Middle East Technical University ME 438 Combustion Theory

Faculty of Engineering Fall 2021-2022

Department of Mechanical Engineering

Decarbonization of Cement Production

Ezgi Melike Saday, Huzeyfe Şirin, Ayşe Seray Şeker, Ali Yılmaz Dinçer, Furkan Enes Yıldırım, Uğur Yolaç

2235463,2259133,2235638,218863,2235901,2235984
Department as in Mechanical Engineering
ezgi.saday@metu.edu.tr, huzeyfe.sirin@metu.edu.tr, seray.seker@metu.edu.tr, e218863@metu.edu.tr,
furkan.yildirim@metu.edu.tr, ugur.yolac@metu.edu.tr

Abstract
This paper presents the necessity of decarbonizing the cement sector since it is critical for future international policies
aimed at low-carbon industrial activity. With 8% of CO2 emissions from the business sector, the cement industry plays a
significant role in this decarbonization phase. The importance of decarbonizing the cement sector is also something
Turkey should think about. As a result, the essential processes and approaches, as well as their assessments from Turkey's
standpoint, are discussed. As a result, the key sources of carbon emissions are identified and investigated. The article is
organized into sections based on the CO2 emissions that occur during the cement manufacturing process.

1. Introduction
Greenhouse gas emissions and global warming are
increasingly growing problems in the World. Because of
humankind and its needs, the planet is suffering. This highly
affects the geology of the world; therefore, flora and fauna on
almost everywhere in the world is changing even if some of
the species are extinct.

In 2015, the Paris Agreement was accepted to restrict the

global warming for 2°C from the industrial revolution to the
end of the 21st century. Also, to minimize the effects of
climate change, warming is trying to be decreased to 1.5°C.
This is hard to achieve and it can be possible only with hard
work. [7]

As can seen on Figure 1, main greenhouse gas emission is Figure 1. Total greenhouse gas emissions by Economic Sector in
caused by energy use and it corresponds to 73.2% of the total 2016
emission. After Energy, Agriculture, Forestry and Land use
total emission comes with 18.4%, Industry 5.2% and waste
3.2%. Figure 1 shows greenhouse gas emissions in 2016 with
details but also the 24% of the industrial CO2 emission is given
as energy use in industry. To sum up and specialize this pic
chart, Figure 2 is given below.

Figure 2. CO2 emissions by business sector[18]

On Figure 2, sectors are given in a more generalized manner

and their total emissions are illustrated. According to the pie
chart on Figure 2, Transportation has the highest CO2 by 29%,
Electricity is the second with 28%, then Industry with 14%,
Agriculture with 9%, and Concrete with 8%.

Page 1 of 17
All of these percentages are high enough to harm the
environment. The lowest carbon emission belongs to concrete
with 8%. Concrete is the most widely used artificial material
in existence. 2.5% of this is contributed by dwarfing the
aviation industry’s. Cement, which is produced by grinding
limestone and clay and adding iron ore or ash, is the most
important component of concrete. The mixture is heated to
almost 2,600 degrees Fahrenheit in a kiln, a procedure that
requires a lot of fossil fuel. When calcium carbonate in
limestone is heated, it decomposes into calcium oxide and
carbon dioxide, which are emitted into the atmosphere.
Cement is made by grinding calcium oxide with limestone and
gypsum. The process that breaks down the calcium carbonate
produces half of the CO2 emissions, while the other half comes
from the fossil fuels used to heat the kilns and transport the
ingredients.
2. History of Cement
Cement has been used by humans for thousands of years, with
the first archeological finding of a solidified whitewashed
floor built from burnt limestone and clay in modern-day
Turkey dating back to 12,000 years ago. The Romans invented
new construction techniques that allowed them to construct
massive structures with solid foundations. One such
innovation was "opus caementitium," a lime-based concrete
with sand and crushed rock particles. This was usually utilized
as formwork between masonry stones or bricks. Crushed brick,
tiles, and ceramic pots were utilized as aggregates in other
cements. Marcus Vitruvius Polllio, a Roman architect and
engineer, wrote a detailed description of the time's knowledge
and construction skills, which served as the foundation of
construction procedures for hundreds of years [3].
Although masons are known to have used hydraulic cements
to create structures such as fortresses and canals, the Middle
Ages were a peaceful period in the history of cement. The
1800s European Industrial Revolution saw a flurry of new
developments in cement and concrete, with major
contributions from John Smeaton, who discovered that the
hydraulicity of lime was directly related to the clay content of
the limestone, James Parker, Louis Vicat, and Egor Cheliev.
Joseph Aspdin, a British bricklayer and builder, found the
precursor to modern-day cement in 1824 when he
experimented with heating limestone and clay until the
mixture calcined, grinding it, and then combining it with
water. Portland cement was named after the pretty tough
construction stone from the Isle of Portland in Dorset, UK, by
Aspdin. William Aspdin, his son, invented the first alite
cement. In 1878, Germany established the first cement
standard for Portland cement, setting the initial test techniques
and minimum qualities, and many other nations followed suit.
Rotary kilns have been used to replace vertical shaft kilns since
the 1900s because they employ radiative heat transfer, which
is more effective at higher temperatures. Establishing a
consistent clinkering temperature and resulting in a stronger
cement.
Other developments in the last century include the use of
calcium aluminate cements for better sulfate resistance, the
blending of Rosendale and Portland cements in the United
States to create a durable and fast-setting cement, and the
increased use of cementitious materials to store nuclear waste.
ME 438 Fall 2021
3. How is cement produced?
Limestone, clay, and marn are the most common raw
materials used in cement production. Iron ore may be used to
satisfy iron needs, while bauxite can be used to meet aluminum
needs as a raw material. At the quarry, raw materials are loaded
onto transport vehicles. The jaw crusher equipped with a
dedusting device reduces the size of the raw materials brought
in from the quarry to 25x25 millimeters. Crushed raw
materials are separated and stored according to their
categories. Bag filters are used to recover dust at the transfer
points. The treadmill is used to grind raw materials into raw
meal. The major components of raw meal, which is a blend of
perfectly balanced cement raw materials, are calcium oxide
and silicon dioxide resources.
Calcium oxide is formed in the environment by rocks that are
mostly composed of calcium carbonate, such as limestone or
marn. Clay is the primary source of silicon dioxide. Aluminum
and iron oxide, which are also raw meal components, come
next. Other substances, such as magnesium and alkaline
oxides, are present in the structure even in minute amounts.
Vertical mills or ball mills are used to grind raw meal. Raw
meal is supplied to a preheater tower made composed of
cyclones after being weighed at a raw meal silo. In the
cyclones, heated gas circulates in the opposite direction of the
material flow. The raw mixture is preheated thanks to this gas
channel. As a result, less fuel is utilized to heat the kiln. With
the pre-calcination method, raw meal is heated from 30°C to
1000°C and calcined 90% of the time. Calcination is the
process of breaking down carbonate and hydrates under the
influence of heat to produce oxide components. Limestone's
calcite mineral transforms into free lime mineral.
The oxides in the raw material get liberated initially when raw
meal is burned in the kiln. As the temperature rises, more
crystals develop. The pre-raw meal heater is burned at 1450C
in the revolving kiln, resulting in granular clinker as a by-
product. Clinker is cooled and its temperature is decreased to
100C after it exits the kiln at 1300C. Clinker granules are
crushed with limestone in this mill, which is typically
equipped with balls. Gypsum is required to prevent excessive
solidification (extension of setting time) during the cement-
water interaction. Steel crusher balls fill up to one third of the
volumes in the mills in the shape of steel cylinders with a
diameter of roughly 3 m. As the cylinder rotates, balls collide
with the clinker particles, shattering them into smaller
fragments. Between the dividers, the material is transported.
The necessary fineness is achieved in the final division. Giving
pressurized water into the cement mill during grinding
prevents the temperature in the mill from rising.
4. Importance of cement
Cement is one of the core instruments of humanity and there
are various use areas of it. Some of them are, [4]
● Cement Mortar
Cement mortar is a paste produced by adding a certain amount
of water to a sand - cement mixture. In this scenario, cement is
referred to as matrix, whereas sand is referred to as adulterant.
While different binding materials are available, we know that
cement has strong binding capabilities. Cement is commonly
February 6, 2022
Page 2 of 17
utilized because of its great strength and water resistance. It is
used in brickwork to produce a strong binding between bricks
and stones. Plastering is done with cement mortar, which
provides the building of a smooth surface. Cement mortar may
be used to make various shaped cement molds. It's also used to
seal brick and stonework joints, as well as cracks. Generally,
the cement sand ratio in a mortar is in between 1:2 to 1:6. The
ratio of cement and sand mix is decided based on the
importance of work.
● Cement Concrete
Cement concrete is a key building material used all over the
world due to its excellent structural qualities. Cement, fine and
coarse aggregates, coarse aggregate, and water are the
components of cement concrete. Ordinary Portland cement is
commonly used to make concrete. However, numerous forms
of cements, such as quick hardening cement and high alumina
cement, have been discovered for unique instances or based on
diverse circumstances.
● Fire/Heat Proof Structures
Structures should be designed with superior fire-resistant
materials like cement to withstand high temperatures and
prevent fire mishaps. Concrete made with high alumina
cement is more suited for constructions in high-temperature
areas.
● Hydrographic and Frost Resistant Structures
The majority of the world's hydrographic structures are made
of concrete using cement as a binding ingredient. Structures
built near water or in touch with water should be extremely
resistant to moisture and watertight. Water-retaining structures
can be built with a variety of cements, including hydrophobic
cement, expanding cement, pozzolana cement, and quick-
setting cement. When there is a limited amount of time to
create underwater constructions, quick setting cement comes
in handy. Because hydrophobic cement is more resistant to
frost, it may also be used to construct structures in snowy
areas.
● Chemical Proof Structures
Different chemicals are housed in chemical businesses, and if
sufficient resistance is not there, they might harm the building.
In this instance, acid resistant cement comes in handy. Sulfate
resistant cement is also beneficial for projects in coastal
environments, such as sewage carrying structures.
● Grouting
Grouting is the technique of fixing cracks, gaps, and holes in
foundations or other structural parts in order to strengthen
them. Ordinary Portland cements are often used as grout, with
the needed amount of water and sand added. Micro fine cement
is ideal for filling very fine cracks or deep thin fissures. Micro
fine cement has far finer particles than regular Portland
cement, allowing it to flow quickly into very thin and deep
fractures.
● Cement Concrete Roads
ME 438 Fall 2021
Cement concrete roads are more well-known as high-quality
roads that outperform all other forms. Because of their hard
character, they are also known as rigid pavements. Even
without regular care, C.C. roads have a lengthy life period.
They are also significantly more competent than any other
sorts in terms of load.
● Manufacturing Precast Members
Cement is used as a binding agent in several prefabricated
parts. Cement concrete pipes are commonly used as drainage,
culvert pipes, and other applications. Because of the size of the
blocks, simplicity of building, and strength, cement concrete
brick masonry is more popular. Cement concrete rings are
commonly used to create water tanks and sewage tanks.
Cement is also used to make garden benches, flower pots, and
dust bins among other things.
● Aesthetic Structures
Cement is now available in a variety of hues. This is
accomplished by using a color ingredient in the cement
manufacturing process, although the proportion of coloring
agents used should be less than 10%. Iron oxide, which
produces red or brown, and cobalt, which produces blue, are
examples of coloring agents. Without any painting, the
colorful cement transforms the building into a work of art.
Colored cements are commonly used to finish floors, stair
treads, window sill slabs, and exterior wall surfaces, among
other things.
The worldwide cement industry is one of the least regulated on
a global scale, despite the fact that it has grown rapidly.
Table 1. Top 10 Cement Producing Nations
Because of the large-scale investments and infrastructure
projects that the Chinese government is undertaking, China
leads the world in cement consumption and production.
According to 2007 estimates, Chinese production accounts for
roughly half of all global output, while India accounts for only
about 6%. Table 1 shows the top 10 countries' output. While
the majority of the production is locally consumed, a good
chunk of the cement produced is exported.
February 6, 2022
Page 3 of 17
Table 2. The Top 10 Cement Exporting Countries
From Table 2 between Top 10 Cement Exporting Countries,
China leads the way in this area, which is expected given that
Chinese cement accounts for about half of global output. The
table below shows the total dollar value of cement traded by
the top 10 countries, as well as the volume of cement traded.
Figure 3. Summary of the decarbonization options [10]“
Half of those countries aren't top producers. Exporting nations
have profits, but these profits aren't indexed by their
proportional magnitude in domestic output. This might be
because they have a comparative advantage in cement
production due to cheaper raw material extraction costs.
Table 3. The Top 10 Cement Importing Countries
Table 3 displays the monetary value of imported cement as
well as the net weight of cement imported for the top ten
nations. The United States leads both areas, also a slowdown
ME 438 Fall 2021
is projected owing to the housing market's financial instability.
The top five cement-consuming countries are all in Western
Europe and North America, accounting for around 55 percent
of global consumption. A movement of output in developing
countries towards consumption in rich countries may be seen
in the export-import difference. Korea is included on the
import and export lists. This is most likely owing to the fact
that the term "cement" can refer to both ready-made powder
and components like as clinker. The United States is by far the
greatest cement importer, importing three times as much as
Spain, the second largest importer. This indicates that there is
a severe scarcity of cement in the United States, and domestic
manufacturing is unable to meet demand.
In 2008, when the dollar value of Chinese exports was divided
by the overall value of their exports, and the same was done
for Thailand, Chinese cement was sold for around $32 per
metric ton, whereas Thai cement was sold for $34. Both
Japanese and Korean cement are marketed in the same price
range, with the former costing $27 and the latter costing $34.
In comparison, German cement costs $71 per ton, while
Canadian cement costs $66. Cement prices may be divided
into two geographic groups based on a regional pricing
structure: Asian cement and European and North American
(EU/NA) cement. Such information simply serves to confirm
the importance of cement, as well as the high demand relative
to supply that allows the industry to weather global economic
depressions. It also demonstrates cement pricing's resistance to
external shocks. [6]
Turkey is at 8th place on Top 10 cement producing nations
from Table 1 and also at 8th place on Top 10 cement exporting
countries from Table 2. These data show the importance of the
cement sector in Turkey. According to Report of Cement
Sector '' amount of exported cement in 2018 is 8.2million tons
of cement equals 614 million USD and 10.3% of total cement
production in 2018. According to table 2 Turkey is providing
4% of the total cement production in the world but again
according to “Report of Cement Sector '' Turkey became third
country between top cement exporting countries [5].
February 6, 2022
Page 4 of 17
As of 2018, there are 52 integrated facilities and 20 grinding
facilities in the sector. Employment in the field of production
was 12,039 people in 2018. In 2018, the installed production
capacity in the cement sector was 141.88 million tons and the
production was 75.24 million tons with a capacity utilization
of 53.0 percent. The clinker production capacity was 89.86
million tons and the production was 70.34 million tons with a
capacity utilization of 78.3 percent.
As of the end of 2014, the production capacity of the Turkish
cement sector was 113.5 million tons/year and its production
was 69.7 million tons. The production value of the Turkish
cement industry, which was approximately 12.39 billion TL in
2016, was realized as 14.22 billion TL in 2017. The turnover
of the Turkish cement sector was approximately 12.24 billion
TL in 2016 and 14.38 billion TL in 2017. [5]
5. What is decarbonization?
There are three main strategies that can help to meet energy
needs with zero-carbon emissions: optimize, electrify and
decarbonize. Optimization means reducing the energy
consumption by improved efficiency. Electrifying means
energy demand should be shifted to electricity rather than
fossil fuel combustion. Decarbonization is to generate power,
completely switching to zero-carbon methods. [1]
The first thing to do in this regard is purification of the carbon
because carbon is the major heat trapping element of global
warming. There are various methods like “decarbonization” to
accomplish this.
Decarbonization is the process that decreases carbon
emissions. In the first instance, the process contains carbon
dioxide emissions to the atmosphere. In decarbonization the
aim is to form a global economy with low emissions and
achieve neutralization of the climate with energy transition.
Carbon dioxide emissions are increased by burning fossil fuels
to improve the economy. This is one of the causes of the
greenhouse effect and thus one of the causes of global warming
and climate change. Decarbonization requires an energy
transition, a structural change that removes carbon from
energy production. It is an economical improvement based on
clean alternative energies that only emits energy that the world
can absorb.
The Green Deal is the European Union's (EU) principal new
growth plan for transitioning the EU economy to a more
sustainable economic model. The EU Green Deal, which was
presented in December 2019, has its main goal for the EU to
become the first climate-neutral continent by 2050, resulting
in a cleaner environment, more affordable energy, smarter
transportation, new employment, and a higher overall quality
of life. The EU Green Deal has a number of financial structures
in place, totaling more than €1 trillion. This funding will go
toward policy reforms that are necessary for the EU's
economic development and climate neutrality.
By 2050, this would mean a reduction in greenhouse gas
(GHG) emissions of 80 to 95 percent compared to 1990 levels.
Given that industry accounted for around 28% of global
greenhouse gas emissions in 2014, these objectives will be
impossible to achieve without decarbonizing industrial
activity. Because industrial facilities have long lifespans,
ME 438 Fall 2021
upgrading or replacing them to reduce carbon emissions
requires serious planning and cost. [2]
6. Cement decarbonization
In cement production, carbon emissions occur in chemical
reactions and production processes. It is possible to
decarbonize carbon dioxide, which is formed as a product in
chemical reactions, with carbon capture and usage (CCU) and
carbon capture and storage (CCS). CO2 emissions can be
reduced in a variety of ways by industrial firms. Demand-side
strategies, energy efficiency improvements, fuel and feedstock
substitution, carbon capture, and innovation are all methods
for reducing carbon emissions. The cost of decarbonized
versus conventional commodities, the (local) availability of
the resources they require (such as biomass or geological
storage space for captured CO2), and the feasibility of
implementing them at both new and existing facilities will all
determine whether these options are effective and cost-
effective.
The following categories can be used to categorize
decarbonization options for cement sector [10]:
Demand-side measures: Reduced demand for a
manufactured good should result in decreased production and
CO2 emissions. Light-weighting, for example, can minimize
the requirement for steel, and cement might be substituted with
materials like wood. Furthermore, enhancing product
circularity, for example, by boosting plastic and steel recycling
and reuse, would reduce CO2 emissions by lowering the
manufacturing of virgin materials.
Energy-efficiency improvements: Energy efficiency
improvements can reduce fuel consumption for energy use by
15 to 20% across all industries. 17 The amount of energy
efficiency that may be gained will vary by sector and facility.
In general, established regions will be closer to the low end of
that spectrum, whereas emerging regions will be closer to the
high end. CO2 emissions will be reduced by using less fossil
energy to manufacture industrial products.
Electrification of heat: Switching to zero-carbon electrical
furnaces, boilers, and heat pumps can reduce emissions from
the use of fossil fuels to create heat. Electrifying heat may need
a modification in the manufacturing process. Electric furnaces
and electrically driven compressors, for example, are required
to electrify ethylene manufacturing.
Hydrogen usage: By switching to zero-carbon hydrogen,
emissions from the use of fossil fuels for heat and emissions
from particular feedstocks may be reduced. Hydrogen is
supposed to be produced in this paper by electrolysis of water
using zero-carbon power. Ammonia manufacturing, for
example, may be decarbonized by substituting zero-carbon
hydrogen for natural gas as a feedstock.
Biomass usage: Sustainable biomass, like hydrogen, may be
utilized to replace some fuels and feedstocks. Biomass can be
utilized as a solid (wood, charcoal), liquid (biodiesel,
bioethanol), or gaseous (biogas) fuel or feedstock, depending
on the application. For example, instead of coal, steel makers
in Brazil utilize charcoal as a fuel and feedstock, while
February 6, 2022
Page 5 of 17
chemical producers in various European nations are
experimenting with bionaphtha.
Carbon capture: CO2 may be captured from exhaust gases
produced by industrial processes and kept from entering the
atmosphere using carbon-capture equipment. The CO2 can be
stored underground (CCS) or used as a feedstock in other
processes through carbon capture and usage (CCU).,
Other innovations: Other strategies for carrying out industrial
operations, in addition to the decarbonization alternatives
outlined above, might result in CO2 emission reductions.
Alternatives to limestone feedstock, for example, might lower
cement manufacturing process emissions. Electrochemical
techniques, which use electricity rather than heat to drive
reduction and oxidation reactions, can also be used to replace
high-temperature chemical processes.
Summary of the decarbonization options which are described
above given in Figure 3.
7. Raw Materials and Alternative Fuel
● Waste Recovery
In the cement industry across the world and in our nation,
wastes that meet certain requirements are used to substitute
main fuel and raw materials. Instead of using traditional fuels,
caloric waste is utilized. Lime, which is the basic ingredient
for cement, and other minerals are made from waste having
mineral value.
Industrial wastes, textile wastes, timber wastes, oil and petrol
wastes, municipal solid wastes, and dried urban wastewater
treatment sludge are all sources of alternative fuels. By using
a basic categorization, alternative raw materials that are
recovered as cement raw material may be classified as mine
wastes, heat-treated wastes, and building wastes.
The demand for mining has decreased as main fossil fuels such
as coal, petroleum coke, and lignite, as well as natural raw
materials such as limestone, marn, and clay, are utilized less
throughout this process, allowing for a reduction in the
environmental imprint of such operations.[11]
● Carbon Capture and Usage (CCU)
While carbon capture and storage (CCS) entails sequestering
collected CO2, carbon capture and usage (CCU) involves
utilizing captured CO2 as a feedstock for industrial activities
such as chemical and fuel production. Methane synthesis,
polymer manufacture, and new materials such as carbon fiber
are only a few examples. As a result, CCU can improve carbon
circularity.
When compared to CCS, one projected benefit of CCU is that
it will make carbon capture more cost-effective by producing
money from the sale of collected CO2. However, according to
a recent study conducted by CO2 Sciences and The Global
CO2 Initiative, significant obstacles are now limiting the
development and commercialization of CCU. The most
significant obstacle is that turning CO2 into usable compounds
requires a significant amount of energy, particularly hydrogen,
resulting in high costs and considerable demand for zero-
carbon power. Improvements in catalysts and process
ME 438 Fall 2021
technology, as well as a rise in the availability of low-cost,
zero-carbon power, might boost CCU's chances.
Figure 4 shows that, electrification of heat and hydrogen as
fuel stock or feedstock applied in research phase, biomass as
fuel or feedstock applied in industry and Carbon Capture and
storage (CCS) applied for pilot sites to develop the technology
[10].
Figure 4. Decarbonization options for industry. [10]
8. Calcination process
Calcination process is sort of a heat treatment process whose
purpose is to chemically and thermally decompose certain
materials and minerals, such as limestone and metal ores. The
name of the process comes from a Latin word. The word
“Calcinare” means lime burning. In our case, the process is
used for the thermal decomposition of limestone. Limestone
has been used for centuries. It is used on metal production
processes, especially steel and iron making processes and it is
one of the most basic raw materials required. Limestone can
be found in nature as it comes into existence through natural
ways. The common type of limestone consists mainly of
calcium carbonate (CaCO3), silica (SiO2), alumina (Al2O3),
magnesium carbonate (MgCO3), iron (Fe), sulphur (S). In fact,
this mineral can be found all around the world. However, in
different areas around the world, the chemical content of
limestone and therefore the end products of the process may
change considerably. Limestone variations are categorized as
follows; Dolomitic or Dolomite consists of mostly magnesium
carbonate (MgCO3), around 20%, up to 45%. Magnesium type
limestone includes around 5-20%. High calcium one contains
magnesium carbonate less than 5% of its content. The other
elements and molecules like iron alumina and silica are the
impurities of the limestone. They affect the chemical reactivity
and crystalline structure of it. These differences cause the
processes needed for the limestone vary for each type of
limestone. The main issue about this condition is that each
composition must be examined to comprehend the properties
and of the limestone type and to decide, accordingly, the
necessary processes. Furthermore, the burning characteristics
is the main topic that should be investigated, in addition to the
kinetic parameters since the kilns (some kind of oven) used in
the thermal treatment process should be optimized for the
February 6, 2022
Page 6 of 17
further development of the calcination process [Calcination of
Limestone].
Figure 5. Basic scheme of a vertical calcination kiln. [28]
The process can be explained basically within 5 stages which
are listed as follows:
1. In the preheating zone with approximately 800°C, the
limestone is preheated by the gases inside of the kiln.
These gases originate from the ongoing reactions
through the kiln (carbon dioxide, resultant gaseous
products, and air).
2. As the limestone keeps being heated, thermal
decomposition starts to take place on the surface of
the limestone.
3. The thermal decomposition of the limestone proceeds
further once it reaches and exceeds the temperature of
900°C.
4. The created lime starts to be sintered. The lime is
formed according to the dissociation of the limestone.
5. Formed lime leaves the kiln to cool down since it
leaves the kiln at a temperature of 900°C. The
remaining products are not only the lime but also the
residuals of the processed limestone.
The thermal decomposition temperature is reached when the
standard Gibbs free energy gets zero. The temperature must be
at this temperature or more so that the calcination process takes
place because it is a thermal decomposition process. In a case
in which the limestone consists of only calcium carbonate, the
temperature must reach 850°C (1121 K) to start the calcination
process and it must be kept at that temperature or above. The
critical part is that through the process the amount of carbon
dioxide produced in the process is decreased and it is removed
gradually, as in Figure 5. This is necessary for obtaining the
desired end products. The process in which the pure calcium
carbonate is decomposed is as follows [26].
ME 438 Fall 2021
𝐶𝑎𝐶𝑂3 + 𝐻𝑒𝑎𝑡 ⇔ 𝐶𝑎𝑂 + 𝐶𝑂2 (𝑔)
100𝑔 56𝑔 44𝑔
The Gibbs free energy in this process is around 177,100
(J/mol). The above-mentioned temperature is the temperature
where this free energy is zero. These values change for the
overall process according to the impurities in limestone
calcinated. For example, the calcination rate is affected by the
crystalline structure of the limestone. The heat dissipation rate
of the process that includes calcium carbonate is reported as
754 kcal/kg by F. Schwarzkopf [32] who conducted relatively
later research about lime burning technologies. As it is
mentioned before, there are two more types of limestones
which are named as magnesium carbonate and dolomitic
limestone. Their decomposition processes are slightly different
from the calcium carbonate decomposition process.
𝑀𝑔𝐶𝑂3 + 𝐻𝑒𝑎𝑡 ⇔ 𝑀𝑔𝑂 + 𝐶𝑂2 (𝑔)
84𝑔 40𝑔 44𝑔
MgCO3 is observed to dissociate at a temperature range of
402 and 550°C. This process also dissipates a heat mount of
723 kcal/kg. The carbon dioxide amount is the same as in the
calcium carbonate reaction.
𝐶𝑎𝐶𝑂3 . 𝑀𝑔𝐶𝑂3 + 𝐻𝑒𝑎𝑡1 ⇔ 𝐶𝑎𝐶𝑂3 . 𝑀𝑔𝑂 + 𝐶𝑂2 (𝑔)
184𝑔 140𝑔 44𝑔
𝐶𝑎𝐶𝑂3 . 𝑀𝑔𝑂 + 𝐻𝑒𝑎𝑡2 ⇔ 𝐶𝑎𝑂 . 𝑀𝑔𝑂 + 𝐶𝑂2 (𝑔)
140𝑔 96𝑔 44𝑔
𝐶𝑎𝐶𝑂3 . 𝑀𝑔𝐶𝑂3 + 𝐻𝑒𝑎𝑡1+2 ⇔ 𝐶𝑎𝑂 . 𝑀𝑔𝑂 + 2𝐶𝑂2 (𝑔)
184𝑔 96𝑔 88𝑔
The heat dissipation value of the total dissociation process
which is indicated with heat (1+2) is found as 723 kcal/kg,
according to [26]. In addition, the initiation of the process
occurs around 510 to 750°C which is followed by the stone
and crystal structure formation.
The agglomeration occurs among the limestone crystals, and
they form bigger crystals due to this. The higher the
temperature of the process, the higher the agglomeration rate.
That is, the shrinkage and density increase. Thus, the density
of the limestone depends on the crystalline structure and
process temperature. It should be noted that the impurities
affect these parameters. The carbon dioxide removal is only
possible if the amount of porosity of the limestone suffices.
Otherwise, if the density of the limestone becomes too much,
the escape of the carbon dioxide is prevented. The former type
of limestone is more usable than the latter one. The size of the
limestone is an important parameter that is to be considered.
Since the time that the limestone stays in the kiln has an
optimal value, the limestones with relatively smaller size are
more applicable. However, this may change according to the
kiln type. If the kiln is vertical the limestones with larger
dimensions and calcination process with relatively low
temperature is required. The high temperatures cause the
limestone surface to shrink and porosity of it to decrease,
which is created by the carbon dioxide escaping. After that, the
pressure inside the limestone increases due to surface
shrinkage. So, an explosion of the limestone occurs, followed
February 6, 2022
Page 7 of 17
by the production of the undesired products. Due to this fact,
the quality reduction happens for the lime. Different
temperature levels and kiln types lead to various lime
conditions. For instance, at low temperatures, the end products
are lime and unburnt carbonate. At moderate temperatures, the
end products are softly burnt lime, also known as highly
reactive lime. In the case of high temperatures, dead burnt
lime, which is also known as low reactive lime, is the output
of the process. The optimal process produces lime crystallites
of lime which are small in size, sufficiently porous, properly
reactive and have low density, large surface area. The
temperature must be at a certain level If it gets higher, the
crystals get bigger, agglomeration happens and surface area,
reactivity, porous structure, density of the lime reduces. These
specifications correspond to the dead burnt (low reactive) lime.
● Utilization of Kilns
The kilns consist of three basic zones, as shown in Figure 1;
preheating zone is used to provide a high ambient temperature,
calcining zone is the zone in which the main process occurs
with increased temperature of ~900°C, cooling zone is, as the
name suggests, used to separate the products and the gaseous
materials that are to be used later in preheating zone [30]. As
mentioned before, there are two distinct types of kilns. There
are vertical kilns and rotary kilns. In fact, the vertical kilns
differ, too. Various types of kilns and their capacities are given
in Table 1. The fuel type does not matter for both kiln types.
There are some indexes that are important for different kinds
of kilns. The decrepitation index that is a significant parameter
for the vertical kilns indicates the tendency of the limestone to
disintegrate while being calcinated. High decrepitation index
is desirable since the porosity increases as it gets higher. Kiln
efficiency depends on the porosity amount due to the
importance of the removal of carbon dioxide. Moreover, the
tumbling index should be considered when rotary kilns are
used [25].
Table 4.Types of kilns. Adopted from [30]
● Carbon Emission and Calculation Methods
With the advancements of the technologies, the cement
production plants emit less carbon dioxide, down to 0.9
kgCO2/kgclinker (clinker is the mixture of the limestone and
other materials that is to be thermally decomposed). According
to a CFD modeling study aimed to reduce the CO2 emission
in a particular cement plant, amounts of types of CO2
emissions are calculated as in Table 5. It can clearly be seen
that the majority of the carbon emission is caused by the
calcination process. The problem here is that the CO2 that
originates from calcination is almost inevitable due to the
ME 438 Fall 2021
nature of the reactions. If we consider that there are 52 cement
production plants even in Turkey, we can understand the
impact of this process. Thus, the focus should be on the
combustion stage and carbon capturing capability of the
cement production process. The alternative methods to
mitigate the carbon emission do not have variation due to the
requirements of the reactions. Only way is to capture the
carbon dioxide which is, clearly, one of the end products of the
calcination processes.
Table 5 Emissions per annum for different types of
emissions.Adopted from[31]
CO2 is emitted from primary sources throughout the cement
manufacturing process as indicated in [33]. Direct emissions
are defined as the combustion of fossil fuels and the calcination
of calcium carbonate in the processing stage. Energy for raw
materials transportation and electricity generation consumed
by electrical motors and facilities causes an indirect emission
of CO2. Nearly 90% of CO2 emissions during the cement
manufacturing process come from direct emissions, with the
remaining 10% coming from raw material transport and other
production operations. Due to the different materials and
energy fluxes involved in the cement production process, it is
a complex thermal decomposition process. As a result,
calculating CO2 emissions in the cement business is a special
topic that needs to be further examined. Many organizations
have worked on calculating CO2 emissions in the cement
industry over the last two decades. Those calculation methods’
applicability is investigated in China and details are explained
below. The range of operational boundaries, unique
calculation methods for each emission process, and the precise
CO2 emission coefficients differentiate in these methods.
These are useful resources for calculating CO2 emissions from
cement production processes.
The IPCC offers three fundamental approaches for calculating
emissions from cement manufacturing, all of which rely on
process emissions from carbonate minerals during the clinker
manufacturing process. The default emission factor for clinker
is 510 kg CO2/t clinker, which does not include MgO
emissions. Tier 1 emissions are derived by extrapolating
clinker production from cement production data and correcting
for clinker imports and exports. The IPCC has designated the
clinker-based output method as a tier 2 approach for national
GHG inventory computations. It necessitates the gathering of
clinker production data as well as information on clinker CaO
content and CaO fraction from carbonate. If a facility gets a
large amount of CaO from a non-carbonate source (such steel
slag or fly ash), the non-carbonate component of CaO should
be eliminated first when calculating emissions. Tier 3
emissions are calculated using real CO2 content of carbonates,
February 6, 2022
Page 8 of 17
which necessitates thorough carbonate accounting (species
and sources). This approach must ensure that all carbonate
inputs to the kiln are thoroughly explored (i.e., types, amounts,
and sources), and that the examination be repeated whenever
there is a major change in materials or processes. However,
many cement factories find this technique unworkable due to
the enormous number of raw material inputs and the necessity
for continual chemical composition monitoring.
Over 100 countries have used the CSI calculation approach in
their large cement plants, and it is based on the IPCC
standards. The CSI approach offers two calculation methods
for process emissions: a carbonate mineral-based method and
a clinker composition-based method. The CSI clinker-based
method is similar to the IPCC method, but it takes into account
MgO in clinker, bypass dust, and cement kiln dust (CKD) in
clinker manufacture, as well as no-fuel carbon from the raw
material.
given. The emitted CO2 throughout the combustion process
will be numerically given. Finally, available alternative energy
sources with their advantages and disadvantages will be
discussed according to literature. Finally, the possible
applications of the alternative energy source will be examined.
The main source of CO2 emissions in our world is fuel usage
as a primary energy source of many processes that we need in
our daily life. In cement production, this is also the case. From
the quarries, we get raw materials such as limestone and clay.
Then, we are heating them to obtain the desired chemical
composition which is clinker. In this process, raw materials are
heated up to 1400-1500 °C. The CO2 is emitted during both
heating and chemical formation of clinker from the
decomposed minerals. The process is called calcination. The
figure below shows the rotary kiln and how the combustion
process is utilized to sinter the raw materials and get the clinker
further to be shaped.

Because it works as a flux, a modest amount of MgO (1-2% in

clinker) is beneficial. MgO could come from a carbonate
source. The default emission factors in IPCC tiers 1 and 2 may
be underestimated because they do not incorporate CO2
emissions from MgCO3 calcinations. The CaO and MgO
content in the clinker are used to calculate CO2 emissions from
the calcination process. A default of 525 kg CO2/t clinker
should be utilized, based on the IPCC default value.

The China Building Materials Academy (CBMA) developed a

method that includes a basic CO2 calculation approach for
businesses, particularly those using alternative raw materials
and fuels, as well as a coal ash conversion factor (1.04) for Figure 6. Combustion in Rotary Kiln
clinker. However, instead of the carbonate content in the raw
material, this technique is based on the composition of CaO
● What are the typical fuels used in Cement kilns?
and MgO in the clinker. This will increase the emission factor,
especially if numerous producers use steel slag and fly ash as
Obtaining the high combustion temperatures that are required
raw materials, which contain non-carbonate CaO and MgO.
for clinker formation requires burning a fuel with high energy
output. Therefore, the primary fuels to burn are coal or
9. Combustion Process
petroleum coke. They can be used with some other burners to
eliminate wasting more energy than necessary.
Why do we need combustion in cement kilns?
(Environmental Protection Agency, n.d.)
Combustion is a chemical reaction in which a fuel goes under
There are three types of process in cement manufacturing
oxidation and releases its internal energy as heat, which means
where the combustion occurs but affects differently. These are
the process is exothermic. The combustion of a fuel is used in
dry, semi-wet and wet processes. These processes are affecting
rotary kilns as a primary energy source of the calcination.
the efficiency of the combustion also. For example, in dry
Therefore, what we want is the heat release from the
processes, the raw material is almost hundred percent sintered
combustion to the raw materials e.g. limestone and clay.
before it reaches the rotary kiln since it does not have water
Combustion of any typical fluid involves hundreds of vapor to relieve it. It is just being sintered throughout the
intermediate reactions, species free radicals etc. We are precalciner.
dealing with mostly CO2 emission of the overall process.
● Alternative Fuels used in Cement Kilns
The main contributors of the CO2 emission in cement
How CO2 emissions and cost can be decreased in cement
production are the chemical calcination process of the
production? In the beginning, what we know is, the fuel types
limestone and the combustion that exists as an energy source
that are counted above are not cost-effective. To reduce both
of heating limestone. Their carbon emission percentages along
cost and carbon dioxide emissions several updates were done
a cement production is %60 and %40 respectively. In this part,
by people.
why we need combustion in rotary kilns, which types of fuels
are used, the chemical reactions with numerical values will be

ME 438 Fall 2021 February 6, 2022

Page 9 of 17
 Firstly, some of the kiln operators use hazardous waste environmental issue) in combustion process of the
materials as a supplemental fuel in rotary kilns since the precalcination of the raw materials up to certain temperature
required temperature is so high (Environmental Protection levels. The precalciner is shown in the figure below.
Agency, n.d.). Alternative fuels and energy sources are usually
divided into 8 broad headings that are biofuels; natural gas;
waste-derived fuels; wind energy; hydroelectric power; solar
energy; hydrogen; and nuclear energy. These energy sources
and waste material-based energy sources are low in potential.
The meaning of the potential is about their energy outputs.
Their energy outputs are limited (Chinyama, 2011).

The most common alternative fuels that are used in industry is

tabulated below. It will be mentioned why these can be
applicable in the combustion period at least for some parts of
the cement production.

Figure 7. Demonstration of Vertical Precalciner

In these years, the usage of alternative fuels in cement

Table 6: Alternative Fuels based on their states production helps us to not to use approximately 2.5 million
Category Fuels tonnes of coal every year. The waste materials used as
alternative fuels in the cement industry have numerous
environmental benefits.
Gaseous fuels Refinery waste gas, landfill gas, pyrolysis gas,
natural gas
• The use of waste materials as alternative fuels reduces the use
of non-renewable fossil fuels such as coal as well as the
Liquid fuels Tar, chemical wastes, distillation residues, waste environmental impacts associated with coal mining.
solvents, used oils, wax suspensions,
petrochemical waste, asphalt slurry, paint waste, • It is undoubtedly good for our health and environmental
oil sludge problems since we are rescuing from the waste materials.

Solid fuels Petroleum coke (petcoke), paper waste, rubber
residues, pulp sludge, sewage sludge, used tyres,
battery cases, plastics residues, wood waste,
domestic refuse, rice husks, refuse derived fuel,
nut shells, oil-bearing soils, diapers, etc.
• It also contributes in reducing the emissions such as
greenhouse gasses by replacing the fossil fuels with materials
that would otherwise have to be incinerated with their
corresponding emissions and final residues or shapes.
(Cembureau, 1997)

• Another advantage of using alternative fuels is maximizing

● Advantages and Disadvantages of Alternative Fuels
The cement industry realizes its responsibility to lead the
environmental affect associated with the manufacturing of its
products. Over the past 20 years, specific energy consumption
has been reduced by about 30%, equivalent to approximately
11 million tonnes of coal per year. Dust emissions have been
reduced by 90% as the industry has invested heavily in various
emission abatement techniques. These are mostly done thanks
to the passing from non-renewable energy sources to the
renewable ones or waste materials used as raw materials in
clinker production. (Cembureau, 1997)
the recovery of energy from waste’s potential. All the internal
energy of the waste can be used in the rotary kiln for clinker
production which I mentioned above how this energy is used
in cement production. It also maximizes the recovery of the
non-combustible part of the waste and eliminates the need for
disposal of slag or ash, as the inorganic part substitutes raw
material in the cement. The usage of the combination of both
waste and fossil fuel can be called co-combustion.

Operators cannot use the alternative fuels as a primary energy

source. However, in preheating of the raw materials, the
combustion energy is again used. However, in this process the
temperature level is about 600-700 degrees. Therefore, the
high energy output requirement may not be a must. People start
to use these alternative fuels (Mostly waste materials due to its

ME 438 Fall 2021 February 6, 2022

Page 10 of 17
 is only a fraction of the constituents in concrete. To do basic
comparison, here are the some examples where 400 lbs of CO2
emission occurs:

• The CO2 associated with using a home computer for a year

• The CO2 associated with using a microwave oven in a home
for a year
• The CO2 saved each year by replacing 9 light bulbs in an
average house with compact fluorescent light bulb

Based on the raw materials that are used and the process that
is occuring for clinker formation, a cement plant consumes
fuel amounting to about 3200 to 5500 MJ/tonnes clinker.
Figure 8. Co-combustion Process
Electrical energy consumption is changing from 90 to 120
kWh/tonnes cement produced. Historically, the primary fuel
There are also some disadvantages of the alternative fuels used
used in manufacturing is coal. (Cembureau, 1997)
in the combustion process of the cement production:
A wide range of other primary fuels are also used, including
The alternatively used fuels that are used in cement production
petroleum coke, natural gas and oil. The average European
have various properties than the conventional ones. Burning
energy requirement to produce one tonne of cement is
alternative fuels rather than conventional fuels leads to several
equivalent to the combustion of approximately 120 kg of coal.
difficulties that must be addressed in order to say the research
(Cembureau, 1997)
and development part is successfully exerted to real life.
Poorly distributed heat in the kiln, unstable operation of the
In addition to mathematical results and expressions, there are
precalciner, blockages should be overcome in the preheater
also lots of CFD simulations and analysis done covering the
cyclones, higher SO2, NOx, and CO emissions, and dusty kilns
calcination and combustion processes through the rotary kiln.
are some of the major challenges. (Cembureau, 1997)
Here are some example articles including the mathematical
explanation and theory behind it.
The chemical composition of the primary components of the
raw material has an impact on the correct functioning of the
A mathematical model for cement kilns (1970)
cement kiln, as does combustion and the fuel consumed. The
type of fuel utilized may introduce various material
In this article, the researchers predicate on 2 types of rotary
components that may alter the chemistry of the cement
kilns that work differently in terms of the type of fuel that is
ingredients as well as the system's functioning. As a result, any
used. The second kiln that is used includes used tyres as a
negative impact on cement quality, refractory life, gas and
supplemental fuel. They are plugging the chemical properties
material flow, or possible emissions to the atmosphere
and flow properties and energy equations into a CFD solver.
constrains the usage of a particular fuel. Therefore, since these
Then, they calculated the real life case with the CFD
are usually problems faced, in order to get government
simulations.(Darabi, 1970)
approval, these problems should be eliminated (Cembureau,
1997)
Modeling of Pulverized Coal Combustion in Cement
Rotary Kiln (2006)
The incomplete combustion, poor heat distribution and
unstable precalciner operation are problems associated with
In this article, again a rotary kiln is used for the analyzed
switching from conventional fuel to alternative fuels
geometry. The simulation includes discrete phases and
(Cembureau, 1997)
combustion is defined to the solver. They added a comment
about the combustion process they defined. “Mathematical
● Numerical simulation and Mathematical Expressions of
models of coal combustion have made better progress in other
combustion in Cement kilns
fields. However, modeling of coal combustion for a cement
The process of the calcination is to produce lime from the rotary kiln was mostly carried out in the burning zone close to
limestone. The most basic demonstration of the chemical the burner.” (Wang et al., 2006)
reaction is as follows.
The main reactions are added to the solver as belows.

The chemical formula of the cement is as follows.

CaO.Al2O3.Fe2O3
[1] In general, in manufacturing of cement, it is about 0.9
pounds of CO2 produced per pound of cement manufactured.
Manufacturing a cubic yard of concrete (about 3900 lbs) is
responsible for emitting about 400 lbs of CO2 since the cement

ME 438 Fall 2021 February 6, 2022

Page 11 of 17
 Additionally, clinker production also ranks high in electrical
energy use.

Table 7 Electrical energy distributions in a cement industry

(Hedman, Bruce2014)

10. Waste Heat Recovery Systems in Cement Industry

Cement is a crucial component of concrete, which is the

world's most frequently used building material. Therefore, it
has a great impact on the industry as well. For example, the
typical electrical energy consumption of a modern cement
There are two types of processes for rotary kilns depending on
plant is about 110–120 kWh per ton of cement and the cement
how the raw materials are processed, dry processes and wet
sector consumes approximately 12–15% of total industrial
processes. Raw materials are fed into wet-process kilns as a
energy use (Hedman, Bruce, 2014). Since the industry itself is
mixture with a moisture percentage of 30 to 40%. The amount
source-intensive, it requires significant amounts of raw
of water that must be evaporated before calcination can take
materials, energy, labor, and capital. The cement industry has
place requires a much higher energy need in the wet process.
a significant environmental footprint due to the extensive
A wet-process kiln has a high length and roughly 100% more
amounts of energy and raw materials used in the process.
kiln thermal energy to evaporate the water contained in the
Consequently, cement manufacture releases a great deal of
mixture than an efficient dry kiln (Hedman, Bruce,2019).
carbon dioxide (CO2). Cement production is responsible for
about five percent of total global CO2 emissions (IEA 2009).
Dry process systems have some differences according to the
preheater section. These different processes can be listed as
long dry kilns without preheaters, suspension preheater kilns,
and preheater/precalciner kilns. Before materials reach the
rotary kiln in suspension preheater and preheater/precalciner
kilns, the early phases of processing occur in the preheater
sections, which are a series of vertical cyclones. As the raw
material passes through these cyclones, it comes into contact
with hot exhaust gasses moving in the opposite direction, and
heat is transferred from the gas to the material as a result.
Modern preheater/precalciner kilns also have a precalciner,
which is a second combustion chamber located between the
kiln and the preheaters that partly calcine the material before it
enters the kiln, allowing the necessary chemical processes to
occur more rapidly and efficiently. Depending on the raw
material's drying needs, a kiln may contain three to six stages
of cyclones, with each additional stage increasing heat
recovery. Consequently, compared to other types of systems,
suspension preheater and preheater/precalciner kilns have
larger output capacity and higher fuel economy.

Figure 9 Electrical and Thermal Energy Flow in a Cement Table 8 Specific Thermal energy consumption by Rotary Kiln
Production Process (Madlool,2011) (Renewable and Sustainable Energy Reviews, 2011)

According to the Cement Sustainability Initiative (CSI) of the

World Business Council for Sustainable Development, the
average thermal energy and electricity consumed to produce
one ton of clinker among its reporting companies in 2014 were
3,510 MJ and 104 kWh (Hedman,2014), respectively, though
these values can vary greatly depending on the age and
configuration of clinker kilns. Clinker production is the most
energy-intensive step of cement manufacturing due to the
high-temperature requirement of the process, accounting for
more than 90% of overall energy consumption and practically
all fuel used in the sector (Madlool,2011). As the raw material
To decrease the energy loss and increase the exergetic
goes through the kiln, it is dried and calcined before entering
efficiency in the cement sector, Japanese companies led the
the sintering zone to produce a clinker. The combustion gas
development of WHR power systems as early as the
reaches temperatures of 1800 to 2000 ᵒC in the sintering zone.

ME 438 Fall 2021 February 6, 2022

Page 12 of 17
1980s(Hedman,2014). Capturing and transferring the waste
heat from the preheater and cooler and using that energy as an
extra energy source to create additional heat or to generate
electrical and mechanical power is the general application of
waste heat recovery systems in the cement industry.
Kiln exhaust streams, such as from the clinker cooler and the
kiln preheater system, contain useful thermal energy that may
be transformed into power. Although most of the energy is
used in rotary kiln operations and overall kiln efficiency is
critical to reducing energy consumption and emission of CO 2,
it is also necessary to recover remaining waste heat from the
preheater exhaust and clinker cooler. Clinker coolers typically
discharge enormous volumes of hot air at temperatures ranging
from 250 to 340 ᵒC straight into the environment. The 300 to
450 ᵒC kiln gas coming from the preheaters is often utilized to
dry material in the raw mill and/or the coal mill on the kiln
charging side. The aim is to provide low temperature heating
or generate electricity to compensate for a portion of grid
electricity purchased or power generated by fuel consumption
at the cement manufacturing plant. Since cement facilities
often do not require large low-temperature heating, most waste
heat recovery projects have been developed for power
generation. Waste heat recovery may contribute up to 30% of
a cement plant's overall electricity demand and has several
advantages. (Hedman,2014)
The amount of waste heat that can be recovered is affected by
the structure of the kiln system, the moisture content of the raw
materials, and the amount of heat required for drying in the raw
mill system, solid fuel system, cement mill, and waste heat
recovery system.
There are options to absorb waste heat and use it to produce
power. Generally, systems of the Rankine cycle are used for
waste heat recovery. Additionally, Kalina cycle and heat
recovery from the rotary kiln surface is also used. As
mentioned before, the clinker cooler discharge and the kiln
exhaust gas are the most accessible and cost-effective waste
heat losses available.
Steam Rankine Cycle
Figure 10 Schematic of a Steam Rankine Cycle Used in WHR
Systems (Hedman 2019)
In the waste heat steam generator, exhaust gas from the
preheater and clinker cooler is directed to boilers of the steam
Rankine cycle. Heat is transferred from the hot gasses to the
water in the cycle and steam is produced to drive the turbine
and produce electricity.
ME 438 Fall 2021
Organic Rankine cycle
Figure 11 Schematic of an Organic Rankine Cycle Used in WHR
Systems (Hedman, 2019)
The organic Rankine cycle operates on the same principles as
the Rankine cycle: the working fluid is pumped to a boiler
where it is evaporated, then transferred through an expansion
device, and finally through a condenser heat exchanger where
it is condensed. The difference is that the usage of an organic
molecule such as butane or pentane having a lower boiling
point, higher vapor pressure, higher molecular mass, and
higher mass flow compared to water. ORC systems may be
used for waste heat sources as low as 150ᵒC, whereas steam
systems can only be used for heat sources over 260ᵒC. ORC
systems are generally built with two heat transfer stages. The
first stage allows the exchange of heat from waste gasses to an
intermediate heat transfer fluid (for example, thermal transfer
oil). The heat is transferred from the intermediate heat transfer
fluid to the organic working fluid in the second step.
Kalina Cycle
Figure 12 Kalina Cycle used in WHR Systems(Júnior,2018)
The Kalina cycle was invented in the 1980s and has since been
researched for a variety of power production applications from
various thermal sources, including the energy recovery of
exhaust gasses. The fluid used in the Kalina cycle is a mixture
of water and ammonia. The Kalina cycle shows high efficiency
results in the cement industry (Amiri Rad & Mohammadi,
2018). The findings of WHR with Kalina cycle in the cement
sector showed that the thermal and exergetic efficiencies
ranged from 7-10% and 15-18%, respectively. Research
including heat recovery in different temperatures found that at
temperatures above 180°C, the Kalina Cycle exceeded the
ORC (Y. Wang, Tang, Wang, & Feng, 2017). For thermal
source temperatures ranging from 135 to 200°C, the Kalina
cycle outperforms the Rankine cycle in terms of thermal
efficiency (Lin, Zhu, & Li, 2015). The thermal efficiency of
the Kalina cycle for WHR at temperatures up to 473 K was
26.32 percent (Sadeghi, Saffari, & Bahadormanesh, 2015).
Wang studied the energy analyses and parametric
February 6, 2022
Page 13 of 17
 optimizations for different cogeneration power plants in
cement industry
Table 9 Optimization Results of Different WHR Systems (Wang 2009)
As can be seen from the table, the Kalina cycle system is the
one with the highest exergetic efficiency in the cement sector.
■ Heat Recovery from Kiln Surface
Rotary kiln surface losses heat via convection and radiation.
According to the study of Doheim (1987), the energy content
of hot kiln surfaces was discovered to be around 15.11 percent
of the input energy. An extra insulating shell on the kiln
surface can be used to decrease heat loss. Heat loss can be
reduced by insulating the cyclones and ducts of the pre-heater
unit's exterior surface. As a result, fuel consumption will be
reduced by 2%, with payback time frames ranging from 0.07
to 0.72 years.
■ WHR Systems in Turkey
The Turkish cement industry is the fourth biggest in the world
and the largest producer in Europe, producing 80.5 million
tons of cement and 70.8 million tons of clinker in 2017.
Therefore, waste heat recovery is an important consideration
for Turkey. With a total consumption of 6426 thousand TOE
equivalent in 2016, the cement industry is Turkey's second-
largest user of industrial energy, accounting for around 6% of
overall energy consumption.
In 2011, the first WHR installation was turned on. By the end
of 2016, ten clinker facilities had WHR systems in operation
with a combined design capacity of 100.7 MW. Four more
facilities are developing an additional 34 MW of WHR
capacity after 2016.
Table 10 Existing WHR Systems in Turkey (2019)
Generally, the design capacities of the WHR systems are well
within international practice standards of generating between
25 and 45 kWh/ton of clinker. The actual efficiency of WHR
generated can be lower than design estimates for plants, but
still within the range of international practice expectations.
ME 438 Fall 2021
In Turkey, WHR systems decreased an average of 23% of a
plant's overall power consumption, with individual levels
ranging from 18% to 31%(Hedman,2019). The estimated cost
of power from WHR systems, including operating and
construction expenditures, ranged from $18 to $45 per
megawatt-hour, compared to current purchased electricity
rates of $91 to $106 per megawatt-hour. The expected savings
per ton of clinker varied from $1.4 to $2.7. Existing project
paybacks for the examined WHR systems ranged from 6 to 27
percent, while predicted project paybacks ranged from 3.2 to
10.1 years. Sizing, capital cost, and capacity utilization of the
fluid are key design and operational elements that influence
the project economics of a WHR system of Turkey
(Hedman,2019).
11. Secondary Sources of Carbon Emission in Cement
Industry
For overall carbon emission in cement production, secondary
sources should be examined in detail. The main two processes
that emit CO2 in the production are the calcination process and
combustion of the fossil fuels for required heat in this process.
According to Cement Sector Scope 3 GHG Accounting and
Reporting Guidance which presents a methodology for cement
companies to calculate the emissions, emission sources are
divided into three categories as Scope 1,2 and 3. Scope 1.
World Business Council for Sustainable Development, a
council that works on sustainable development with over 200
international CEO-led firms, states in this publishment that
Scope 1 emissions are direct GreenHouse Gas (GHG)
emissions such as come out of a kiln, and Scope 2 emissions
are indirect GHG emissions related to the consumption or
purchasing of energy sources such as electricity, steam, or
heat. In this guidance, Scope 3 is the concern, which is
emissions related to the transportation, outsourced activities,
waste disposal and purchased materials. For different
companies, the contribution of the Scope types differs in
weight. For example, financial service companies are more
effective in emitting CO2 in Scope 1 and 2. The below table
shows the percentages of emissions according to the Scope
types. In the Figure, it can be shown that approximately 17%
of the emission is due to secondary sources in the cement
sector.
Table 11. Emissions for Companies in Different Sectors
When looking into the overall processes in a cement factory, it
can be seen that in almost every step, there is CO2 emission.
The importance is the amount of emitted gas during these
processes. In the first stage, mining or purchasing of raw
materials such as alumina, silica, limestone, and gypsum are
done. In mining, the usage of industrial machines, electricity
consumption are some sources for emission. After obtaining
the raw materials, cement manufacturing occurs, and the
primary emission sources are detailed in previous sections as
chemical reaction of CO2 and fossil fuel usage to obtain
February 6, 2022
Page 14 of 17
required energy for the process. When the production stage is
over, the mixing should be done to obtain concrete for
construction. However, transportation and mixing stages can
be replaced according to the types of cement. There are two
types: ready-mix concrete and precast concrete. For ready-mix
concrete, mixing occurs after the cement is transferred to the
construction site and vice versa. In both processes, the
emission is present. Then in usage and end of life stages,
concrete can absorb some amount of CO2.
Figure 13. Carbon Impacts of Concrete
In an article named as Laying the Foundation for Zero Carbon
Cement conducted by McKinsey and Company in 2020, the
portions of CO2 emissions and required energy are stated in
the Figure [BLABLA]. As can be seen, the most energy-
intensive and CO2 emission, after the main two sources,
calcination and fossil fuel usage, are in the cement mill
process. Behind the main sources, approximately 127
kilogram/ton CO2 is emitted from secondary sources.
Figure 14. Overall Cement Manufacturing Processes
The cement sector should obey the regulations about CO2
emissions. These regulations include a calculation about the
amount of the emitted CO2. Hence, cement companies are
divided into three categories to follow their own calculation
procedure. The first one is blenders which supply raw
materials or cement to producers. These materials can be
imported or bought. Hence, the main sources are transportation
ME 438 Fall 2021
and electricity consumption dependent, which are in Scope 1.
Secondly, grinding plant operators are the companies that
produce cement from bought clinker and other materials.
Then, this manufactured cement is transferred to the other
companies for use. Therefore, the main emissions are due to
the energy consumption from the required power for
production of cement from clinker, in other words grinding
process, and transportation. The Scope of these kinds of
companies are mainly the Scope 2. Finally, for the vertically
integrated manufacturers, the manufacturing of cement is
common with the previous types of companies, however, the
difference is that these companies also produce clinker
themselves. Hence, the calcination process is the most
important emission source for these companies. As for others,
transportation is also an issue in vertically integrated
manufacturers. In this section of the report, Scope 3 emissions
are examined, and 2 approaches are presented for Scope 3 as
upstream and downstream emissions. Secondary sources are
due to the purchased and sold goods and services,
transportation and distribution of the products, and energy
required activities during the production stage. The upstream
approach according to these types of emissions only considers
purchased goods and services in the company. Whereas the
downstream approach considers sold goods and services. By
doing this categorization, the effects of each bullet point of
CO2 emission are examined.
Figure 15. Scope 1, 2 and 3 emissions
In these analyses of calculating CO2 emission of a cement
company, all aspects of purchasing, servicing, having capital
goods, fuel and energy related activities are considered. Main
considerations are presented in the Figure [BLABLA] and
their applicability of mentioned three cement company types
is defined as required, optional on basis of relevance, optional
on basis of intermediate product status and not relevant to
cement companies. Among these assessment criteria, most
related ones are purchased goods or services, fuel and energy
related activities and upstream transportation and distribution
for upstream assessment. On the other hand, for downstream,
the common required criterion is downstream transportation
and distribution. When examining capital goods, it can be
concluded that the lifetime of them is an average of 50 years.
February 6, 2022
Page 15 of 17
Hence, this long time period makes this criterion negligible for
most cement companies. Moreover, for the cement sector,
waste amount, business travel and employee commuting are
not significant among other issues. Downstream assessment
criteria have a significance as cement is an intermediate
product. Hence, cement production has a variety of
downstream activities and carbon emission related to these
activities. These criteria are downstream transportation and
distribution, processing and use of sold products. As the
company should have information about the before and after
stages of the production line, Scope 3 emissions are the most
difficult measurement criteria compared to Scope 1 and 2.
Table 12. Scope 3 Categories Relevant to Cement Companies
12. Conclusion
The main focus of this article was to emphasize the
importance of the decarbonization of the cement industry, due
to the importance of it for international policies that aim at low
carbon industrial activities in the future. The present role of the
cement industry in this decarbonization phase is considerably
large with 8% of CO2 emission by the business sector. The
significance of the decarbonization of the cement industry is
also a subject for Turkey to be considered. Therefore the key
processes and methods and their analyses for Turkey’s
perspective is also mentioned. Accordingly, the primary
carbon emission sources are identified and examined. The
article is divided according to processes of the cement
production in which CO2 emission occurs. These are
combustion, calcination and other important processes. These
processes are investigated and then possible solutions for both
energy waste and CO2 emission problems in literature are
reviewed. Besides these processes, mathematical expressions
and numerical simulatıons are also given based on several
articles and researches. Additionally, since Turkey has a very
effective role in the cement sector in the world, waste heat
recovery studies should be supported. Because a well-designed
WHR system can contribute up to 30 percent of electricity
consumption. In this way, it helps to reduce CO2 emissions.
References
[1] Mackres, E. (2020, January 22). 6 lessons on energy
decarbonization from countries leading the way. World
Resources Institute. Retrieved February 6, 2022, from
ME 438 Fall 2021
https://www.wri.org/insights/6-lessons-energy-
decarbonization-countries-leading-way
[2] The EU Green Deal explained. Global law firm | Norton
Rose Fulbright. (n.d.). Retrieved February 6, 2022, from
https://www.nortonrosefulbright.com/en/knowledge/publicati
ons/c50c4cd9/the-eu-green-deal-explained
[3] History of cement. World Cement Association. (n.d.).
Retrieved February 6, 2022, from
https://www.worldcementassociation.org/about-
cement/our-history
[4] Uses of cement. The Constructor. (2017, December 29).
Retrieved February 6, 2022, from
https://theconstructor.org/building/uses-of-
cement/20704/
[5] https://www.sanayi.gov.tr/assets/pdf/plan-
program/%C3%87imentoSekt%C3%B6rRaporu2019.pd
f
[6] Global Cement Industry: Competitive and institutional ...
(n.d.). Retrieved February 6, 2022, from
https://www.researchgate.net/publication/46446244_Gl
obal_Cement_Industry_Competitive_and_Institutional_
Dimensions
[7] Portillo, G. (2021, August 4). Dekarbonizasyon: Ne
Olduğu, özellikleri ve önemi. Renovables Verdes.
Retrieved February 6, 2022, from
https://www.renovablesverdes.com/tr/karbonsuzla%C5
%9Ft%C4%B1rma/#:~:text=Dekarbonizasyon%20bir%
20enerji%20ge%C3%A7i%C5%9Fi%20gerektirirkarbo
nu,m%C3%BCmk%C3%BCn%20ve%20ekonomik%20
a%C3%A7%C4%B1dan%20mant%C4%B1kl%C4%B1
[8] https://www.morogluarseven.com/wp-
content/uploads/2016/12/%C3%87imento-
Sekt%C3%B6r-Raporu-Ticari-s%C4%B1rlardan-
ar%C4%B1nd%C4%B1r%C4%B1lm%C4%B1%C5%9
F.pdf
[9] https://ourworldindata.org/ghg-emissions-by-sector
[10] Decarbonization of industrial sectors ... - mckinsey &
company. (n.d.). Retrieved February 6, 2022, from
https://www.mckinsey.com/~/media/mckinsey/business
%20functions/sustainability/our%20insights/how%20in
dustry%20can%20move%20toward%20a%20low%20c
arbon%20future/decarbonization-of-industrial-sectors-
the-next-frontier.pdf
[11] Alternative fuel and raw materials. Türkiye Çimento
Sanayicileri Birliği. (n.d.). Retrieved February 6, 2022,
from
https://www.turkcimento.org.tr/en/alternative_fuel_raw
_materials
[12]Hedman, Bruce. (2014). Waste Heat Recovery for the
Cement Sector: Market and Supplier analySiS Waste
Heat Recovery for the Cement Sector.
10.13140/RG.2.2.31140.53126.
[13]U.S. Department of Energy, “Energy and Emissions
Reduction Opportunities for the Cement Industry”
(2003).Deployment of CCS in the Cement Industry,
Report 2013/19 (2013)
[14]Hedman, Bruce. (2019). Waste Heat Recovery in Turkish
February 6, 2022
Page 16 of 17
 Cement Industry Review of Existing Installations and Engineering, 132, 410–422.
Assessment of Remaining Potential. https://doi.org/10.1016/j.applthermaleng.2017.12.076
10.13140/RG.2.2.19396.48006.
[28] Limestone calcination in Normal Shaft Kilns, Retrieved
[15] Doheim M, Sayed S, Hamed O. Analysis of waste heat at 6 February 2022 from,
and its recovery in a cement factory. Heat Recovery https://www.researchgate.net/publication/275027427_Si
Systems and CHP 1987;7(5): 441–4 mulation_of_the_limestone_calcination_in_normal_shaf
t_kilns/figures?lo=1
[16]Júnior, E. P. B., Arrieta, M. D. P., Arrieta, F. R. P., &
Silva, C. H. F. (2019). Assessment of a Kalina cycle for
waste heat recovery in the cement industry. Applied
[29]Lin, D., Zhu, Q., & Li, X. (2015). Thermodynamic
Thermal Engineering, 147, 421–437.
Comparative Analyses between (organic) Rankine Cycle
https://doi.org/10.1016/j.applthermaleng.2018.10.088
and Kalina Cycle. Energy Procedia, 75, 1618–1623.
[17]Wang J, Dai Y, Gao L. Energy analyses and parametric https://doi.org/10.1016/j.egypro.2015.07.385
optimizations for different cogeneration power plants in [30] Calcination of limestone, Retrieved at 6 February 2022
cement industry. Applied Energy 2009;86:941–8. from, https://www.ispatguru.com/calcination-of-
[18] Detz, J. (2022, January 29). Global warming has concrete limestone/
problem when it comes to CO2. ecoRI News. Retrieved
February 6, 2022, from https://www.ecori.org/climate- [31] H. Mikulčić, M. Vujanović, D.K. Fidaros, P. Priesching,
change/2019/10/4/global-warming-has-a-co2ncrete- I. Minić, R. Tatschl, N. Duić, G. Stefanović, The application
problem of CFD modelling to support the reduction of CO 2 emissions
in cement industry, Energy. 45 (2012) 464–473.
https://doi.org/10.1016/j.energy.2012.04.030.
[19] Environmental Protection Agency. (n.d.). Toxics Release
Inventory (TRI) Guideme. EPA. Retrieved February 6, [32] F. Schwarzkopf, Lime Burning Technology – a manual
2022, from for lime plant operators (3rd ed.). Svedala Industries
https://ordspub.epa.gov/ords/guideme_ext/f?p=guideme Kennedy, Van Saun, 1994.
%3Agd%3A%3A%3A%3A%3Agd%3Adioxin_4_5_3
[33] T. Gao, L. Shen, M. Shen, F. Chen, L. Liu, L. Gao,
[20] Darabi, P. (1970, January 1). A mathematical model for Analysis on differences of carbon dioxide emission from
cement kilns. Open Collections. Retrieved February 6, cement production and their major determinants, Journal
2022, from of Cleaner Production. 103 (2015) 160–170.
https://open.library.ubc.ca/cIRcle/collections/ubctheses/ https://doi.org/10.1016/j.jclepro.2014.11.026.
831/items/1.0080783
[21] Ko, A., Chang, K., Sheen, D.-J., Lee, C.-H., Park, Y., &
Park, S. W. (2020, June 3). Prediction and analysis of the
aerodynamic characteristics of a spinning projectile
based on computational fluid dynamics. International
Journal of Aerospace Engineering. Retrieved February 5,
2022, from
https://www.hindawi.com/journals/ijae/2020/6043721/
[22] Modeling of pulverized coal combustion in cement rotary
kiln. ACS Publications. (n.d.). Retrieved February 6,
2022, from https://pubs.acs.org/doi/10.1021/ef060027p
[23] Chinyama, M. P. M. (2011, August 9). Chapter:
Alternative Fuels in cement manufacturing. IntechOpen.
Retrieved February 6, 2022, from
https://www.intechopen.com/chapters/17593
[24] Alternative fuels in cement manufacture Cembureau
brochure. (n.d.). Retrieved February 6, 2022, from
http://www.partnersforinnovation.com/sustainablebeton/
Landen%20&%20regio's/LinkedDocuments/Alternative
_Fuels_in_Cement_Manufacture_CEMBUREAU_Broc
hure_EN.pdf
[25] Calcination of Limestone, no author, (n.d.)
[26] Lime Calcination, Kumar G. S., Ramakrishnan A., Hung
Y., (n.d.)
[27]Amiri Rad, E., & Mohammadi, S. (2018). Energetic and
exergetic optimized Rankine cycle for waste heat
recovery in a cement factory. Applied Thermal

ME 438 Fall 2021 February 6, 2022

Page 17 of 17