Energy Conversion and Management 75 (2013) 98–104

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Energy Conversion and Management

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Exergy analyses in cement production applying waste

fuel and mineralizer
Maria Luiza Grillo Renó a,⇑, Felipe Martins Torres a, Rogério José da Silva a,
José Joaquim Conceição Soares Santos b, Mirian de Lourdes Noronha Motta Melo a
a
Federal University of Itajubá, Av. BPS 1303, CP 50, Itajubá, MG, Brazil
b
Federal University of Espírito Santo, Av. Ferando Ferrari 514, Vitória, ES, Brazil

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

Article history: The cement industry is an energy-intensive industry and emits large quantities of carbon dioxide, so
Received 24 May 2012 waste fuels could usefully substitute part of the fossil fuels. They can also help resolve air pollution prob-
Accepted 22 May 2013 lems associated with the use of fossil fuels. Other wastes have properties of reducing the thermal energy
consumption of clinker production. They are named mineralizers. Then the application of both in the
cement industry contributes to the reduction of environmental liabilities and provides lower cost of
Keywords: acquisition of fossil fuels. The aim of the present study is confirm the advantages of the application of
Cement production
waste SPL (spent pot lining) as a mineralizer in clinker production from an exergetic viewpoint.
Mineralizer
Waste fuel
Ó 2013 Elsevier Ltd. All rights reserved.
Exergy analysis

1. Introduction
Industrial growth is accompanied by a growth in waste produc-
tion. This is a challenge to overcome and has been an environmen-
tal problem in recent years, mainly for the industries that generate
hazardous residues. According to the Brazilian Association of
Waste Treatment Companies [1], 2.9 million tons of hazardous
industrial wastes are generated annually in Brazil. Only 600
thousand tons (about 22%) receive appropriate treatment. The
remaining 78% are deposited in landfill without treatment [1].
Brazil, for example, in 2010 produced 67.3 million units of tyres
[2] that are incorrectly classified as useless and cause negative
impacts on the environment and serious problems for public
health. One alternative for waste tyres is to burn them in the rotary
kilns of the cement industry, in this way recovering the energy
from the tyres and simultaneously promoting a thermal treatment
of the waste. In 2008, 32 million waste tyres were burned in ce-
ment plants [3].
The cement industry has characteristics that make the burning
of wastes viable, since it is characterized by high energy thermal
consumption due mainly to the high temperatures necessary to
produce the clinker which is the main component of the cement,
and it is responsible for its hydraulic properties. The clinker is
obtained from the grinding, homogenization and burning (high
⇑ Corresponding author. Tel.: +55 3536291493.
E-mail addresses: malureno@yahoo.com.br (M.L.G. Renó), betinho.torres@
yahoo.com.br (F.M. Torres), rogeriojs@unifei.edu.br (R.J. da Silva), jose.j.santos@
ufes.br (J.J.C.S. Santos), mirianmottamelo@unifei.edu.br (M.de.L.N.M. Melo).
temperatures – 1450 °C) inside rotary kilns of raw materials (lime-
stone, clay, sand, iron ore). The next steps are the cooling of the
clinker, grinding the clinker with gypsum and other additives to
produce cement and finally storing, packaging and transporting
the cement to the end user [4,5]. The use of wastes in the cement
industry has another important advantage, which is the property of
mineralizing some wastes. Their incorporation in small propor-
tions improves the clinkering conditions as well as decreasing
the maximum clinkering temperature, or improves the phase
formation in the clinker without altering the final properties of
the product [6].
One waste applied as mineralizer is the SPL (spent pot lining)
originating from the aluminum industry, whose properties allow
the clinkering temperature to be reduced by up to 80 °C [7]. With
this advantage this work selected this mineralizer, and an exergy
analysis of clinker production was computed based on the second
law of thermodynamics. This analysis identified the exergy losses
and irreversibility, producing suggestions on how the process
could be improved [8]. At the end of the present study, the exergy
efficiencies of each stage of clinker production are compared.
1.1. Exergy analysis in cement industry
In the literature, there are many works that have applied exergy
analysis for the cement industry. For example, the work [9]
reviewed exergy analysis, exergy balance and exergetic efficiencies
for the cement industry. The results showed that exergy efficiency
remains lower than 26% and the main source of irreversibility in
the cement industry is the rotary kiln where the pyro-process

0196-8904/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
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 M.L.G. Renó et al. / Energy Conversion and Management 75 (2013) 98–104
occurs. Pyro-processing also accounts for the major share of the to-
tal energy use (93–99% in some cases). Thus the use of alternative
fuels or waste heat recovery could be important for future research
and development [10].
The work [11] examined heat recovery from the rotary kiln at a
cement plant in Turkey. First, an exergy analysis was carried out
based on the operational data of the plant. The results indicated
the presence of 217.31 GJ of waste heat, which is 51% of the overall
heat of the process. Then a mathematical model was developed for
a new heat recovery exchanger for the plant. It was determined
that 5% of the waste heat can be utilized with the heat recovery
exchanger. This system is expected to reduce domestic coal and
natural gas consumption by 51.55% and 62.62% respectively. CO2
emissions may also be reduced by 5901.94 kg/h and 1816.90 kg/h
when waste heat is used instead of coal and natural gas.
The work [12] performed energy and exergy analyses of a coal-
preparation unit in a cement plant and investigated the effect of
varying dead state (ambient) temperatures on exergy efficiency.
The mean values of energy and exergy efficiencies of the unit were
found to be 74.03% and 21.36% respectively, while the average
potential improvement of the unit was calculated as 78.24%. The
analyses also demonstrated that the exergy destruction ratio
affected the CO2 emission rate of the unit. The technique can there-
fore be a tool used for the purpose of developing energy policies
and providing energy conservation measures, especially concern-
ing similar types of industrial processes.
The raw mill in a cement production plant has also been inves-
tigated in relation to exergy analysis. The work [13] performed an
energy and exergy analysis of a raw mill and raw materials prepa-
ration. The results obtained for the energy and exergy efficiency of
the raw mill were 84.3% and 25.2% respectively. The results identi-
fied heat losses by conduction; convection and radiation from the
surface of the raw mill were about 14,300 MJ/h, which indicates an
energy recovery of 15.70% of the total input energy into the raw
mill. The work [14] also studied the raw mill, especially the effects
of ambient air temperature and the moisture content of raw mate-
rials on the performance of the raw mill. The results showed that
an external hot gas supply provides a 6.7% reduction in energy con-
sumption, corresponding to a saving of 1.66 kW h per ton of farine
production.
1.2. Co-processing (waste fuel)
The cement industry has one of the most intensive energy con-
sumptions. For example, to produce one ton of cement, it is neces-
sary to use 60–130 kg of fuel and 110 kW of electricity [15]. Due to
the large consumption of energy, which represents over 30% of the
total production cost for the cement industry, the reduction in
spending on energy inputs is a motivation for technological ad-
vances in the production process.
In this context, the burning of waste materials in cement kilns
represents a ‘‘win–win’’ situation. The cement manufacturer wins
because kiln fuel costs are dramatically reduced by replacing
primary fuel from the kiln with waste material and potentially
earning disposal fees from waste generators for treating the waste
in the kiln. In the co-processing, hazardous waste is not only
destroyed at a higher temperature (around 1450 °C), with a long
residence time (retention time up to 8 s), alkali combustion mate-
rial, and an oxidizing atmosphere [16], but its inorganic content is
fixed with the clinker, quite apart from using the energy of the
waste.
The decision on what type of substance to use is based on the
clinker production processes, the raw material and fuel composi-
tions, the feeding points, the air pollution control devices and the
waste management problems involved. Certain kinds of waste
must be dried and pulverized. In addition, the calorific value from
99
the organic part of the waste and the material value from the min-
eral part of the waste are also important [17].
Another aspect is the influence of the use of alternative fuels on
the clinker properties. The burning behavior of most alternative
fuels differs significantly from the behavior of fossil fuels due to
higher particle sizes and different material densities and transport
characteristics. This can change the temperature profile of the kiln,
including the sintering temperature, the length of the sintering
zone and the cooling conditions. All of these changes can affect
different clinker characteristics like the burning grade of the clin-
ker, the porosity of the granules, the crystal size of the clinker
phases or their reactivity [18].
The work [19] found that the addition of different types of
waste fuels requires an excellent control of the temperature in
the clinkering zone, because even slightly exceeding the required
temperature would excessively fluidize the clinker and might
cause damage to the refractory lining of the furnace.
Currently, a wide range of hazardous waste materials may be
co-processed, such as rubber residues, pulp sludge, used tyres,
plastic residues, wood waste and more. There are also hazardous
liquid wastes such as tar, chemical wastes, distillation residues,
waste solvents, used oils, wax suspension, and oil sludge [20].
Examples of waste which is not suitable for co-processing in the
cement industry include nuclear waste, infectious medical waste,
entire batteries and untreated mixed municipal waste. Thus, the
co-processing needs an adequate quality control system for all
materials used. This ensures that they are co-processed in an envi-
ronmentally safe and sound manner, safeguarding the [21]:
1. Health and safety of the workers in the plant and the people
living in the neighborhoods.
2. Environmental impact of the production process.
3. High quality of the final product.
4. Correct and undisturbed functioning of the production
process.
Due to the danger inherent in some wastes, in Brazil there is a
system of federal agencies designed to ensure the efficacy of envi-
ronmental legislation. The main Federal Standards controlling
emissions from cement kilns are Resolution CONAMA 264/1999,
which provides the procedures and the specific criteria of co-incin-
eration, and Resolution CONAMA 316/2002, which sets out the
procedures and criteria for the operation of waste treatment
systems [22].
In Brazil, the waste fuels are exploited by the cement industry
using a co-processing technique that has been used in Brazil since
the 1990s. The co-processing has the following characteristics dur-
ing the production process [23]:
– The alkaline conditions and the intensive mixing favor the
absorption of volatile components from the gas phase. This
internal gas cleaning results in low emissions of components
such as SO2 and HCl.
– The clinker reactions at 1450 °C allow incorporation of ashes
and chemical binding of metals to the clinker.
In 2008, approximately one million tons of industrial wastes
were co-processed in cement kilns. 44% of the wastes were em-
ployed as substitutes for raw materials, 39.4% were applied as fuels
in the kiln, and 16.6% were tyres. In the period 2001–2006, 40
million tyres were sent for use by the cement industry [24].
1.3. Mineralizer and spent pot lining (SPL)
Mineralizers have been applied in the cement industry for
years, with the purpose of reducing thermal energy consumption
100 M.L.G. Renó et al. / Energy Conversion and Management 75 (2013) 98–104

without altering the final properties of the product. For example, It is important to take into account that in the cement industry
the mineralizing properties of the compounds CaF2 and CaSO4 have it is usual to burn 60% of the fuels inside the calciner (including all
already been described in the literature. It has been confirmed that waste fuel) and the remaining 40% inside the rotary kiln. So these
the combined addition of CaF2 and CaSO4 to raw materials results considerations were also included in this study.
in a decrease of the maximum clinkering temperature to approxi-
mately 1350 °C. This temperature reduction by 100 °C is expected 2.1. Calculation of solids exergy
to result in a fuel saving of 80–100 kcal/kg clinker [25,6].
The other potential mineralizer is the SPL, which is a solid res- The solids exergy of the raw material and clinker were calcu-
idue of the aluminum industry that presents fluoride and cyanide lated according to the following equation [32]:
compounds, which are classified as hazardous waste of group 1, X
n
o
according to ABNT NBR 10004/04. The chemical composition of Bs ¼ nms bMs þ  ½ðh  h0 Þ  T o ðs  so Þk ð1Þ
the SPL is presented in Table 1. k
The amount of SPL generated in modern industrial plants is
where Bs is the solids exergy (kJ/s), nms is the number of moles of the
around 20–30 kg/ton aluminum [27]. The particular characteristics o
solid mix, bMs is the total chemical exergy of the mixture (kJ s), nk is
of this hazardous waste have consumed a lot of investment and
the number of moles of each component k, h and s are the enthalpy
research to find solutions that are economically and environmen-
(kJ/kg) and entropy (kJ/kg K) of chemical compounds, respectively,
tally acceptable, but no satisfactory solution has yet been found.
h0 and s0 are the enthalpy and entropy of chemical compounds in
The incineration of SPL waste in cement kilns is an alternative
standard condition and T0 is the standard conditions of temperature
to its destruction. The SPL has a calorific value that may partially
(K).
replace the fuel supply of the system, besides acting as a mineral-
The variation of enthalpy (h  h0) and entropy (s  s0) of chem-
izer of the clinker, providing a fuel saving without changing the
ical compounds of clinker and raw material can be computed
physico-chemical properties of the final product [7,28].
according to the temperature, as in the following equations:
This is due to the fluxing property of the fluoride found in the
SPL composition, which lowers the melting point in the clinkering h  h0 ¼ ðA  T þ B  T 2  103 þ C  T 1  105 þ DÞ  4:186 ð2Þ
process. The reduction observed in the process at Cimento Poty S/A

was approximately 80 °C (from 1450 °C to 1370 °C). With the drop T
s  so ¼ A  ln þ 2  B  103  ðT  T o Þ
in temperature it was noted that the heat consumption of the kiln To
dropped on average 10 kcal/kg of clinker produced [29]. ! !
C 1 1
þ  105   þ D  4:186 ð3Þ
2 T 2 T 2o
2. Exergetic analysis of clinker production where A, B, C and D are constants obtained from Refs. [33–35], T is
the temperature of the clinker and raw material, T0 is the standard
The exergy is a property that determines the useful work poten- conditions of temperature (298.15 K).
tial of a given amount of energy in a specific state [30]. More
broadly, one can say that exergy is the capacity to do work. Exclud- 2.2. Calculation of gases exergy
ing electric, magnetic, nuclear effects and interfaces, the total exer-
gy of a substance is the sum of kinetic exergy, potential exergy, The gases exergy is calculated using Eq. (4) below [32]:
physical exergy and chemical exergy. Clinker production includes o
X
thermal and chemical processes, so the emphasis will be on Bg ¼ nmg bMg þ ðT g  T o Þ  ðngk  C bgk Þ ð4Þ
k
thermal exergy, which is the sum of physical and chemical exergy
[31].
The analyzed system of clinker production comprises a pre-hea-
ter (with four stages), a calciner, a rotary kiln and a cooler, as
shown in Fig. 1. Thus, the system was divided into four control vol-
umes (pre-heater, calciner, rotary kiln and cooler) for the purpose
of calculating the exergy flows of solids and gases, as soon as the
exergy destroyed.

Table 1
Chemical composition of the SPL waste [26].

Composition % mass
C 46.5
Na2O 20.2
Al2O3 10.5
CaO 7.6
SiO2 2.5
S 0.82
Fe2O3 0.71
K2O 0.45
TiO2 0.11
MgO 0.10
SrO 0.03
Cl 0.03
P2O5 0.02
ZrO2 0.01
F 10.3
CN 0.12
Fig. 1. Control volumes of the clinker production.
 M.L.G. Renó et al. / Energy Conversion and Management 75 (2013) 98–104 101

Table 2 3. Case studies

Composition of raw material.

Component % mass The composition of the raw material considered for this study is
CaCO3 75.214 shown in Table 2. For computing the composition of the chemical
SiO2 12.79 components in kmol/s, it was considered that the production of
Al2O3 3.44 clinker is 34.72 kg/s and the production of 1 kg clinker requires
Fe2O3 1.86
1.56 kg of raw material for a cement plant operating as a dry
MgCO3 3.57
SO3 0.92 process (based on real data on the Brazilian cement industry).
Na2O 0.03 Therefore, the cement plant consumes approximately 54.16 kg
K2O 0.8 raw material/s.
With respect to the fuel supply, two case studies are considered.
In Case Study 1, 30% of the energy needed for the production of
clinker is provided by petroleum coke, 20% by charcoal, 23.6% by
Table 3 coal and 26.4% by wastes (scrap tyres (20%) and SPL (6.4%)). On
Chemical composition and LHV of the fuels and wastes applied in clinker production
[36–38,31,26].
the other hand, in Case Study 2 has 30% of petroleum coke, 20%
of charcoal, 30% of coal and 20% of scrap tyres.
Composition Petroleum Scrap SPL Charcoal Mineral The chemical composition and the lower heating value (LHV) of
coke tyres coal
the fuels used in the analysis of this study are given in Table 3.
Carbon 81.32 74.30 46.50 71.91 70.12 It was estimated that burning in the kiln occurs with 1.7% of
Hydrogen 2.87 7.20 0 4.20 4.51
Sulfur 6.02 1.71 0.82 – 1.28
free oxygen, and in the calciner it follows with 2.4% of free oxygen
Oxygen 0.45 15.89 0 11.36 1.13 (medium value of the cement industry). The specific heat con-
Nitrogen 0.88 0.90 0 1.11 2.25 sumption in the system when the SPL mineralizer is applied is
Water 8.00 – 0 7.80 0.85 around 3558 kJ/kg (Case Study 1), according to [29]. Usually the
Ash 0.46 – 0 3.62 19.86
cement industry presents a specific heat consumption of around
LHV (kJ/kg) 31,750 30,500 2720 27,900 26,928
3600 kJ/kg (Case Study 2) [39].

where Bg (kJ/s) is the gases exergy, nmg is the number of moles of the 4. Results
o
mixture of gases, bMg is the chemical exergy of the mixture (com-
puted as Eq. (5)), Tg is the gases temperature (K), T0 is the standard To compute the exergy flows of raw materials and clinker pro-
conditions of temperature, ngk is the number of moles of each gas of duced, it is necessary to take into account that the raw materials
the mixture. C bgk takes into consideration the enthalpy and entropy mix enters the kiln and is continuously and slowly moved to the
between the temperature range, as computed by Eq. (7): lower end by rotation of the kiln, and the raw material then reacts
X X at very high temperatures to form 3CaOSiO2 (C3S), 2CaOSiO2
o o
bM g ¼ ðygk  bgk Þ þ R  T o ðygk  lnygk Þ ð5Þ (C2S), 3CaOAl2O3 (C3A) and 4CaOAl2O3Fe2O3 (C4AF). The main
k k chemical reaction in the formation of clinker is presented below
From Eq. (5), ygk is the molar fraction of the gas, bgk is the stan-
o [40]:
dard chemical exergy (kJ/kmol), defined in the following equation 2CaO þ SiO2 ! ðCaOÞ2 SiO2 ð8Þ
[35]:
o
X CaOAl2 O3 þ 2CaO ! ðCaOÞ3 Al2 O3 ð9Þ
b g k ¼ DG o þ E0el ð6Þ

where DGo is the standard molar Gibbs function of formation (kJ/ CaOAl2 O3 þ 3CaO þ Fe2 O3 ! ðCaOÞ4 Al2 O3 Fe2 O3 ð10Þ
kmol) and E0el the standard chemical exergy of the constituent ele-
ments (kJ/kmol). ðCaOÞ2 SiO2 þ CaO ! ðCaOÞ3 SiO2 ð11Þ
Z Tg Z Tg 
1 dT From these compounds, C3S and C3A are mainly responsible for
C bgk ¼ cpk dT  T 0 cpk ð7Þ the strength of the cement. High percentages of C3S (low C2S) re-
Tg  T0 T0 T0 T
sult in high early strength but also high heat generation as the con-
From Eq. (7), cpk is the specific isobaric heat capacity (kJ/kmol K) crete sets. The reverse combination of low C3S and high C2S

Table 4
Exergy flows of gases and solids: Case Study 1 and Case Study 2.

Case Study 1 Case Study 2

Flux Temperature (°C) Exergy (kJ/s) Flux Temperature (°C) Exergy (kJ/s)
1 60 8483 1 60 8483
2 660 24,423 2 660 24,423
3 800 52,249 3 800 52,249
4 1643.15 66,464 4 1723.15 69,102
5 120 36,835 5 120 36,835
6 350 20,189 6 350 19,993
7 820 46,850 7 820 46,264
8 1000 22,062 8 1000 22,234
9 764 14,063 9 764 13,590
10 25 74,120 10 25 74,995
11 25 49,413 11 25 49,997
12 1115 10,651 12 1115 10,774
102 M.L.G. Renó et al. / Energy Conversion and Management 75 (2013) 98–104

Fig. 2. Grassmann Diagram of clinker production – Case Study 1.

develops strength more slowly (over 52 rather than 28 days) and Na2 O þ SO2 þ 0:5O2 ! Na2 SO4 ð15Þ
generates less heat. C3A causes undesirable heat and rapid reaction
properties, which can be prevented by adding CaSO4 to the final
product [31]. K2 O þ SO2 þ 0:5O2 ! K2 SO4 ð16Þ
Other compounds are formed: for example, the sulfur dioxide
that originates from raw material and fossil fuel burning may react
CaO þ SO2 þ 0:5O2 ! CaSO4 ð17Þ
with compounds of calcium, sodium and potassium contained in
the raw materials, according to Eqs. (13)–(18), generating products The equations from Sections 2.1 and 2.2 were used to compute
that are incorporated into the clinker [41]. the exergy flows from the gases and solids presented in Fig. 1. The
CaCO3 þ SO2 ! CaSO3 þ CO2 ð12Þ results are shown in Table 4.
From the exergy flows of Table 4 it was possible to plot the
CaO þ SO2 ! CaSO3 ð13Þ Grassmann diagrams related to the process (Fig. 2 (Case Study 1)
and Fig. 3 (Case Study 2)), where the exergy destroyed (ED) of four
CaSO3 þ 0:5O2 ! CaSO4 ð14Þ control volumes (pre-heater, calciner, rotary kiln and cooler) is
computed.

Fig. 3. Grassmann Diagram of clinker production – Case Study 2.

 M.L.G. Renó et al. / Energy Conversion and Management 75 (2013) 98–104
Table 5
Exergetic efficiency of Case Study 1 and Case Study 2.
Case Study 1 Case Study 2
Exergetic efficiency 0.298 0.294
From Figs. 2 and 3, the results indicate that the rotary kiln and
calciner present more irreversibility (as [9]), and approximately
30% and 47% of total exergy was destroyed respectively in the
two case studies. The main causes are calcination reactions inside
the calciner, as well as heat loss through the wall of the kiln and
clinkerization reactions. The total exergy destroyed was
2157 kW/kg clinker in Case Study 1 and 2208 kW/kg clinker in
Case Study 2. This result proves the advantage of using the SPL
mineralizer.
To compute the exergetic efficiency of both case studies it was
used the concept presented in [9] was used, which corresponds to
the following equation:
Desired exergetic effect Product
g¼ ¼ ð18Þ
Exergy used to drive the process Fuel
Applying Eq. (18) in the case studies, in which the product is the
clinker formation exergy, and the fuel is the sum of the exergy
content of the fuels and waste fuels used. The result is shown in
Table 5.
The values of exergetic efficiency are similar to the values com-
puted in the work [12]. Despite the small difference between the
exergetic efficiencies of the two case studies, the case study that
employed SPL reduced the fossil fuel consumption by 0.20 kg/s.
For an industry operating 24 h, this corresponds to a reduction of
17.32 t/day of fossil fuel. From the economic point of view, this
would be a great advantage.
Another way of improving the exergetic efficiency would be by
recovering the waste heat from hot gases and hot kiln surfaces
[42]. According to Sogut et al. [43], the use of energy recovery
systems improves the exergy efficiency values by approximately
48%. The waste energy may be recycled, as in the example of a
recycling system that heats and cools energy for residential areas
around the cement plant [44]. Another way is to use the waste
energy to generate electricity by means of a heat recovery steam
generator [42].
5. Conclusion
This study presented an exergy analysis of clinker production, a
powerful tool which has been used in the performance evaluation
of energy-related systems. The results indicated that the main irre-
versibility source in the cement industry is the rotary kiln and
calciner process where the clinkerization process occurs. Therefore
the use of mineralizers and alternative fuels is important, espe-
cially for reducing the fossil fuel consumption (in this study the
reduction was 17.32 t/day of fossil fuel) and waste management
problems. However, it is necessary to take into account that the
choice of alternative fuel depends on price and availability, and
that the energy and ash contents are also important, as are the
moisture and volatiles contents. This is a potential area for future
research and development.
Acknowledgements
The authors would like to acknowledge FAPEMIG – Fundação de
Amparo à Pesquisa do Estado de Minas Gerais, CNPq – Conselho
Nacional de Pesquisa and CAPES – Coordenação de Aperfeiçoamen-
to de Pessoal de Nível Superior for the financial support that al-
lowed this study to be conducted.
103
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