Global Warming and Cement Industry: An Indian perspective

Avinash Mathur

Introduction
World cement production is over 1600 million tonnes. Demand for
cement is to reach over 2500 million by 2008. Cement
manufacturing involves burning of fossil fuel for calcination and
clinkerization, which generates CO2 and is emitted to atmosphere
through chimney. CO2 traps and absorbs heat in atmosphere and
increases temperature of the Earth. Global warming is the result of
this increase of Earth temperature. Greatest danger to the world
today is not from terrorism, weapons of mass destruction (WMD)
but from global warming. Consequence of global warming is
storms and flooding which reduces resource capacity like
agriculture land, cities and clean water. Flooding increases
resource consumption by way of relocation and resettlement.
Impact of global warming is also in the form of war, famine,
diseases and death. CO2 is the main GHG responsible for global
warming. 5% of global CO2 is originated from cement production.
One-ton cement production emits around one ton CO2 to
atmosphere. CO2 emission can be reduced by reducing
consumption of fossil fuel in kilns, calciners etc. Since technology
is the driver for CO2 reduction. Paper examines various
technologies and options for their application in cement production
for CO2 reduction leading to reduction of global warming.

Install Waste Heat Power recovery System

In China Huhhot Cement Plant. Inner Mongolia, is producing, 4
MW, 196 kWh / ton clinker from their one 550 TPD, φ 3 x 54 m
long kiln. Circulating fluidized bed calciner is used for
calcinations. Calcination degree over 90 % is obtained from
calciner. Exit gas temperature after calciner ranges 800- 8500C as
per process flow shown below. Sponge iron manufacturer’s kiln is
similar to cement kiln. Typically, 20 – 30 MW are being generated
there from kiln waste heat. Because of this gain from power
generation even during the worst recession period, they could
survive. Question is if sponge iron industry could generate power
from waste heat of kiln gases then why can’t cement industry? It is
because of this strength, sponge iron industry is better paymaster
than cement.
Waste Heat Power Generating System

Reduce calcination temperature of metamorphic limestone for

CO2 reduction
There are two qualities of clinkers being manufactured. One is
based on metamorphic limestone & other on sedimentary fine-
grained limestone. Metamorphic crystalline limestone deposits are
handicapped ones with high-energy consumption in calcining.
Calcination temperature is 930 - 1050 0C against 850 - 900 0C
with sedimentary fine grained limestone. An increase of 80 - 150
0C in calciner. Increase of fuel consumption by 40 - 75 kcal / kg
clinker. Free lime in clinker increases because of liquid formation
over a wider zone against requirement of narrower zone. Material
temperature at kiln inlet goes up from desired 8000 C to 9000C.
Since kilns are designed for a material temperature of 8000C at kiln
inlet. Rate of burning is reduced which affects clinker quality.
Liquid formation is quite different in both type of limestone as
could be seen below.

Metamorphic Sedimentary
Start of appearance 1290 0C 1270 0C
Liquid formation 1390 0C 1320 0C
Clinkerization 1450 0C 1450 0C
C2S→C3S less time more time
Clinker Quality inferior good

Effect of burning rate on CO2 emission

Metamorphic Sedimentary
Material kiln inlet 9000C 8000C
Residence time 20 minutes 20 minutes
Burning rate/ minute 27.50C 32.50C ▲
C2S to C3S zone 1390 - 14500C 1320 – 14500C
C2S to C3S time 2.18 minute 4.0 minute
C3S +exothermic heat low high
CO2 emission high low ▼

Use fluxes to reduce calcination temperature to increase burning

rate, to improve the kinetics of reactions and accelerate the
clinkering process. Once it is done, clinker quality of metamorphic
limestone would be improved & which in turn will reduce fuel and
CO2 emissions. It will also allow more percentage of fly ash &
slag addition into blended cements for economic prosperity.

Effect of kiln speed on CO2 emission

Before After
Speed, rpm 3.5 4.0▲
 Residence time, minutes 20 16.6
Burning rate / minute 27.50C 32.50C
C2S to C3S zone 1390 - 14500C 1390 – 14500C
C2S to C3S time 3.0 minute 1.8 minute ▼
Heat +CO2 emission low High ▲

Increased kiln speed though increases production but reduces

clinker quality and environment quality as it increases CO2
emissions.

Manufacture mineralized clinker for CO2 reduction

Conventionally raw mix has four components of lime, silica,
alumina and iron oxide. One or two component of mineralizer is
added to modify raw mix to produce mineralized clinker for
increasing clinker production, reducing fuel consumption and CO2
emission. With mineralized clinker, high percentage of fly ash and
slag can be added in blended cement. A cement plant in China has
used gypsum & Ca F2 for production of mineralized clinker & got
remarkably increase in 28 days strength to around 60 MPa. Clinker
production increased & coal consumption and CO2 emission
decreased by 5– 15 %. C3S content increased from 5 to 10 %.
Cement plants having metamorphic crystalline limestone deposit
should also consider adding mineralizers in their raw mix design to
reduce CO2 emission because it’s de-carbonation temperature is
higher and ranges 930 - 1050 0C against 850 - 900 0C with general
sedimentary fine grained limestone deposit. Calcination
temperature increases in calciner by 80 – 150 0C resulting into
increases of fuel consumption in calcination by 40 - 75 kcal / kg
clinker. Use of mineralizers, CaF2, barite, ZnO etc, is needed to
improve the kinetics of reactions and accelerate the clinkering
process to reduce fuel consumption and CO2 emission to
atmosphere.
Throw material curtain at kiln inlet for CO2 reduction
Kiln inlet jamming is a perennial problem. Use air-cooled steel
slag in clinker manufacturing for CO2 reduction. Throw calcined
industrial waste like air-cooled steel slag etc to reduce temperature
and to reduce fuel resulting into Co2 reduction. India generates 4.0
million tonnes /annum air-cooled steel slag only from electric arc
furnaces with negligible utilization. Steel slag is composed of
particles that are very hard. Some initiatives were taken to use it in
slag cement manufacturing but were abandoned due to difficulty in
grinding and reduction in cement strength. Slag is generated during
steel production where in liquid steel slag floats on the pool of
steel in electric arc furnace or induction furnace. Disposal of slag is
a big problem for the manufactures as it is being dumped in the
steel plant occupying huge land. However, steel slag has similar
chemical composition and mineral phases as of cement clinker.
There is great economic sense upon cement plants using and
converting this waste into wealth. It has the potential of recycling
national industrial waste into higher value cement clinker. Almost
all iron and steel slag can be viably used provided economics of
supply and transportation are feasible. It is prime example of
industrial ecology – a process that mimics nature by maximizing
efficiency and eliminating waste.

Crushed air cooled slag is added directly into the kiln typically in
lumps from 18 – 25 mm, Slag is added at kiln inlet through a
relatively uncomplicated and inexpensive feeding and metering
system. Slag is essentially proto-clinker and as per XRD analysis,
steel slag shows a highly fluxed beta di-calcium silicate phase
(C2S).Since slag does not require any further calcination as the
bulk of the thermal work already having been completed in the
electric arc or induction furnace, so no heat is required.

Slag melts at 1300 0C while clinker formation takes place around

1400 0C. Because of its lower melting point, slag begins to react
with the other oxides before entering the burning zone... In the
liquid phase, the slag becomes extremely reactive and will seek
other material with which to combine. As the material moves
through the kiln, mineralizer present in the slag, such as
manganese, helps to catalyze clinker formation reactions. C2S in
the slag combines with the free lime of the calcined kiln feed and
is converted into C3S. Since C2S to C3S is an exothermic reaction
heat is released and overall heat, consumption is reduced. This
conversion of C2S to C3S holds the key to the development of
desired cementitious properties in the clinker. Process has the
potential to increase clinker production by as much as 15 %, but it
depends upon raw mix design that takes into account the chemical
composition of the slag. Feed chemistry is adjusted to compensate
for the iron, aluminum, silica and calcium in the steel slag.

There are too many advantages of adding steel slag in rotary kilns.
Fuel consumption and CO2 emissions are decreased. Low capital
cost for incorporation whether new or existing cement plant.
Minimum time for implementation. Potential for eliminating or
reducing the need of mill scale. Lowering of burning zone
temperature. More stable kiln operation. Improved clinker quality.
Softer clinker reduces grinding energy. Increase in clinker
production is directly proportional to the slag amount. No prior
drying, grinding and blending of steel slag. Promotes a stable
coating on the refractory lining in the burning and lower transition
zones, which increases lining life. No building up at the kiln inlet,
rather the coarser steel slag has a cleaning effect on material build
up as it moves through the kiln. Slight lime enrichment of raw mix
to accommodate the steel slag. Slag structure transforms to the
desired clinker structure by diffusion. Million tonne plant can gain
at present market price Rs 60- 70 million per annum.

Throw material curtain above the kiln flame for CO2 reduction
Heat above the kiln flame is as high grade as below the kiln flame
This high-grade heat is melting the burning zone coating,
overheating the refractory bricks, transferring the heat to
combustion products and increasing the kiln shell temperature
resulting into increased radiation heat losses. By throwing the
material curtain above the kiln flame, benefits would be de-
carbonation of cold feed in less than a second, direct solid liquid
reaction, clinker synthesis at 1300 0C, fine crystal formation, 12 -–
15 % higher hydraulic reactivity, saving of fuel consumption @ 7
– 8 % in dry and 20 % in wet process cement kilns resulting into
equivalent CO2 reduction.

In pit crushing for CO2 reduction

In pit, crushing eliminates the need of dumpers using high-speed
diesel. 1 million ton cement plant’s mine typically consumes
350,000 liters diesel per annum. By avoiding dumpers, equivalent
amount of CO2 emission to atmosphere would be reduced besides
making quarry super efficient.

Install circulating fluidized bed calciner

Use fluidized bed system for limestone calcining In fluidized bed
calciner; raw material is used as “bed material” for fluidization.
Hot gas is blown into the furnace through a specially designed air
distributor at the bottom of the furnace. Once the necessary
conditions are reached in the kiln, cold powdered raw material,
particle size 5 mm or less is fed into the calciner forming a
“fluidized bed”. The raw material is vigorously mixed and
agitated in the fluidized bed, allowing it to disperse quickly and
evenly in the fluidized bed. Accordingly, the calcining temperature
throughout the bed can be kept constant, with little fluctuation and
over 90 % calcinations degree can be obtained. Exit gases of
calciner at 800 – 850 O C would be passed to waste heat boiler for
steam generation after getting de-dusted in multi -weir.

Maximize blended cement production to reduce CO2 emission

As per Bureau of Indian Standards, 70% blast furnace slag can be
added with clinker to manufacture PBFS (Portland Blast Furnace
Slag) cement. India is generating over 10 million tonnes per annum
blast furnace slag. It means a potential of manufacturing over 14
million tonnes of PBFS cement from 4.2 million tonnes clinker.
However, actual manufacturing is 8.5 million tonnes. Slag
utilization is around 60%. Reason for low percentage of slag
addition is due to poor quality of clinker, high power consumption
in grinding mills and non-alkali -activation of slag before use. To
reduce high power consumption in mills, slag and clinker should
be separately grounded and then blended in the mechanical mixers
instead of inter grinding in the mills. Plants should explore the
possibility of increasing the reactivity of slag by alkali activation.

Similarly, 35% fly ash can be added with clinker to manufacture

fly ash cement. India is generating over 100 million tonnes of fly
ash each year. It means a potential of manufacturing over 150
million tonnes of fly ash cement from 100 million tonnes of
clinker. However, fly ash utilization is around 8.6%. Reason for
low percentage of fly ash addition is due to poor quality of clinker ,
poor quality fly ash, non- alkali activation of fly ash and non
classifying of fly ash before use. To retain the spherical shape of
the fly ash particles, it should not be inter ground in the mills.
Instead, a mechanical mixer is used for blending fly ash with
cement.

Use ceramic insulation for CO2 reduction

Kiln shell temperature from inlet to outlet ranges from 250 – 400
deg C. Radiation losses through kiln surface varies from 25 – 30
kcal / kg clinker, which amounts to 3 – 4 % of specific heat
consumption. Reduction of radiation loss has not got as much
attention as the potential therein. By using ceramic lining as back
up insulation shell temperature can be brought down to 100 O C.
Reason is simple. Coefficient of
thermal conductivity of ceramic lining is 0.02 kcal / m / hour / O C
whereas of basic brick is 2.4 kcal / m / hour / O C i. e. 120 times
lesser than basic brick.
Produce zero clinker base fly ash cement
In USA, fly ash cement with zero clinker base has been developed
& patented with “C” class Fly Ash. Eliminating large kilns &
grinding mills. US field tests on concrete made with the fly-ash
cement without clinker indicate that mixes are user-friendly. Mixes
using this cement require less water, and field tests indicated
substantially less shrinkage cracking .Additives are blended with
the enhanced type C fly ash to create three cement formulations.

Type1: Blended Hydraulic Cement: Suitable for any type of

concrete with a specification requiring US Portland cement types I,
II & III.
Type2: Rapid Hardening Cement: Contractors and producers can
use for patching, pre cast products that requires high early strength
and quick-setting concrete.
Type3: Masonry Cement: Masonry contractors can blend with sand
for all types of mortar applications.

Significant cost savings. Even with the cost of the formulation

chemicals and blending operations, these new cements should be
very economical.

With fly ash as the primary ingredient, total material costs are
reduced. The manufacturing process requires relatively little in
energy and capital investment for the manufacturer .Contractors do
not need any special finishing tools or practices when placing fly
ash mixes. Timely introduction as India generates over 100 million
tonnes of fly ash whose nationwide utilization is less than 10%.
Many thermal power plants are struggling with disposal of its coal
fly ash. This cement as a new building material will help both
industries turning ASH into CASH.

Produce zero clinker base slag cement

Slagstar is one such new hydraulic binder developed by an
Austrian company. It consists ground granulated blast furnace slag,
gypsum & alkali activator. Due to sulphatic activation, no
calcination process required. Fuel used only for drying. Concrete
with SLAGSTAR has high late strength & low early strength. High
sulphate resistance. Preservation of limestone mineral CO2
emission 20% of OPC. Energy saving of 80 – 90%. High
performance concrete without micro-silica.

Manufacture Geopolymer Cement

Geopolymer is new material for the third millennium discovered
by Davidovits a French scientist. It tremendously improves cement
characteristics. Geopolymer cement is the new state of the art
cement. It results from geo synthesis (a reaction that chemically
integrates minerals) that involves silicon-aluminates. The Si & Al
atoms react to form molecules that are chemically & structurally
comparable to those binding natural rock. World industries
produce millions of tons of fly ash & slag containing Si & Al.
Geopolymers could turn this waste into wealth. Geo polymer
cements reduce CO2 emission by 80% i.e. 200 kg CO2 / ton
cement compared to 1000 kg / ton normal cement. Great thing
about geo polymers is that wide range of waste materials can be
used as long as Silica & Alumina is there. Compressive strength:
20 MPa after 4 hours for high early strength formulation. Setting
time can entirely be controlled. 7- 60 minutes at + 200C.
Compressive strength 90 MPa at 28 days. No alkali silica reaction
(ASR) problem as there is any expansion even after 250 days.
Specific heat consumption is only 300 kcal/kg clinker against 800
kcal/kg Portland clinker.

Energy and CO2 comparison

Cement Process Energy CO2

Temperature0 consumption emission
0
C
 Portland 1450 100 100
Geo polymer 750 40 20

Explore alternative materials

Cement is the commodity & concrete is the product. When water is
added to cement, silicate contents, C3S, C2S, reacts with water &
form two compounds of Ca (OH)2 and a Ca- Si- Hydrate gel which
is the binder and keeps aggregates and steel together. Surface area
of this C-S-H gel is around 300,000 m2/kg. Thus what we need is
C-S-H gel & not cement.

Explore use of Xonotlite as natural binder

Xonotlite, Ca6Si6O17 (OH) 2, is a calcium silicate hydroxide
mineral related in structure to wollasonite. No wonder some
natural binder like this might have been used in construction of Taj
Mahal, one of the Seven Wonders of the World still looking good
after 350 years. Xonotlite composition: SiO2 48.60%, CaO
44.64%, MnO 0.49%, MgO 0.25%, H2O 3.97%, Hardness 6,
Density 2.7, Color white-gray.

Commercial comparison between Xonotlite and cement

Xonotlite Cement
Bulk density, gm/cc 0.85 – 1.3 1.1 – 1.3
Mean particle size, um 35 - 85 05 - 85
Sp. Surface, m2/kg 40,000 400
(BET)
Value, per kg Rs 2100 Rs 3

Explore use of Wollastonite

Limestone calcinations are responsible for 55% CO2. Explore
Wollastonite to get C-S-H gel as binder.Wollastonite, CaSiO3 ,
is formed from the interaction of the limestone with silica in hot
magmas. It is in use in refractory ceramics, in paints and in
construction industry. Expected CO2 emission to atmosphere
around 1.0 kg / t against CO2 emission of 970 kg / t Portland
clinker

Indian cement CO2 reduction potential

Indian cement production is 118 million tonnes. Clinker
production is 103 million tones. Fly ash in PPC is 25% against
35%. Slag in PBFS cement is 40% against 70%. Potential of
PPC is 150 m t from 100 m t clinker & 50 tonnes fly ash.
Potential of PBFS cement is 15 m t from 5 million t clinker &
10 million tonne slag. Thus, there is CO2 reduction potential
over 35% from current level.

Initiate Cement India Vision 2020

Indian cement industry should initiate Cement India Vision
2020 in line with India Vision 2020, which envisions
transformation of India from developing to a developed nation.
Besides global warming loading reduction it should describe the
desired state of cement industry in 2020 from current level. It
should thus focus on improvement in eco efficiency, product
performance, HRD, technology adoption, R & D and industry
image.

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