UNIVERSITY OF GUJRAT

Department of Chemistry

Control and eliminate the production of CO2 during calcination process

in Cement industry.

by

Zeeshan Ashraf- 20014107-044 (BS)

BS- 7th Evening (Analytical Major)

Chem-453
Research and Methodology

Submitted to the Ms. Warda Rukh

11th January 2024

 TABLE OF CONTENTS

Abstract ........................................................................................................................................... 2
1. Introduction ............................................................................................................................ 3
Figure 1. World cement production by region evolution 2000 -2007 [4] ................................. 3
2. The Cement Plant Process ..................................................................................................... 4
Figure 2. Schematic of process flow of cement plant without CO 2 capture ............................ 4
3. Convention al Options for Reducing CO 2 Emissions .......................................................... 7

3.1. Energy Efficiency Improvement ..................................................................................... 7

3.2. Fuel Switching ................................................................................................................ 7
3.3. Blended Cements ............................................................................................................. 7
4. CCS Potential in the Cement Industry .................................................................................. 8
Table 1 ............................................................................................................................................ 8
4.1. Amine scrubbing ............................................................................................................. 8
4.2. Oxy firing .......................................................................................................................... 9
4.3. Calcium looping ............................................................................................................... 9
Figure 4. The equilibrium pressure of CO 2 over CaO .............................................................. 10
Figure 5. Decay in carbonation conversion with number of cycles......................................... 11
5. Conclusion ............................................................................................................................ 12
6. Acknowledgments ................................................................................................................ 12
7. References ............................................................................................................................. 13

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 Abstract

The effect of the increasing concentration of CO2 in the atmosphere on climate change
is a major driving force for the development of advanced energy cycles incorporating CO2
management options. Growing interest in the technical and economic feasibility of CO 2
capture from large coal -based power plants has led to increased efforts worldwide to develop
new concepts for greater CO2 reductions in the future. Greenhouse gas emissions, especially
CO2, must be reduced by 50 -80% by 2050, according to the IPCC [1]. The type of fuel used
in cement manufacture directly impacts on CO2 emissions, with coal accounting for around
60 −70% of CO2. Emissions from cement installations. Therefore, the large amount of carbon
dioxide emitted during cement manufacturing process. - 5% of the total emissions of CO2
from stationary sources worldwide - is a cause of great concern and must be tack led to
comply with current legislation. Several technologies are available and have been proposed
for the separation of CO 2 from the flue gases from new and existing plants with retrofit
capture units. Few studies have been undertaken on CO2 capture re in cement plants to assess
the suitable technologies, with oxy -combustion and amine scrubbing as the possible options
(pre-combustion capture not being viable). Another envisaged benefit of this new technology
is that the lime purged from the cycle could be used as a raw material to produce cement
clinker. Therefore, the calcium looping cycle can potentially have an important impact in
reducing CO2 emissions from the cement industry and may also be applicable in other sectors.

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1. Introduction

Climate change is one of the greatest and most challenging environmental threats facing the
world this century. Therefore, mitigation measures to reduce the extent of global warming are
crucial. The Kyoto Protocol — the first international agreement on tackling climate change
— stipulates that industrialized countries must act first to curb emissions, giving time for
developing countries to grow their economies. At the end of the summit held this year i n
Hokkaido, Japan, G8 countries’ leaders reaffirmed their commitment to the UN goal of
achieving at least a 50 per cent reduction of global emissions by 2050.
With carbon dioxide representing the largest share of greenhouse gas emissions, CO 2 capture,
and storage (CCS) technology is increasingly being seen as a critically essential element needed
to tackle climate change, offering important potential for further utilization of fossil fuels
particularly for power generation and energy intensive industrial ap plications.
The cement industry contributes to about 5 % of the global anthropogenic CO 2 emissions,
making the cement industry an important sector for CO2 emission mitigation strategies. As
Figure 1 shows, worldwide cement production has grown consistently over the last few years,
with cement production figures rising to 2.77 billion tones for 2007 [4].

Figure 1. World cement production by region evolution 2000 -2007 [4]

Of the CO2 emitted by the cement industry 50% result from the calcination process of limestone,
40% from combustion of fuels (coal/pet coke/tires/waste oil/solvents/sewage sludge etc.) in
the kiln, 5% from transportation and the remaining 5% from the electricity used in
manufacturing operations. The type of fuel used in cement manufacture directly affects CO2
emissions, with coal accounting for around 60 −70% of CO2 emissions. Therefore, the large
amount of CO2 emitted during cement manufacturing is causing a great concern and has to
be tackled in order to comply with current legislation.
Cement plants are large industrial sources of CO 2 emissions, with a high CO2 concentration in
their flue gas es of about 14-33%, compared to 12 -14 % CO 2 for coal -fired power plants and
4% CO 2 for gas -fired power plants, and therefore represent a good opportunity for
implementing CCS.
Several technologies are available and have been proposed for the separation of CO 2 from
the flue gases from new and existing power plants with retrofit capture units. This paper reviews
the use of oxy-combustion and amine scrubbing technologies as possible options for CCS in

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cement plants, and focuses on the calcium looping cycle [2, 3] as a new route for carbon
capture which could be developed for use in cement plants in the near future. Pre combustion
was not addressed as not being a viable option for the cement industry as it would only be
able to capture the CO2 produced from combustion of the fuel used and not the higher quantity
of CO2 emitted during the limestone calcination process.

2. The Cement Plant Process

At present, approximately 5 % of global anthropogenic carbon dioxide emissions result from the
manufacture of cement, with 0.7-1.1 tone of CO 2 being emitted for every tone of cement
produced. A cement plant comprises the following steps: raw material preparation: crushing
and milling, pre-heating, pre-calcining, kiln firing, clinker and additive mixing and cooling,
cement milling and finally storage/packing.
The raw materials are crushed and milled into a fine powder before entering a preheater and
being fed i nto a rotating kiln [5]. Fuels are burned at the lower end o f the kiln so that it reaches
about 2 000°C, allowing the materials to be heated to around 1 500°C, where they become
partially molten. When the limestone (CaCO3) reaches about 900°C, it undergoes the chemical
reaction known as calcination, whereby CO 2 is released and calcium oxide formed, before
this convert to clinker.
:

CaCO3 → CaO + CO2

The clinker or kiln product is then cooled, and the excess heat is typically routed back to the
preheater units. Prior to packaging, appropriate additives or clinker substitutes are added to the
clinker to form the end-product known as Portland cement.

6oo kg CO2
1566 kg N 2
262 kg O2 Pre-Heater

Pre-Calciner

1150 kg raw material

0.94 kg air

Figure 2. Schematic of process flow of cement plant without CO 2 capture

Figure 2 provides a process flow diagram of the general cement manufacturing process with
an example of a mass balance to produce one tons of cement [6].
Cement production is either “wet” or “dry,” depending on the water content of the raw
material feedstock. The wet process allows for easier control of the chemistry and is better

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when moist raw feedstocks are available S lurry water before heating the raw materials to the
necessary temperature for calcination. The dry process avoids the need for water evaporation
and is, therefore, much less energy intensive.

3. Convention al Options for Reducing CO 2 Emissions

Many opportunities exist for CO2 emission reduction in the cement industry, with three
preferred measures by which CO 2 emissions have been mitigated over the last years:
• Energy efficiency improvement
• Fuel switching by use of waste as alternative fuel.
• Blended cements by reduction of clinker/cement ratio using industrial by-products.

3.1. Energy Efficiency Improvement

Through energy efficiency improvement, the CO2 emissions from fuels and the costs of
cement manufacturing can be reduced. Using energy-efficient equipment and replacing old
installations represent another way to improve the energy efficiency of the process. As the heat
used in the large rotary kiln represents the largest proportion of energy consumed in cement
manufacture, improving fuel efficiency will reduce the energy input. Since the dry process
with pre -heaters and pre-calcination is more energy efficient than the wet process, converting
from the wet to the dry process represents an opportunity to further improve the energy
efficiency of the kiln, and therefore the efficiency of the entire process. Converting the from
wet to the semi-wet process could also lower the energy intensity for clinker production with
only a modest increase in power consumed. Optimization of the clinker cooler, improvement of
preheating efficiency, improved burners and process control and management systems are also
part of process upgrading.

3.2. Fuel Switching

Fuel switching to lower carbon fuels and fuels qualifying for emissions offsets represent
another potential route for CO2 mitigation. The use of w aste -derived alternative fuels in
the cement industry has increased over recent years, to become today ’s current practice.
Using certain wastes is seen as an important opportunity to reduce the long-cycle carbon
emission s, diminishing their disposal requirements, and reducing the use of fossil fuels.
However, waste material might have adverse effects on the cement quality and increased
emissions of harmful highly volatile elements like mercury and thallium. As waste used can be
regarded as CO 2 neutral, some governments have already credited the cement industry for the
reduction o f equivalent CO2 emissions.

3.3. Blended Cements

The production of clinker is the most energy -intensive step in the cement manufacturing
process resulting in large process emissions of CO 2. In blended cement, the clinker/cement
ratio is reduced by replacing a part of the clinker with coal fly ash or blast furnace slag. These
industrial by -products are mixed with the ground clinker to give a blended cement product.
The global potential for CO2 emission reduction s through producing blended cement is

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estimated to be at least 5% of total CO 2 emissions from cement making but may be as high as
20% [7].

4. CCS Potential in the Cement Industry

The effects on climate change of the increasing CO 2 emissions in the atmosphere represent a
major driving force for the development of advanced energy cycles incorporating CO 2
management options. Therefore, CO 2 capture and storage is seen as another opportunity, apart
from the conventional ones presented above, to further mitigate the CO2 emissions generated
during cement process. CO2 capture can be performed using either pre -combustion or post-
combustion technologies and there are a number of potential storage destinations: saline
aquifers, porous geologic formations, depleted oil and gas reservoirs and coal seams.

As described above, during the cement manufacturing process, CO2 is generated from three
diverse sources [4]
• De-carbon ation of limestone in the kiln - about 525 kg CO2 per tons of clinker
• Fuel combustion in the kiln - about 335 kg CO2 per tons of cement
• Use of electricity - about 50 kg CO2 per tons of cement.

The typical exhaust gases from cement process are shown in Table 1 below.
Table 1
Component Concentration
CO2 14-33% (w/w)
NO2 5-10% of NOx
NOx <200-3000 mg/Nm3
SO2 <10-3500 mg/Nm3
O2 8-14 % (v/v)

4.1. Amine scrubbing

Post combustion capture by amine scrubbing (e.g., using Monoethanolamide (MEA) is a

commercially mature technology commonly used in chemical industry for separation of CO
2. The CO 2 is stripped from the amine solution, dried, compressed and transported to the
storage site. The main challenge, however, lies in the scale up of this process and its
implementation for scrubbing of CO2 from flue gases that contain a number of contaminants
potentially detrimental to the operation of the scrubber unit.
Several other methods can in principle be also considered for the large -scale separation:
scrubbing of gases solid sorbents, separation with membranes and cryogenics.
Post-combustion capture has been widely studied for application in power generation plants, but
there are few studies that have examined its application in cement plants [8].
The process flow of a cement plant allows the capture equipment to be fitted without major
modifications to the
existing plant.
The required equipment to capture the CO 2 emitted is as follows:
• SCR fitted between the preheater and the raw mill to reduce NOx in order to comply
with MEA process requirements.
• FGD fitted to remove Sox from the flue gas stream.

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• CO2 capture pl ant based on amines (absorber, stripper, and the auxiliary equipment)
• CHP plant or independent steam generators with grid connection for electricity
requirements to generate the steam needed for MEA stripping and to provide the electrical
power for the am ine scrubber operation and CO 2 compression plant.
• CO2 compression plant, where the CO2 captured stream is cleaned, compressed, and
dried, prior to transport by pipeline at a typical pressure of about 110 bar.

4.2. Oxy firing

In oxy-firing technology, the combustion air is replaced by pure oxygen from an air separation
unit (ASU), with the CO2-rich flue gas being recycled to moderate the flame temperature.
The equipment required for ox firing is as following:
4.2.1. Air S separation Unit (ASU) - to separate the oxygen from air prior to feeding into the
pre-calciner.
4.2.2. Ducting for recirculation of CO 2-rich exhaust gas back to the pre-calciner burners (around
50% of the total exhaust gases produced in the pre -calciner)
4.2.3. CO2 treatment and compression plant where the captured CO2 stream is cleaned,
compressed, and dried, before transport by pipeline.
Control of air leakage into the kiln, cooling of the cement after the kiln, the consequence
of the higher CO 2
partial pressure on the calcination process and the control of CO2 emission s during start/stops
of the cement plant need further exploration. If cement kilns could be successfully operated
with a high CO 2 atmosphere (which will increase the temperature required for calcination)
and in -leakage could be reduced, oxy -combustion of the kiln could be a feasible option.
4.3. Calcium looping

As the cost of the separation of CO 2 from flue gases introduces a large economic penalty, a
range of emerging approaches to separate CO2 with more cost -effective processes are being
explored. Intense, worldwide research activity exists to develop lower cost processes to separate
CO 2.
. The separation of CO 2 is conducted at high temperature u sing CaO as regenerable sorbent -
Figure 3. The reverse, calcination reaction produces a gas stream rich in CO2 and regenerates
the sorbent - CaO - for subsequent carbonation cycles.

O2

Figure 3. Lime Carbonation/Calcination Cycle [ 9]

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CaO particles will react with CO2 from combustion flue gases, at atmospheric pressure and
temperature around 650oC, to produce CaCO3. The carbonation reaction takes place in a
reactor like a circulating fluidised bed (FB) combustor. The CaCO3 particles are then separated
from the flue gas and sent to a different vessel for regeneration - calcination to produce pure
CO2 suitable for storage and CaO for further use. The newly formed CaO is recycled to the
capture reactor. The main option considered at present for calcination is coal ox firing in a
fluidised bed calciner at temperature over 900oC, with the calcined solids cycled continuously
to the carbonate or establishing a CO2 chemical loop between the carbonation and calcination
reactors.
An upper limit to the CO2 capture efficiency is given by the equilibrium of the carbonation
reaction at the temperature and pressure of the carbonator which imposes a limit on the operating
conditions. The equilibrium calcination temperature is dependent on the CO 2 pressure as
presented in Figure 4, following the equation:

log10 Peq (atm)=7.079-8308/T (K) (1)

It is assumed that the calcination temperature should be at least 50 oC above the equilibrium
condition.

100.000

10.000
600 700 800 900 1000 1100

1.000
P co2, eq

0.100

0.010

0.001
T(C)
Figure 4. The equilibrium pressure of CO 2 over CaO

The other limitation placed on CO2 capture in this process is that of the CaO capacity itself. It
is known that sorbent reactivity and durability decrease with the number of cycles and that the
decrease is promoted by presence of Sox in the flue gas [3]. Figure 5 compiles data obtained
by several authors in quite different carbonation– calcination conditions. It shows that all the
results follow a similar trend.

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 Figure 5. Decay in carbonation conversion with number of cycles

As a result of the sorbent deactivation, a small fraction of fresh sorbent must be continuously
added to the system to maintain the overall sorbent activity. The deactivated sorbent is then
purged from the system and could be used as a recalcined feedstock for the clinker kiln.
However, the utilization of the solid purge in the cement process places a restriction on the
purge composition, especially with respect to ash and sulfur contents. The composition of the
purge depends on the non-volatile content of coal ash, the sulfur content of coal and the
specific composition of limestone.
There are four different options for using this technology for cement industry as follows:
(i) FB calcium looping for supplying cement kiln lime.
This option offers maximum savings of raw material, fuel, and CO 2 emissions. However,
additional investment required.
(ii)Adding the purge coming from the calcium cycle applied to a coal power station to
the cement plant’s raw material mixture.
For this option only little investment is needed. Clinker chemistry, alkali/SO3 ratio in the cement
kiln and SO3 content in the cement clinker represent limiting factors that need further
assessment. In addition, transport distance for the solid material will play a significant role in
the economic assessment of this option.
(iii) Adding of sintered purge to cement clinker.
Sintering of the purge material at temperatures £ 1,250°C without decomposition of CaSO4,
grinding of sintered purge together with ordinary Portland cement clinker; only a little thermal
energy is needed because of the exothermic reactions during sintering. Limiting factors are
SO 3-content in the cement clinker chemistry.
(iv) Modification of clinkering for high sulfur raw material.
Sintering of the purge material at temperatures > 1,400°C in order to achieve decomposition
of CaSO4, reformation of gypsum by flue gas desulfurization with limestone; the thermal
energy demand is much higher than in previous option and additives are required to achieve
the desired clinker chemistry.
To make the spent lime purged from the calcium looping cycle , suitable as an input for cement
production, the concentrations of ash and CaSO 4 in the purge stream need to be limited to
Ashmax = 30 wt .% and CaSO 4max = 10 wt.% [10]

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5. Conclusion

This article summarizes the different CO2 capture technologies suitable for cement industry
proving that oxy- combustion and amine scrubbing are possible options, with pre-combustion
capture not being a viable route.
The article assesses the potential of a modern technology - the calcium looping cycle - as
a new route for CO 2 capture in the cement industry. The potential advantage of this system
is the exceptionally low efficiency penalty expected (<6%) compared with other capture
technologies. Since limestone is already used for cement manufacture, and because it is a
cheap material with good geographical distribution, it allows the use of local limestone
resources with minimal limestone-related infrastructure investment.
Another envisaged benefit of this new technology is that the lime purged from the cycle could
be used as a raw material for the production of cement clinker. Therefore, the calcium
looping cycle can potentially have an important impact in reducing CO2 emissions from the
cement industry and may also be applicable in other sectors.

6. Acknowledgments

The authors wish to thank the European Community (SES6 - 019914) for their funding of
this study and our partners in this project: Instituto Nacional del Carbon Spain, ENDESA ,
CEMEX and University of Stuttgart.

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7. References

1. IPCC, Third Assessment Report - Climate Change (2001)

2. T Shimizu, T Hirama, H Hosoda, K Kitano, M Inagaki, K Tejima, A Twin Fluid-
Bed Reactor for Removal of CO2 From Combustion Processes. Trans IChemE Vol 77-part
A, 62 (1999)
3. JC Abanades, EJ Anthony, D Alvarez, DY Lu, C Salvador, Capture of CO2 from
Combustion Gases in a Fluidized Bed of CaO. AIChE Journal, 50 (7), 1614 -1622 (2004)
4. Association Européenne du Ciment the European Cement Associ ation, Activity
Report (2007), [http://www.cembureau.be/]
5. DN Huntzinger, TD Eatmon, A life-cycle assessment of portland cement
manufacturing: comparing the traditional process with alternative technologies. J Clean Prod
(2008), doi: 10.1016/j.jclepro.2008. 04.007
6. IEA Greenhouse Gas R&D (1999)
7. LP ErnstWorrell, N Martin, C Hendriks, L Ozawa Meida, Carbon dioxide emissions
from the global cement industry. Annu. Rev. Energy Environ. 26, 303 –29 (2001).
8. IEA GHG, CO2 Capture in the Cement Industry, Report 2008/3, (2008)
9. A Bosoaga, JE Oakey, Lime carbonation/calcination cycle for CO2 capture. The
International Conference on Coal Science and Technology (2007)
10. T Weimer, R Berger, C Hawthorne, JC Abanades, Lime enhanced gasification of
solid fuels. Fuel 87 (2007) 1678 -1686

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