UTILIZ ATION OF

PET COKE IN
CEMENT
MANUFACTURING
AND ITS
COMPARATIVE
PROPERTIES WITH
BITUMINOUS
COAL

COMPILED BY NITESH CHAHARIA

 OIL

CONVENTIONAL NATURAL GAS

COAL & PETCOKE

Fuels in Cement
Industry
SOLID :
Tyres, Tyre Chips,
Plastic, Paper, Agr.
Waste, Organic Material

LIQUID :
ALTERNATIVES Solvent, Greases, Oily
wastes

GASEOUS :
Landfill gas,Pyrolysis gas
 INTRODUCTION
Bituminous coal has been in use as fuel in cement kilns
for a long time. With coal costs continuously rising,
cement plants have been looking for alternative less
expensive fuels.
Petroleum coke presents a viable alternative because of Shree Cement was the
its lower cost since it is a byproduct of the refining first Indian cement maker
process. It has a high heat value and low ash content, to use petcoke
which favor its use in cement kilns. However, petroleum successfully and the fuel
coke presents some challenges, such as high sulfur savings helped the
content and poor grindability, compounded by the need company restore its
financial health. It
to grind it finer due to a low volatile content.
pioneered the use of
100% petcoke in cement
production.
 COMPARISON BETWEEN BITUMINOUS COAL AND PETROLEUM COKE
Coal Coke Comments Mitigation Measures
EMISSION
SO2 emission: (Depends on Typically Petroleum coke
Lime injection, Alkali Balance &
% S in fuel and alkali content Low High comes with 4 – 7% Sulfur
Process Strategy
in the raw mix) content.
NOx emission:(Petroleum
High flame temperature in the Multi staged combustion technique
coke is low in volatiles and
Low High kiln generates higher and SNCR (Selective Non Catalytic
the combustion occurs at a
thermal NOx Reduction) technology.
higher temperature)
OPERATION

High sulfur increases circulation

Coating formation and Alkali balance and operational
Low High of volatiles and potentially
preheater plugging strategy.Sulfur Bypass
cause plugging in preheater

No remedy. However, lower fuel

Petcoke is hard to grind and
Grinding load Low High requirement due to higher heat
needs finer grinding
value.
Higher ash Raw mix needs to be adjusted
Raw mix design Low in ash
levels for ash absorption
SAFETY
Low volatile content Inerting systems and explosion
Fire and explosion hazard high low
makespetcoke safer to handle vents are required.
 COMPARISON BETWEEN BITUMINOUS COAL AND PETROLEUM COKE
Low volatile content Inerting systems and explosion vents
Fire and explosion hazard high low
makespetcoke safer to handle are required.
CLINKER QUALITY
Permissible SO 3 content in
SO3 content in clinker low high clinker limits the use of
somepetcokes
CHARACTERISTICS
Petroleum coke is superior in
% Ash Content 14 – 20 0.5 – 1.0 heat content due to lower ash
content.
Higher carbon content gives
% Fixed Carbon 55 – 60 82 - 87
higher calorific value (CV).
Creates emission of SOx and
% Sulphur 0.5 – 1.0 04-Jul Please refer to point A1 and B1
Operational problems.
With higher calorific value less
Gross C. V. kcal/kg 6000 - 6200 8000 - 8200 amount of Petroleum coke is
required.
Hardness – HGI. The lower the Higher grinding (electrical)
50 – 55 35 - 40
HGI, the harder to grind. energy due to lower HGI.
Petroleum coke is a slow reactive Special burner for petcoke. High
fuel difficult to burn, making it a flame momentum kiln burner. Finer
% Volatile matter 22 - 27 07-Aug
less of a fire and explosive grinding.Longer retention time in Pre-
hazard. calciner.
UTILISATION OF PET-COKE IN CEMENT
MANUFACTURE

Extent of Use.

The level of substitution of pet-coke in an existing kiln having no by-pass When Bangur Cement
arrangement is decided on the basis of sulphur content in pet-coke and decided to used Pet coke
clinker. This is because of the fact that higher concentrations of sulphur along with coal as a fuel,
cause coating formations in cyclones and kiln inlet areas resulting into at least 10 breakdowns
operational disturbances. In extreme cases, kiln has to be stopped for were reported in its first
cleaning of these build-ups. Consequently, the availability and hence year but after a year of
productivity of the kiln is adversely affected. The decision of extent of experimentation they
succeeded in using it
sulphur input to kiln depends on the type of kiln and raw mix design
properly.
(molar ratio of alkali oxides to sulphur tri oxide should be between 0.8
to 1.2).
MODE OF USE.

Pet-coke can be used by two methods.

One is to mix it with the raw meal. In this method the reducing atmosphere is created. This may
result into change in temperature profile and increase in preheater outlet temperature and
uncontrolled CO formation.
In preheater cyclones, the reducing atmosphere may cause clogging.

Another method which is being used widely, is to blend pet-coke with the fuel firing in calciner and
kiln. In this method of use, it must be ensured that the pet-coke is burnt properly.

It is also possible to introduce pet-coke along with the raw meal and simultaneously fire along with
fuel in calciner and kiln.
GRINDING

Pet-coke being highly abrasive and hard, is difficult to grind. The grinding system is designed to minimize the wear
of mill components, ducting, transport system etc., In most cases, the target for the fineness of ground pet-coke
from the mill is 4 to 6% residue on 90 micron sieve.

COMBUSTION CHARACTERISTICS

Due to lower volatile content in pet-coke, it is difficult to ignite, burn and maintain a proper shape of flame. The
ignition temp. of pet-coke is 590-620oC as compared to the ignition temperature of coal 400-500oC.

In this case, the particles need a higher ignition temperature and a longer time to burn as the rate of chemical
reaction is very slow.

An important factor influencing the rate of combustion is the specific surface area of the fired pet-coke. So, the
fineness of pet-coke is increased to improve its burning behavior.

Based on the experience of other plants, pet-coke fired in cement kiln and calciner is of fineness of 4% to 6%
residue on 90 micron sieve.
USE IN KILN

If the plants have single channel burners for kiln then these will have to be replaced by specially designed Multi-
Fuel burners.

Such a burner will ensure the complete mixing of pet-coke and air, burn out time of individual particles and
creating the required flame impulse. Burner must be suitable to handle highly abrasive material. A little quantity of
support fuel like coal with high volatile matter or oil or gas can be used to ensure ignition. Several plants have
successfully use pet-coke up to 100% in main firing.

USE IN PRECALCINER

The desired conditions for the proper combustion of pet-coke in calciner are high temperature, high oxygen
contents and high temperatue. These conditions can be achieved by the following modifications:

Design of ‘Hot spot’ in ‘In line Calciner’ by shifting upstream the meal entry point by about 1.5 - 2 m. A better
solution may be the provision of a pre - combustion chamber.

The pre-calciner is designed for gas residence time of a minimum 3.5 seconds.

Creation of adequate turbulence in the calciner.

ADVANTAGES OF USE OF PET-COKE

The various advantages of using pet-coke as an alternate fuel are as highlighted here :

1. As compared to use of coal which has higher volatile contents than pet-coke, requirement of combustion
air is less. Similarly, the generation of the flue gas is lower which results into saving in energy
consumption of fans handling it. Alternatively, the reduction in gas volume can be used to increase the
production from the kiln provided there are margins in other equipment in the system.

2. As the pet-coke is a high heat value fuel, the temperature of the flame increases and hence the heat
transfer in the kiln improves.

3. If the alkali contents in the system are high then some sulphur rich raw materials or high sulphur coals
are used which may cost more. However, the pet-coke fulfills the sulphur requirements at lower cost.

4. Pet-coke is mostly available at lower price than coal. Hence, the specific cost of fuel lowers when pet-
coke is used.
LIMITATIONS OF USE OF PET-COKE

A few of the limitations of the use of pet-coke are as under mentioned:-

1. Since the sulphur content in the pet-coke is high, the quantity of its use is limited by the molar ratio of
oxides of alkalies to sulphur in hot meal entering the kiln which must be maintained as 1 to 1.2. On the
basis of experience of the users, the total sulphur content in the clinker is maintained below 1.4%.
2. As the grinding capacity of the coal mills lowers by 50% to 80%, there should be adequate coal grinding
capacity after use of the pet-coke.
3. If at a certain level of use of pet-coke, system is not capable of its proper burning (as indicated by the CO
contents higher than 0.2%), then its quantity cannot be increased further.

4. Temperature of the exhaust gas increases if pet-coke is introduced with raw meal resulting into increased
gas volume and increased specific heat consumption. In that situation, the benefits should be worked out
considering reduction in kiln production and increased fuel consumption.

5. Pet-coke has some toxic contents like vanadium, nickel etc., which go along with the dust. Hence, plants
which dispose the return dust have to ensure that the concentration of these compounds do not exceed
the limits defined by the environmental laws.

6. When cost of pet-coke is more than cost of coal or fuel being used, there is no economy of using it.
PROPERTIES OF PET-COKE

The various properties of the pet-coke proposed to be used are given as follows:

Parameter Unit Value

Moisture content (avg.) % 12
Size 50 mm sieve 100% passing
Bulk density t/m3 0.9
Calorific value net K.Cal./kg 8000
Volatile matter % 9 - 11
Ash content % 0.2
Hard groove index 50 - 55
Sulphur % 6
Carbon % 89.05
Hydrogen % 3.5 - 4.0

Substitution level
The substitution level of existing fuel by pet-coke is decided on the basis of
following criteria:

Criteria Limiting value

SO3 / Alkali molar ratio 0.8 - 1.0
Volatile matter incoal mix, % 20 (min.)
Calculation was carried out for different additions of pet-coke in existing fuel. The
results are presented as under mentioned:

S.No Pet-coke SO3/alkali SO3 in Volatile Ash

use, % molar ratio clinker, matter in absorption,
(M R) in % coal mi %
clinker (VM), %
1 -- 0.529 0.700 23.00 1.806
2 15 0.645 0.849 21.70 1.628
3 20 0.762 1.003 20.40 1.450
4 25 0.821 1.080 19.75 1.360
5 24 0.798 1.049 20.01 1.396

From the above results it is observed that for use of pet-coke up to 25% (SN 4) to M R and SO3 in clinker remain
within limits. But for use of pet-coke upto 25%, the V M content lowers than minimum requirement. Hence the
criteria for deciding optimum substitution level is V M content. Another calculation was done for substitution by
pet-coke up to 24% wherein the V M value comes in.
EFFECT OF SULPHUR ON QUALITY CLINKER

The cement broadly consist of following minerals CaO, SiO2, Al2O3 and Fe2O3 beside these major
components it also contains minor constituents (ie.) MgO, Alkalies and Sulphur.

As sulphur reacts before C2S and C3S formation it will consume part of lime available. Remaining
lime will now react to form C4AF, C3A, C3S and C2S. Lime consumed by SO3 is :

CaO (56) + SO3 (80) = CaSO4(136)

CaO / SO3 = 56 / 80 = 0.7

In case study it was observed that :

Case-1 - with 100% import coal - SO3 in clinker was 0.4

Case-2 - with 8% Petcoke - SO3 in clinker was 0.55

Case-3 - with 25% Petcoke - SO3 in clinker was 0.9%

Case-4 - with 50% Petcoke - SO3 in clinker is 1.2%

PROCESS IMPLICATIONS

The expected implications on process due to use of pet-coke are maintained as following:
1. The specific fuel consumption was likely to lower slightly.
2. Moisture in pet-coke was within the reasonable limits.
3. The volatile matter in the blended fuel was to be maintained above 20%.
4. The higher Sulphur content in the fuel will increase the SO2 emission in exhaust gases which will be
within acceptable range of prevalent environmental laws. However the corrosion will increase in the
transport ducts and equipment, particularly in corners.

QUALITY IMPLICATIONS

The implications on the quality were as under mentioned :

1. Reduction in ash absorption in the clinker from 1.93 to 1.69% and 1.53% for substitution of 10% and 17%
respectively of total fuel.
2. The quality of clinker will be maintained same except that SO3 content will increase.
3. The total sulphur input in fuel is limited to avoid problems of build ups as 1.23% and 1.60 % sulphur for
substitution of 10% and 17% respectively.
4. In burning zone high alumina bricks are not suitable with pet-coke and basic bricks may be required.
IMPACT ON PROCESS AND QUALITY OF CEMENT

An Indian cement companies encountering operational difficulties after the introduction of petcoke firing in
their cement kiln. These problems are due to poor nodulisation of the clinker and loss of cement mill output in
grinding this clinker. A review of the underlying reasons for this are presented below.

Factors inherent in pet-coke.

(1) Its low volatiles content and

(2) Its high sulphur content.

Low volatile content of the coke means that it needs to be ground more finely in the coal mills in order to ignite
and burn in the kiln flame. This requirement for fine grinding can become a capacity constraint on the amount of
petcoke that can be prepared for firing in the kiln. The low volatiles content and resultant longer combustion
time also means that modification to the kiln burner is often needed.

In pre-calciners, carry over of unburnt or burning coke into the bottom stages of the preheater can occur,
resulting in
elevated temperatures and potential blockage problems. Steps need to be taken to increase the petcoke’s
residence time in the pre-calciner to ensure complete combustion and separate calciner combustion chambers or
‘down draft’ calciners are introduced to achieve this.
High Sulphur content brings with it a number of problems.

In modern kilns with preheaters virtually all the Sulphur from the coke will be retained in the
clinker as sulphates, meaning the clinker sulphate content can approach or exceed two percent.

International standards limit total sulphate in cement to three or 3.5 percent, a high clinker
sulphate limits the amount of additional sulphate that is added, at the cement grinding stage.

Addition of sulphate as gypsum is required to retard the hydration and setting of cement. If
insufficient gypsum can be added then the cement may be inadequately retarded leading to
rapid setting and loss of workability of the cement. Unfortunately sulphate bound in the clinker
is not often as effective as gypsum added at the cement grinding stage in retarding the cement
due to sulphate in the clinker being ‘dead-burnt’ and unreactive.
High sulphur content can also mean operational problems with the kiln.

Petcoke firing usually results in the sulphates in the kiln being in excess of the alkalies with that
excess being present in combintion with CaO as anhydrite CaSO4 or double salts with CaSO4
in combination with K2SO4 such as calcium langbeinite.

In the calcining zone and kiln inlet this calcium sulphate can form intermediate compounds,
such as sulphate spurrite which can lead to ring formations and restrictions at the back of the
kiln. In the worst cases the hot feed is dammed behind these rings and falls through the kiln
inlet presenting a hazard and demanding a kiln rate reduction.
The nodulisation problems are also related to the Sulphur content of the pet coke.

High sulphate content is one of the primary causes of dusty clinker and can present major problems with dust
recirculation from the grate cooler to the kiln in the secondary combustion air. In the worst cases this recirculating
dust absorbs a significant quantity of the thermal energy provided in the fuel and hence inadequate energy is
available to combine the clinker into the clinker minerals. The excess sulphate in the clinker adds to the volume of
flux in the burning zone and also reduces the viscosity and surface tension of these liquid phases fluxing the kiln.

Two effects result from this:

(1) the reduced viscosity means that formation of alite is promoted and there is a tendency for large crystals of
alite to be formed, and

(2) the reduced surface tension means the clinker particles are more easily ‘wetted’ and the particle adhesion
forces in the clinker are reduced. This reduction in the adhesion forces is why the clinker structure is loosened
resulting in a finer particle size distribution and greater proportion of dust.
Explanation of a problem is the first step in identifying a potential solution.

In this case as the problem is increased viscosity and reduced surface tension of the flux, adjusting the
mix to reduce this viscosity and increase the surface tension of the clinker liquid phase should solve
the problem.

One way to do this by increasing the alkali content of the clinker, perhaps by the addition of feldspar
to the raw mix, as this has the required effect on the flux viscosity.
However, many producers go to great lengths to produce low alkali clinker and this is likely to be
impractical in many instances.

Silica is reported to markedly increase the viscosity of the flux and therefore lifting the silica
modules of the kiln feed may solve the problem.

Alumina is also reported to do this is to a lesser extent.

Also calcium fluoride promotes the crystallisation of alite from the clinker liquid which serves to
stiffen the flux and would have the same effect in addition to mineralizing the kiln.
i) MOLAR BALANCING (WITH OUT PETCOKE)

Molar balancing with 100% coal (Ind. Coal = 93.0%, Imp. Coal = 7.0%) and it is
0.985, which is normal.

MOLAR BALANCING

BASE

IND. COAL = 93.0 % NCV= 5733 K.Cal/Kg. Coal

IMP. COAL = 07.0% Heat Cons. = 735 K.Cal/Kg. Clk
KILN FEED VENT
SO3 =0.19%
K2O = 0.33%
Na2O = 0.09%
Cl- = 0.012%
KILN SYSTEM

COAL CLINKER

SO3 = 2.00 SO3 = 0.58

K2O = 0.06 K2O = 0.71
Na2O = 0.06 Na2O = 0.17
Cl- = 0.005 Cl- = 0.017

Section Qty. SO3 K2O Na2O Cl-

(MT)
Kiln Feed 4960 9.424 16.368 4.464 0.5952
Fuel 459 9.180 0.2754 0.2754 0.0228
Total 18.604 16.6434 4.7394 0.6180

Formula for molar balancing :-

SO3/80
------------------------------------- = 0.98502
K2O/94 + Na2O/62 – 2XCl/71
a) MOLAR BALANCING

Molar balancing with 20% Pet coke and 80% Coal.

BASE

COAL = 80 % NCV= 6052 K.Cal/Kg. Coal

PET COKE = 20 % Heat Cons. = 735 K.Cal/Kg. Cl
KILN FEED VENT
SO3 =0.19 %
K2O = 0.33 %
Na2O = 0.12 %
Cl- = 0.012%
KILN SYSTEM

COAL+PET COKE CLINKER

SO3 = 4.85 SO3 = 0.65

K2O = 0.481 K2O = 0.69
Na2O = 0.481 Na2O = 0.15
Cl- = 0.004 Cl- = 0.0119

Section Qty. SO3 K2O Na2O Cl-

(MT)
Kiln Feed 4960 9.424 16.368 5.952 0.5952
Fuel 414 20.079 0.1991 0.1991 0.0166
Total 29.503 16.5670 6.1512 0.6118
Formula for molar balancing :-
SO3/80
------------------------------------- = 1.4282
K2O/94 + Na2O/62 – 2XCl/71

The value of molar balancing comes to 1.4282, which is higher than recommended value of
1.0. which indicates abnormal and hard deposit at kiln inlet/kiln riser duct.
CONCLUSION

Petroleum coke is a viable alternative fuel to Bituminous Coal provided the challenges associated
with it are properly addressed. The quality of Petroleum coke varies from source to source.
Depending on the refining process, various types of Petroleum coke are produced.
To ensure a successful operation, a detailed study based on the characteristics of the raw material
and Petroleum coke to be used is required. Additional investment may be envisaged for
incorporating technology that supports use of Petroleum coke as fuel and for controlling
environmental emission levels.
The use of petroleum coke may be limited by its high sulfur content. Technological measures such as
finer grinding, pre-calciners designed to have a higher retention time, an external combustion
chamber before the calciner, a special high-momentum kiln burner, etc. will help to effectively utilize
Petroleum coke.
Based on the quality of Petroleum coke, typically a mixed fuel firing is designed. The percentage of
Petroleum coke is determined based on quality and operational trials.
 INFERENCE
• 100% Pet-coke not possible without modifcation and substantial investment.

• 20-25% petcoke is possible in dry process kiln without any modification and investment.

• It is concluded that use of pet-coke as a partial substitute fuel is feasible in most cases. The critical factor
to decide level of substitution by pet-coke is the molar ratio of oxides of alkalies to oxides of sulphur in
clinker. A detailed study is recommended to modify the existing process and equipment to suit the
properties of proposed quality of pet-coke.

• In view of company of production of cement and attractive payback periods, the use of pet-coke is likely to
increase rapidly.

• The CMA Technical Committee has been convinced of several advantages including socio-economic
benefits from use of Petcoke as cheaper, energy-economic and environment-friendly substitute of non-
renewable fuel like coal.

• CMA had therefore proposed to the Bureau of Indian Standards (BIS) to revise the relevant standards to
increase the permissible SO3 content up to 3.5% for all cements and up to 4% when petcoke is used as a
fuel.