in forthcoming future. Moreover, some may argue
other life forms as well, if not properly conducted (Zhang that the appearance of new technologies and materials for
and Wong 2007; Conesa et al. 2008; Iliuta et al. 2002). construction could dismantle cement industry. However,
However, other aspects should be considered in terms of cement and cement-based materials have great potential
123
not only to overcome these challenges but, especially act- replacement of traditional Portland cement: b-Ca2SiO4–
ing as an important industrial sector, to improve environ- rich cements and calcium sulfoaluminates cements. It
mental and life quality. should be pointed out, however, that pozzolanic cements
are also very attractive materials. There are many paper
and reviews dealing with pozzolanic cements (Siddique
Perspectives and Klaus 2009; Kani and Allahverdi 2009; Velosa and
Cachim 2009; Mertens et al. 2009; Shi and Qian, 2000),
Cement industry, researchers and academics are not and this subject will not be treated here.
secluded from general claims to improve sustainability and b-Ca2SiO4 presents a great potential to reduce envi-
to develop cleaner processes (Chan et al. 2007; Phair 2006; ronmental impact on cement industry. As pointed out
Damtoft et al. 2008; Jegatheesan et al. 2009; Chen and before, b-Ca2SiO4 consumes less calcium oxide (carbon-
Juenger 2009; Mandal and Madheswaran 2010). Many new ate) than Ca3SiO5. Energy requirements for the synthesis of
materials and methods are currently under development, b-Ca2SiO4 are also much lower than Ca3SiO5. Standard
and it is almost impossible to cover all major aspects and formation enthalpies for b-Ca2SiO4 and Ca3SiO5 are
efforts toward a ‘‘greener’’ cement chemistry and respectively 1,810 and 1,350 kJ kg-1 (Kurdowski et al.
manufacture. 1997).
From the many aspects presented so far, it appears that An interesting point is that many methods were devel-
substitution of Portland cement would be a great oped for the synthesis of b-Ca2SiO4, such as hydrothermal
improvement to the environment. In these authors’ view- methods, sol–gel, ultrasonic treatment and also solid-state
point, however, other similar materials can be successfully chemical reaction. Ishida et al. (1994) developed a
used in constructions, together with conventional Portland method based on hydrothermal synthesis of hillebrandite
cement. Instead of think about substitution, probably it is (Ca2(SiO3)(OH)2), an hydrated calcium silicate, having
more adequate to work with the concept of partial ratio Ca/Si = 2. Quartz was used as starting material,
replacement, complementary materials and technological together with calcium oxide. Solids were treated at dif-
innovation. Literature reports many aspects of these ferent hydrothermal conditions. For example, hillebrandite
materials (Pellegrino et al. 2009; Chaipanich et al. 2007; was obtained after treatment of reactants for 10 h and
Chung 1997). However, this work will describe only a 200°C. After this, thermal decomposition of hillebrandite
limited number of options available nowadays. was performed at 600°C, forming b-Ca2SiO4.
Cement is so widespread and popular to simply be cir- A different approach is based on the preparation of
cumvented. In this sense, a more realistic and reasonable b-Ca2SiO4 using renewable materials. Silica (SiO2) is a
approach is to use other materials in conjunction with basic raw-material for preparation of b-Ca2SiO4. It is usu-
cement. Any candidate to partial replacement of commer- ally obtained from mineral sources. However, many organic
cial cement should fulfill at least some requirements. It materials have important amounts of silica. Rice hull con-
should be inexpensive, available in many parts of world, tains about 10–30% of silica. Silica can be extracted from
minimize or completely avoid emission of carbon dioxide rice hull by many methods (Kalapathy et al. 2000; Dahlan
and other greenhouse gases and particles. Furthermore, this et al. 2006). More interesting is the use of rice hull ash
material should present about the same characteristics of derived from thermoelectric power plants. Rice hull is
ordinary cement, as rheological and mechanical properties, burned to generate electricity giving a silica-rich material.
to start with (Sabir et al. 2001; Raupp-Pereira et al. 2008; From this residue, silica can be easily extracted. Under
Gartner 2004; Kacimi et al. 2006). Even if we had now this usual conditions, this material is simply discarded in land-
‘‘ideal’’ candidate, it would take probably many years to fills. A complete green cycle could be devised to generate
use it in large scale. Many tests should be carried out to basic food, electricity and to produce cement to be used
assure safety and long-term performance. Regulatory locally. Rodrigues and Monteiro (1999) developed initially
codes, standard methods and many other issues should be the synthesis of b-Ca2SiO4, from rice hull ash, using
detailed treated to guarantee its safe use and acceptance hydrothermal treatment. Chemicals were mixed together in
(Hooton 2008; Becchio et al. 2009). stoichiometric proportion and treated hydrothermally for
As in many other areas, cement manufacture is contin- 2 h and 150°C. After this, an intermediate silicate with a
uously looking for new and/or innovative solutions to face ratio Ca/Si & 1.6 plus the excess of calcium hydroxide
the environmental concerns and economic restrictions as were obtained. After drying, solids were heated at 800°C,
well. Nowadays, industry and scientific community con- giving b-Ca2SiO4. It can be seen that silica derived from
duct many efforts in order to address these relevant ques- rice hull ash presents a very good reactivity under these
tions. Here, it will be discussed only two classes of conditions. Latter, the synthetic method was improved;
materials that can be thought as ‘‘candidates’’ for partial instead of using hydrothermal method, the solids were
123
treated in ultrasonic bath (Rodrigues 2003a, b). Once again, rapid implementation, in the places where raw-materials
after drying, a mixture of solids was obtained: the inter- are available.
mediate silicate and calcium hydroxide. The solids were
fired at 800°C, forming b-Ca2SiO4. Ultrasonic treatment
was able to replace hydrothermal processing, making the Concrete and the recycling of waste materials
method much more suitable in terms of economic per-
spectives. Also since the method is highly versatile, many Some aspects about recycling were discussed in conjunc-
modifications can be devised in order to modulate solid final tion with Portland cement preparation. Here, we are con-
properties (Romano et al. 2006, 2007). As presented before, cerned about the incorporation of solid residues into the
kinetics hydration of b-Ca2SiO4 is slower when compared cement matrix, during concrete preparation. All around the
to Ca3SiO5. The introduction of ‘‘foreign’’ atoms (doping) world, many industrial by-products such as plastic bags and
may have influence on the reactivity of b-Ca2SiO4 in rela- bottles (Ambrose et al. 2002), used tyres (Ferrão et al.
tion to water (Mahfouz et al. 2008). Also an important 2008), electric and electronic wastes (Zoeteman et al.
aspect is related to chemistry of this solid. To date, very 2009), just to mention a few, are increasingly a cause of
little information of b-Ca2SiO4 chemistry is available from environmental concern. The disposal of these and other
scientific viewpoint. Most information is devoted to prop- residues can be very difficult or expensive. From the many
erties such as mechanical resistance and durability. How- aspects presented so far, it appears that concrete can be an
ever, there are many examples in material science where the extraordinary ‘‘storage space’’ for many types of residues.
relation between chemical composition (and crystallogra- Unfortunately, the actual situation is far more complex.
phy) and macro properties is well established leading to In plain concrete, there is an important interface
important developments. between large aggregates and hydrated cement matrix,
Calcium sulfoaluminate cements are mainly composed called interfacial transition zone (ITZ). This solid–solid
by tetracalcium trialuminate sulfate (4CaO3Al2O3SO3), interface is about 50 lm thick (Mehta and Monteiro 1993);
b-Ca2SiO4 and gypsum (Ca2SO41/2H2O), although other nevertheless, it plays an important role in concrete prop-
phases may also be present (Péra and Ambroise 2004). erties. Figure 6 shows schematically the interfacial zone in
Most development of calcium sulfoaluminate cements concrete.
was conducted by China Building Materials Academy Although many other factors are important, it is gener-
(CBMA). Calcium sulfoaluminate cements also present ally assumed that the interfacial zone is the weakest link
great potential to be used along with commercial cement. for this composite (Akçaoğlu et al. 2003; Akçaoğlu et al.
Usually, the temperature needed to produce sulfoaluminate 2004; Paulon et al. 2004). As a consequence, the intro-
cements is around 1,350°C. Also the production of calcium duction of solids in concrete (for example, waste materials)
sulfoaluminate cements limits CO2 emissions, even when will always create new interfaces and probably compro-
compared to b-Ca2SiO4. Table 3 (Glasser and Zhang 2001) mise the mechanical behavior of concrete. In other words,
compares amounts of carbon dioxide released by the main addition of waste materials will probably damage concrete
components of commercial Portland cement and tetracal-
cium trialuminate sulfate.
In contrast to Portland cement, the alkalinity of sulfoa-
luminate is very limited, and it can be used for the prep-
aration of composite materials (Živica 2000). Studies on Solid-solid interface: transition zone
hydration of this material have been conducted (Janotka coarse aggregate
et al. 2003; Luz et al. 2006).
Another important issue is that calcium sulfoaluminate
cements can be prepared using the same rotary kilns used
for Portland cement preparation, which may facilitate its
Table 3 Comparative analysis

Compound CO2 release
of carbon dioxide released by
(kg mol-1) Hydrated cement matrix
components of cement
Ca3SiO5 0.58
b-Ca2SiO4 0.51
Ca3Al2O6 0.28
4CaO3Al2O3SO3 0.22 Fig. 6 Solid–solid interfaces in plain concrete: representation of
interfacial transition zone
123
properties. It means that thinking of concrete as ‘‘storage consumer history, which may determine many physical and
space’’ for residues is tempting, but it is a far too simple chemical characteristics (Hoang et al. 2010). Usually,
idea to be considered. Durability of concrete structure is a recycling of plastics can be performed in many ways, such
key aspect in sustainability (Gaspar and Brito, 2008). as chemical, thermal and mechanical processing. Some
Improper design will reduce the lifetime of the structure, polymers as polyethylene (PE), polypropylene, polyethyl-
demanding more cement. It may create also a new and ene terephthalate (PET) or polystyrene (PS), used in large
unwanted solid waste: debris, which means, more and more amounts, are very hydrophobic and if used ‘‘in nature’’ will
residues. render a solid–solid interface with very low adherence to
There are a large number of studies dealing with the the cement matrix (Pingale and Shukla 2008; Burat et al.
insertion of solid residues in concrete (Guo et al. 2009; 2009; Phuong and Villoutreix 2008).
Frı́as et al. 2009; Nehdi and Sumner 2003). Here, we will Polymers have lower density than concrete and if used
discuss only tyres, plastics in general and debris. as aggregate, will show this effect, lower the density of the
Waste tyres represent a world environmental problem. composite. Many aspects of the inclusion of a polymer into
European Union countries dispose approximately 600,000 a cement matrix were studied (Bayasi and Zeng 1993;
tons of waste tyres yearly (Aiello et al. 2009). In Spain, Soroushian et al. 2003; Batayneh et al. 2003). In general, it
80% of waste tyres are placed in dumps and about 40% in can be considered that concrete is not the best available
illegal way (Merino et al. 2007). USA generates about choice to the disposal of common plastics, although it can
250,000,000 of used car tyres each year (Holst et al. 1998). be one more useful option to alleviate this problem.
Also discarded tyres may healthy problems since they are a Although there are many other residues that can be
potential place to grow mosquitoes, even in unexpected incorporated into concrete (Shi et al. 2008; Tam and Tam
places (Harding et al. 2007). 2006), this topic will be finished considering concrete itself
There are many works dealing with the addition of tyres as a possible waste. Although concrete may be a very
into cement matrix (Turki et al. 2009; Hernádez-Olivares useful matrix to ‘‘accommodate’’ many kinds of waste
et al. 2002; Bignozzi and Sandrolini 2006; Siddique and materials, it should be considered that concrete will
Naik 2004). Probably, the major problem is associated with become a waste material, when we look at long-term per-
the reduction in compressive strength (Chou et al. 2007), spective. The lifetime of a common building may be esti-
although some properties can be enhanced (Turatsinze mated at 50–100 years (Horvath 2004; Scrivener and
et al. 2007). In order to improve compatibility between Kirkpatrick 2008). For instance, in China, it was estimated
rubber and hydrated cement matrix, tyre surface can be (Shi and Xu 2006) that debris will reach about 239 million
treated with different agents (Colom et al. 2006, 2007). The metric tons in 2010, and in 2020 this number will be close
main idea is to reinforce the adhesion between matrix and to 638 million metric tons.
rubber, an approach largely used in composite technology The utilization of construction and demolition debris to
(Atsu et al. 2006; Moya et al. 2007; Chandra et al. 2002). prepare new concrete structures is an excellent alternative
However, unlike other composites, in concrete the costs of to its disposal to landfill; also, this practice can be eco-
surface treatment may difficult its wide application, at least nomically feasible (Limbachiya et al. 2007) and save nat-
in the forthcoming future. On the other hand, perhaps the ural resources (Poon et al. 2002). Some limitations to the
use of limited waste tyres could reduce significantly envi- use of debris are specific gravity, durability and the pres-
ronmental problems without damaging concrete properties. ence of contaminants (Robinson et al. 2004).
Polymers, in general, and particularly plastics are widely The use of crushed concrete presents an inherent prob-
used in many industrial activities, such as automobiles, lem; since the material must be processed in some way
packaging, computers, housing, aerospace, aircrafts, boat- (crushed, for example), there will be the formation of
ing just to name a few (Shah et al. 2008). Perhaps the major macro- and microcracking in the solid. On the other hand,
concern about plastics is the long time needed for its nat- mechanical resistance may not be affected in a significant
ural degradation. The improvements in biodegradation and way (Rahal 2007).
photo oxidation are two technologies commercially used Finally, it should be pointed out that in many situations,
that tend to minimize this issue (Siddique et al. 2008). natural disasters will also be responsible for the production
Thermal decomposition of polymers is also an alternative of concrete wastes. In 2010, Haiti has suffered a strong
to produce chemicals (Zassa et al. 2010). earthquake that almost dismantled the country. It is
Since there are many classes of polymers and differ- impossible to determine the production of waste material
ences among polymers of the same nature (for instance, and, of course, human losses. In 2005, Hurricane Katrina
molecular weight, density and branching), there is not a caused the partial or total destruction of 275,000 homes,
simple protocol for recycling (Luttropp and Johansson causing an estimated $100 billion in damages (Denhart
2010). Perhaps, even more important is the plastic post- 2010). The demolition or implosion of concrete structures
123
and even more dramatic events (Tang et al. 2004; Herdt- Ahmed SFU, Mihashi H (2007) A review on durability properties of
Losavio et al. 2008; Hopke 2009) generates large amounts strain hardening fibre reinforced cementitious composites
(SHFRCC). Cem Concr Compos 29:365–376
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The construction business is a very important segment in size and matrix quality on ITZ and failure behavior of
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Environ Chem Lett (2011) 9:151–166

Cement industry: sustainability, challenges and perspectives

(hydrated calcium silicate). Literature reports many dif-

2. Intial processing (crushing)

3. Blending, mixing, adjusting composition

production, taking into account the potential generation of

CO2 released (103 tons)

Fig. 4 Distribution of carbon dioxide release during cement 60

Table 3 Comparative analysis

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