Portland Clinker

Portland Clinker
Basic Chemistry
CRT Activities
Apr’2023
Page No. 1 25 April 2023
Clinker Chemistry - Overview
 Clinker Specifications / Definition/ Composition/ Parameter

 Clinker Chemical Modules / Mineral and Phase values
 Additives
• Raw materials
• Fuel
• Alternative Fuel / Co-processor – Waste to Co-product

Clinker – Specifications [IS 16353 : 2015]
MANAK BHAVAN, 9 BAHADUR SHAH ZAFAR MARG, NEW DELHI 110002
Table-1 (Clause 5) Chemical Requirements Table-2 (Clause 6.1) Physical Requirements

SN Characteristic Requirement Remarks SN Characteristic Requirement Remarks
1 Lime Saturation Factor (LSF) 0.66 - 1.02 LSF = CaO/ (2.8 SiO2 + 1.2 Al2O3 + 0.65 Fe2O3) 1 Fineness ( m2/kg) 220 ± 25 IS 4031 (Part-2)
2 Alumina Ratio (AR) 0.66 (Min) AR = Al2O3/Fe2O3 2 Total Sulphuric anhydrite (%) 3.5 (Max) Clinker + Gypsun
3 C3S (%) 35.0 (Min) C3S % = 4.071 (CaO - fCaO) - 7.60 SiO2 - 6.72 Al2O3 - 1.43 Fe2O3 3 Setting time IS 4031 (Part-5)
4 C3A (%) 3 - 12 C3A (2.650 Al2O3 - 1.692 Fe2O3) % Initial (Minutes) 30 (Min)
5 C2S + C3S (%) 70.0 (Min) C2S = (2.87 SiO2 - 0.75C3S) Final (Minutes) 600 (Max)
6 Total Sulphuric anhydrite (%) 2.7 (Max) 4 Soundness IS 4031 (Part-3)
7 Freelime (%) 3.0 (Max) Le - Chat expansion (mm) 10 (Max)
8 Chloride content (%) 0.05 (Max) Cement for Prestressed Concrete structure Autoclave ( % ) 0.8 (Max)
0.10 (Max) 5 Compressive strength (MPa) IS 4031 (Part-6)
9 Magnesia (%) 6.0 (Max) 72 ± 1hr 16 (Min)
10 Available alkalis as Na2O Equ (%) 0.6 (Max) Clinker for Low Alkali Cement 168 ± 2 hrs 22 (Min)
11 Total Loss on ignition (%) 1.5 (Max) 672 ± 4 hrs 33 (Min)
12 Insoluble residue (%) 1.0 (Max)

Clinker - Definition
 Dark grey nodular material Table-3 (Clause 6.2) IS 16353 : 2015

Granulometric Composition
 Usually 3 to 35 mm in diameter Clinker Size Proportion
SN
(mm) by Mass %
 Produced by sintering limestone and additives at 1 <5 35 (Max)
2 5 to 50 60 (Min)
temperature of about 1400oC-1500oC in cement kiln 3 > 50 10 (Max)
Hot Clinker Fresh Clinker Aged Clinker

5
Clinker – Typical Composition

Sulphates
CaO MgO
C C4AF
C3A
C3S
C2S
S M
A F
Oxides Notation Desirable range Mineral Desirable range

SiO2 S 21 - 23 % 3CaO·SiO2 [C3S] 50 - 60 %
Al2O3 A 5-6%
2CaO·SiO2 [C2S] 20 - 30 %
Fe2O3 F 3-4%
3CaO·Al2O3 [C3A] 5 - 11 %
CaO C 63 - 65 %
Minors M 4-5% 4CaO·Al2O3·Fe2O3 [C4AF] 4 - 10 %

Clinker – Parameter
Compositional Burnability
C3S, C2S Lime Saturation Factor (LSF)
C3A, C4AF Silica Modules (SM)
fCaO (Uncombined Lime) Alumina Modules (AM)
fCaO (Uncombined Lime)
MgO Coarse Quartz content
Preferable range <2%
K2O, Na2O Coarse Calcite content
 Uncombined lime during clinkerization caused by;
SO3 Volatile Contents
• Insufficient burning of the clinker
Cl Mineraliser • Decomposition of C3S in the clinker
• To high LSF of the clinker
 Free lime >2.0% is indicative of unsound Clinkers.
 fCaO (Free Lime) forms Ca(OH)2(Portlandite);

Which is twice volume of fCaO

Clinker – Chemical Modules
Lime Saturation Factor (LSF) – Ratio of actual amount of Lime to the theoretical amount of lime
required by other major oxides in the clinker
LSF (Clinker) = CaO / CaOmax
CaOmax = 2.80 x SiO2 + 1.18 x Al2O3 + 0.65 x Fe2O3
Typical range for LSF (Clinker) : 0.90 to 0.95 Higher LSF
 Make raw mix difficult to burn
 Trend to produce high free lime
 Increases C3S content, reduces C2S content
 Causes slow setting with high early strength

Clinker – Chemical Modules…Contd.
SM Or Silica Ratio (SM/ SR) - The amount of the melt phase is the burning zone is the function of SM
MS/ SR = SiO2 / ( Al2O3 + Fe22O3)
Typical range: 1.8 – 3.2 (Preferred : 2.2) Higher SM
 Results harder burning & high fuel consumption
 Characterizes the ratio of solid to liquid
 Causes difficult in coating formation
 Deteriorates kiln lining
 Results in slow setting & hardening of cement

Clinker – Chemical Modules…Contd.
Alumina Module Or Alumina Ratio (AM/ AR) - The temperature at which the melt forms depends on AM
AM/ AR = Al2O3 / Fe22O3
Typical range: 1.3 – 2.5 (Preferred : 1.5) Higher AM
 Increases C3A content and reduces C4AF
 Tends to cement quick setting and high early strength
 Decreases viscosity of liquid phase at fixed temperature
 It determines the role of fluxes in a raw mix
 The lowest temperature is obtained when AM (~1.6)

Clinker – Mineral and Phase value
Phase / Mineral Significance
C3S (Alite)  Hardens faster than C2S supports early strength
 Resistant to sulphur attack
 High value increases strength at all stages
C2S (Belite)  Hardens slowly and supports ultimate strength
 Generates low heat of hydration
 High value increases strength at later stages
C3A (Aluminate)  Sets quickly and gives high early strength
 Generates high heat of hydration
 Low value has resistance to Soil & water containing sulphates
 High value reacts with sulphates causing volumetric instability
 High value results Flash set in cement
 High value needs high sulphur in cement
C4AF (Ferite)  Minimal supports in ultimate strength
 Gives characteristic grey colour
 Avoids in the manufacture of white cement clinker

Determination of Clinker Mineral and Phase value
 Instrumental Method (Optical Microscopy)

Qualitative and Quantitative
 Instrumental Method (X-Ray Diffractometer)
Quantitative *All these chemical formulae are "rough" because
 Calculation Method (Bogue Calculation) Phases are actually solid solutions, and atoms of the formula are
Quantitative substituted to a small, but significant extent by other elements
Composition Typical range Desirable range

Tricalcium silicate (Alite) *Roughly 3CaO·SiO2 [C3S] 35 - 70 % 50 - 60 %
Dicalcium silicate (Belite) *Roughly 2CaO·SiO2 [C2S] 10 - 45 % 20 - 30 %
Tricalcium aluminate (Aluminate) *Roughly 3CaO·Al2O3 [C3A] 3 - 18 % 5 - 11 %
Tetracalcium alumoferrite (Ferrite) *Roughly 4CaO·Al2O3·Fe2O3 [C4AF] 1 - 15 % 4 - 10 %
Page No. 11 11 25 April 2023

Determination – Optical Microscopy
Porosity
C2S
Porosity
Free CaO
Liquid Phase
C3S
Portland Cement Clinker – Microscopic View

Determination – X-Ray Diffractometer (XRD)
Portland Cement Clinker – XRD View (Side by side)

Determination – Bogue Calculation
 C3S = 4.071CaO - 7.602SiO2 - 6.718 Al2O3 - 1.43 Fe2O3
 C2S = 2.867SiO2 – 0.754C3S

 C3A = 2.650 Al2O3 - 1.692 Fe2O3 C3S C2S C3A C4AF
Oxide Phase
W X Y Z
 C4AF = 3.043 Fe2O3
CaO C 0.7368 0.6511 0.6226 0.5462
SiO2 S 0.2632 0.3489 - -
Al2O3 A - - 0.3774 0.2099
Fe2O3 F - - - 0.3286
C = 0.7368 W + 0.6511 X + 0.6226 Y + 0.54625 Z
S = 0.2632 W + 0.3489 X
A = 0.3774 Y + 0.2099 Z
F = 0.3286 Z


 Additives
 Raw materials
• Type (Unusual / Industrial Waste / Natural)
• Nature (Crystalline / Amorphous)
• Reactivity and Grain size effect
• Determination of Coarse Grain
 Fuel
 Alternative Fuel / Co-processor – Waste to Co-product

Raw Materials Type – Unusual
• Sedimentary rocks might have traces of residues originating from plants and /
or animals which cause Emission known as Kerogen Matters ( have characteristics of Insoluble Organic Matter)
• Kerogen Matter is a mixture of large molecular weight hydrocarbons and is often accompanied by
presence of sulfide sulfur.
Hydrogen/carbon ratio can be compared;

• Wood = H/C ~ 0.10
• Coal = H/C ~ 0.50
• Kerogen matter H/C ~ 0.5 - 1.3
• Oil = H/C ~ 2.0
• Natural gas = H/C ~ 4.0
Page No. 16 16 25 April 2023

Raw Materials Type – Unusual (Kerogen Matters)
Decomposes into :
Organic Carbon
• Total hydrocarbon (THC) : 1-2 %
• Carbon monoxide (CO) : 10-20 %
• Carbon dioxide (CO2) : Balance
Sulfide Sulphur
Sulphur dioxide (SO2) : 100 %
Small quantity of water (H2O)

Kerogen Matters – Carbon & Sulphur
Carbon
• Organic Carbon - Freshly deposited litter (e.g. leaves, twigs, branches) to highly decomposed forms such as humus.
Other Forms of Carbon
• Inorganic Carbon - Calcite, Dolomite and Siderite;
• Elemental Carbon - Charcoal, Soot, Graphite and Coal;
Sulphur
• Sulphides - Di-sulphide (pyrite FeS2)
Other Forms of Sulphur
• Elemental Sulphur (S0)
• SO2 in volcanic gas (S4+)
• SO3 in volcanic gas (S6+)
If slag is being used (as raw material for raw mix) the available Sulphur of slag is found in the form of Sulphide only. The sulphide capacities of slags
is found in the multi component system (all oxides Si Al Fe Ca Mg, Mn etc. if copper slag than Cu also).

Kerogen Matters – Carbon in Rawmix
Page No. 19 19 25 April 2023

Kerogen Matters – Sulphur in Rawmix
SOx Emission from Kerogen matter
Worked Example
Measured – S Total = 0.30% (Total Sulfur in Kiln Feed)
Measured – S as Sulphide = 0.20% (Whole S-Sulphide Considered as Pyrite FeS2)
Calculated - S as Sulphur trioxide (Except S as sulphide) =0.25%

(0.3 - 0.2 = 0.1 × 2.5 = 0.25%)
Calculated - SO3 (Total) = 0.75% (0.3 × 2.5 = 0.75%)
SOx Emission [MoEF: 25.08.2014 (100 mg/Nm3 max)]

Calculated - SO2 @ 10% O2 (25°C; 1 atm) = 1186 mg/Nm3
SO2 @ 10% O2 (25°C; 1 atm) = 442 ppm
Sulphur in Raw meal by 1% will give a heat of 32 kcal/kg Clinker.
Page No. 20 20 25 April 2023

Raw Materials Type – Industrial Waste
Argillaceous/
Calcareous Ferruginous Ferruginous Argillaceous Mineralizer
Waste Hydrated Mill Scale Waste Fluoride SPL
Red mud Calcined Bauxite
lime
Sugar Sludge Flue dust

LD Slag Calcareous/ Argillaceous/
Siliceous Siliceous
Bottom Ash
Waste Slag
Calcined Lime Copper Sludge
Lime sludge
Suitability must be checked before use..
Page No. 21 21 25 April 2023

Raw Materials Type – Industrial Waste… Contd.
Material Approximate Content Type
Waste Hydrated lime - Sugar/Acetylene plant CaO = 50-70% Calcareous

Sugar Sludge - Sugar plant CaO = 40-45% Calcareous
Calcined lime – Soda ash plant CaO = 40-45% Calcareous
Lime sludge - Calcium carbide plant CaO = 60 – 65% Calcareous
CaO= 30-40% Calcareous
Waste slag - Steel/Phosphorous/Alumina plant
SiO2= 30-40% Siliceous
Flue dust - Steel plant Fe2O3= 40-50% Ferruginous
Mill scale – Metal extrusion plant Fe2O3= 60-90% Ferruginous
Al2O3=15-25% Argillaceous
Red Mud – Alumina plant
Fe2O3= 45-85% Ferruginous
Fluoride Waste - Alumina plant F = 12-20% As Mineralizer
SiO2=50-60% Siliceous
Waste Bottom ash – Thermal power plant
Al2O3= 20-30% Argillaceous
Suitability must be checked before use..

Type – Natural
Raw Materials Type – Natural
Lime Based Alumina Based
Silica Based Iron Based
Page No. 23 23 25 April 2023

Raw Materials Type – Natural… Contd.
Primary materials
% CaCO3 % Clay Nomenclature Mineral form
Calcitestone, Marble, Chalk

95 – 0 0–5 High grade Limestone
Limesand, Coral Limestone
85 -95 5 – 15 Limestone Lime Sand, Shell Deposit
75 – 85 15 – 25 Marly Limestone Marly Limestone
65 – 75 25 – 35 Calcareous Marl Calcareous Marl
35 – 65 35 – 65 Marl Marl
25 – 35 65 – 75 Clayey Marl Clayey Marl
15 – 25 75 – 85 Marley Clay Clay, Loess
5 – 15 85 – 95 Clay Claystone, Mudstone
0–5 95 – 0 High Grade Clay Siltstone, Shale
Page No. 24 24 25 April 2023

Raw Materials - Nature
Crystalline solids Amorphous solids

Characteristic geometrical shape Don't have definite geometrical shape
Translational symmetry, ordered structures that can Unsymmetrical, disordered cannot be described using
be built from repeated substructures - unit cells unit cells
Melt at a fixed and sharp temperature Melt over a wide range of temperature
Physical properties are different in different Physical properties are same in all directions - isotropy
directions - Anisotropy
Break at fixed cleavage planes Don't break at fixed cleavage planes
Amorphous solids support Burnability
Page No. 25 25 25 April 2023

Raw Materials – Nature… Contd.
Kinetic behaviour of crystal patterns
Crystal Pattern Reactivity Degree of crystallinity
Ideal crystal (Crystalline)

Lowest Highest
(ordered lattice)
Real crystal
(partially disordered lattice)
Glass (Amorphous)
Highest Lowest
(strongly disordered lattice)
Crystalline form  Reactivity low, require more energy for transformation
Amorphous form  Reactivity high, require less energy for transformation
Page No. 26 26 25 April 2023

Raw Materials – Nature… Contd.
Silica has different structures with same chemical formula (SiO2)

Ordered crystalline structure (Quartz) & Disordered amorphous structure (glass)
Page No. 27 27 25 April 2023

Raw Materials – Noteworthy Point
 Silicon dioxide is known as Silica and silica is found in Quartz
 Quartz has impurities (iron/manganese/calcium) with crystalline form of silica

(including agate, chert, flint, and jasper)
 Free Silica mainly consists of silicon dioxide, but it has mixture of amorphous silica and crystalline silica.
 Free Silica can be determined by conventional analytical methods but Quartz can be determined by Optical
Microscopy or Diffractometer only.
Page No. 28 28 25 April 2023

Raw Materials – Reactivity and Grain size effect
 Chemical
• Individual dissociation / Breakdown characteristic and thermal combinability.
 Physical
• Amenability to crushing and grinding
Page No. 29 29 25 April 2023

Reactivity - Chemical CSD-OS & Retrofits
Mineralogical assessment of raw mix

Mineral Effects on technology
Burning → impairs burnability

Calcite
Grinding → abrasion, wear and high power consumption
Burning → impairs burnability

Quartz
Grinding → abrasion, wear and high power consumption
Feldspar Burning → impairs burnability, low reactivity
Preparation → water absorption, stickiness

Clay minerals Burning → improved burnability
(Aluminosilicates) Dust production → reduced dust production
Coating properties → facilitates coating
Page No. 30 30 25 April 2023

Reactivity – Chemical… Contd.
Polymorphous Important constituents of Aluminum ore – Bauxite (Aluminum oxyhydroxide)
Polymorphs < Boehmite ((α-AlO(OH)) < Diaspore ((γ-AlO(OH))
Page No. 31 31 25 April 2023

Reactivity - Physical
Calcite; Quartz - Grain Size effect

Crystallinity Grain size Rate of Dissociation
mm dissociation temp
Very coarse grained > 1.00 Lowest Highest
Coarse grained 1.00-0.50
Medium grained 0.50-0.25
Fine grained 0.25-0.10
Very fine grained 0.10-0.01
Microcrystalline < 0.01 Highest Lowest
Limestone Compressive strength < 100 MPa Supports Grindability.
Page No. 32 32 25 April 2023

Reactivity – Physical… Contd.
• Calcite (125μm);
Mohs Hardness 2.5 – 3.0
• Feldspar (45 - 63μm);

Mohs Hardness 6.0
• Quartz (45μm);
Mohs Hardness 7.0
Courtesy;
Fundal (1979, 1996) & Kirsten Theisen (1992)
Page No. 33 33 25 April 2023

Reactivity – Physical… Contd.
Page No. 34 34 25 April 2023

Grain size effect – Microscopic View
Typical Calcite grain>125 µm
Page No. 35 35 25 April 2023

Grain size effect – Microscopic View… Contd.
Page No. 36 36 25 April 2023

Freelime from
coarse calcite
Page No. 37 37 25 April 2023

Typical Quartz grain>45 µm
Page No. 38 38 25 April 2023

Belite cluster from

coarse Quartz
Typical Quartz grain>45 µm
Page No. 39 39 25 April 2023

Determination of Coarse grain
 Instrumental Method (Optical Microscopy)

Qualitative and Quantitative
 Instrumental Method (X-Ray Diffractometer)

Quantitative
 Analytical Method (Sieving, Wet chemical)

Quantitative
Page No. 40 40 25 April 2023

Determination – Optical Microscopy
Quartz
Acid insoluble residue >45µm in the microscope
Page No. 41 41 25 April 2023

Determination – Optical Microscopy… Contd.
Calcite
Quartz
Total Raw Mix residue +125µm
Page No. 42 42 25 April 2023

Determination – X-Ray Diffractometer (XRD)
XRD pattern of the investigated

limestone sample showing calcite as a
major mineral phase followed by quartz
and dolomite phases.
Courtesy – ResearchGate
Page No. 43 43 25 April 2023

Determination – Analytical
 Wet Sieving
• Wet Sieving Residues % Residue125µm
• Wet Sieving Residues % Acetic Residue45µm
The two sieving residues should remain constant. If they vary, the burnability will vary as well.
An increase in sieving residues will normally mean harder Burnability.
 Determination of free Silica

• IS 1760-6 (2001): Chemical Analysis of Limestone, Dolomite and Allied Materials, Part 6: Determination of Free Silica.
• Suggested to carry out Free Silica test in;
Wet Sieving Residues % Hydrochloric Residue45µm
Page No. 44 44 25 April 2023


 Additives
 Raw materials
 Fuel
• Type/Nature/Formation/Generation
• Significances of Proximate/Ultimate/Heat value
• Role of Petcoke in Clinker manufacturing

Fuels - Type and Nature
 Coal
Vegetable matter/fossil fuel; naturally occurred as a sedimentary rock
 Petcoke
Solid high-carbon material produced as a by-product of oil refining process
Coal – Natural Non Natural – Petcoke
Petcoke typically has higher energy content and low ash content than coal.
This makes it cheaper to ship and to burn than coal.
Page No. 46 46 25 April 2023

Formation of Coal
~6 -7 feet ~1 foot
~6 to 7 feet of compacted plant matter is required to form 1 foot of bituminous coal
Page No. 47 47 25 April 2023

Generation of Petcoke
Fuel grade
or
Anode grade
Fuel grade (high in Sulphur); Anode grade (low in Sulphur)
Page No. 48 48 25 April 2023

Natural Fuel – Coal
Graphite Anthracite Bituminous SubBituminous Lignite
Metallic luster Lustrous Bonded Smooth Soft

appearance appearance appearance appearance appearance
Carbon % Carbon % Carbon % Carbon % Carbon %

97-99 85-97 45-85 35-45 25-35
Moisture % Moisture % Moisture % Moisture % Moisture %

0 - 0.01 1-2 5-10 10-15 20-60
Page No. 49 49 25 April 2023

Natural Fuel – Coal
Approximate chemical contents of coal burned
Component Bituminous coal Sub-bituminous coal Lignite coal
SiO2 (%) 20 - 60 40 - 60 15 - 45
Al2O3 (%) 5 - 35 20 - 30 20 - 25
Fe2O3 (%) 10 - 40 4 - 10 4 - 15
CaO (%) 1 - 12 5 - 30 15 - 40
LOI (%) 0 - 15 0-3 0-5
Page No. 50 50 25 April 2023

Significance of Proximate & Ultimate Analysis
 Proximate Analysis indicates the percentage by weight of;

Fixed Carbon; Volatile Matters; Ash Contents; Moisture Content
 Amounts of fixed carbon and volatile combustible matter directly contribute to the heating value of Fuel
 Fixed carbon acts as a main heat generator during burning. High volatile matter content indicates easy ignition of fuel
 Ultimate Analysis indicates the various elemental chemical constituents;

Carbon; Hydrogen; Nitrogen; Oxygen; Sulphur
 It is useful in determining the quantity of air required for combustion and the volume and
composition of the combustion gases. This information is required for the calculation of flame
temperature and the flue duct design etc.
Page No. 51 51 25 April 2023

Proximate Analysis
 Fixed carbon (FC)

It’s the solid fuel left after volatile matter is distilled off. It consists mostly of carbon but also contains some hydrogen, oxygen,
sulphur and nitrogen not driven off with the gases. Fixed carbon gives a rough estimate of heating value of fuel
 Volatile Matter (VM)
It’s an index of gaseous fuels present. VM’s are the methane, hydrocarbons, hydrogen and carbon monoxide, and incombustible
gases like carbon dioxide and nitrogen found in coal. It proportionately increases flame length, and helps in easier ignition of coal
 Ash Content
Ash is an impurity that will not burn off. Amount and chemistry of ash content is very important as it adulterates the clinker
during clinkerization
 Moisture Content
It replaces combustible matter and decreases the heat content per kg of fuel. Increases heat loss, due to evaporation and
superheating of vapour, but helps to a limit, in binding fines and aids radiation heat transfer
Page No. 52 52 25 April 2023

Significance of Energy Value
 Energy value/calorific value of a fuel, is amount of heat released during combustion of a specified amount of it
 Energy value is a characteristic for each fuel. It is measured in units of energy per unit of the mass, Heating value
is commonly determined by use of a Bomb calorimeter
 Gradation of Indian coal based on its Energy value/calorific value
Grade Calorific Value Range

A Exceeding 6200 kcal/kg
B 5600 – 6200 kcal/kg
C 4940 – 5600 kcal/kg
D 4200 – 4940 kcal/kg
E 3360 – 4200 kcal/kg
F 2400 – 3360 kcal/kg
G 1300 – 2400 kcal/kg
Page No. 53 53 25 April 2023

Characteristics of Fuels
 Lower moisture – Good flowability
 Lower ash - Less ash absorption
 Lower Volatiles - Difficult to burn
 Higher heating value – Less fuel consumption
 Higher Sulphur value - Operational problems
 Higher NOx generation - Emission problems
 Lower Hard Grove Index - Harder to grind

Role of Petcoke in Clinker Manufacturing
Petcoke – Characteristics
 High Carbon Content - It’s high carbon content makes it an excellent heat energy source
 High calorific value - It’s high calorific value, ranging from 7000 to 8500 Kcal/kg, which makes it an economic fuel
 Low volatile matter - It’s low volatile matter makes it a slow burning fuel so it requires high ignition temperature
 High Sulphur Content - It’s high Sulphur content, which necessitates the deployment of SOx capture or removal
system to reduce SO2 emissions. However, Petcoke is ideal for burning in cement kilns, where the sulphur
combines with alkalis to form sulphates, thus limiting the SO2 emission
 Low Ash Content : It’s low ash content, which reduces the ash absorption in clinker hence, reduces the high
grade consumption in rawmeal
 Low Hardgrove Grindability Index : It’s low Hardgrove Grindability Index, which makes it relatively harder
material to grind and pulverise
Page No. 55 55 25 April 2023

Petcoke – Comparison with Coal
Proximate analysis, Energy value and Hardness
Petcoke Indian Coal Indonesian Coal South African Coal

Parameters
Indigenous Sub-bituminous Bituminous B-Grade
Inherent Moisture (%) 0 - 0.5 3-5 8 - 10 3-5
Ash Content (%) 0.5 - 5.0 35 - 40 10 - 15 15 - 20
Volatile Matter (%) 8 - 12 20 - 25 27 - 32 25 - 30
Fixed Carbon (%) 85 - 95 32 - 37 45 - 50 50 - 55
Gross Calorific Value (kcal/kg) 7000 - 8250 4000 - 4500 5200 - 5700 5500 - 6000
HGI Value 35 - 65 45 -75 45 -75 45 -75
Page No. 56 56 25 April 2023

Petcoke – Comparison with Coal
Ultimate analysis
Petcoke Indian Coal Indonesian Coal South African Coal

Parameters
Indigenous Sub-bituminous Bituminous B-Grade
Carbon (%) 80 – 90 40 - 45 55 - 60 60 - 65
Hydrogen (%) 3.3 - 4.3 2.5 – 3.0 4 - 4.5 3.5 - 4.0
Sulphur (%) 2.0 - 5.5 0.25 - 0.5 0.5 - 0.8 0.8 - 1.0
Nitrogen (%) 0.5 - 2.0 1 - 1.25 1 - 1.2 1.5 – 1.8
Oxygen (%) 0.1 - 3.2 8 - 10 10 - 12 8 - 10
Page No. 57 57 25 April 2023

Petcoke – Utilization
 Low volatile content : Difficult to burn/ requires finer grinding
Petcoke Quality  Hard Grind ability: Lower HGI /higher specific power for grinding
 Sulphur: Sulfur Cycle , Coatings
 Calorific value vs Grindability: Requirement vs Grindability.

 Intergrinding with high volatile coal:
Fuel preparation  Mill considerations for grinding
 Lower Moisture
 Raw mix based upon the characteristics of petcoke: Less ash absorption
 Proper residence time in calciner for complete combustion
Kiln Process
 Higher Fuel NOx
 Kiln inlet oxygen
 Sulphur content in the clinker under permissible limits
Critical Limits  Alkali / Sulfur ratio under permissible limits
 Proper process study on emission to be done.
 Increases liquid quantity and reduces viscosity of liquid.

Quality Control  Clinker Granulometry - Fines generation/issues in cooler operation
 Clinker Grindability – practical observation shows increase by ~5%
Page No. 58 58 25 April 2023

Petcoke – Process Constraints
 Sulphatisation
High sulphur results in blockage/ build ups.
 NOx Emissions
Petcoke generate higher NOx than coal in calciner.
 Calciner Operation
Don’t want un burnt carbon in cyclone stage -cause build ups,
increase CO and sulphur cycle/High retention time
 Milling (Petcoke)
Grinding material finer due to low volatile; to be ground 90µm 1 to 3% for Kiln burner and Calciner.
 Clinker Liquid property
Increases liquid quantity and reduces viscosity of liquid.
 Clinker Granulometery
Fine generation/issues in cooler operation
 Clinker Grindability
Replacement of 100% coal by 100% Petcoke on main burner increases power demand for milling cement by 1 to 3kWh/t .
Page No. 59 59 25 April 2023

Petcoke – Process Constraints… Contd.
Low volatile content
 Low volatile content gives slower combustion. Needs finer grinding to promote complete combustion
 Slow combustion increases the residual carbon in the charge
 Carbon react with sulphates forming SO2
 SO2 condense/react on the dust and riser walls
 Coarse particles will ignite later, may create CO & temperature increase later in kiln system
 In general the pulverized petcoke residue must be as low as possible ~1 – 3% on 90m Hard Grindability
 HGI of Petcoke ranges between 30 – 55.
 Green delayed cokes present higher permeability & HGI between 45-55.
 Requires high specific grinding force which is important when grinding.
High - Sulphur content  Very hard material & grinding to a very fine product.
 Needs more grinding power.
 Sufficient alkalis required in raw mix to neutralize Sulphur from petcoke
 Intergrinding of Petcoke + Imported coal to suffice same mill.
 US and Canada sourced petcoke have high Sulphur than Middle east Petcoke
 High Sulfur causing more plugging (kiln inlet/preheater)
 High Sulfur Petcoke usually are harder and have higher Volatile Matter & Nitrogen content, which affects significantly NOx generation
 Sulphur ring formation in kiln
 Kiln inlet material spillage
 Optimisation of the burner inclination to be done by measuring SO2 in hot meal.
Page No. 60 60 25 April 2023

Formation and Absorption of SO2 in Various Zones of Cement Kiln
Zone Temperature SO2 Formation SO2 Absorption
Raw mill &

Ambient to 100℃ NA CaCO3 + SO2  CaSO3 + CO2
precipitator
Sulphides + O2 Oxides + SO2

Preheating zone 100 to 750℃ CaCO3 +2SO2  CaSO3 + CO2
Organic S + O2  SO2
Calcining zone & 750 to 1250℃ Fuel S + O2  SO2

CaO + SO2  CaSO3
Upper Transition CaSO4 + C  SO2 + CO
CaSO3 + ½ O2  CaSO4
Zone
Na2O + SO2+ ½ O2  Na2SO4

K2O + SO2+ ½ O2  K2SO4
Burning zone 1250 to 1500℃ Fuel S + O2  SO2
CaO + SO2+ ½ O2  CaSO4
Sufficient oxygen is required during clinkerization to ensuring the generation of SO2

and its transformation into other sulfur compounds.
Page No. 61 61 25 April 2023

Problems due to High Sulphur
Cyclone blockage Build-ups in cyclone bottom
Page No. 62 62 25 April 2023

Petcoke – Preconditions for firing
Sufficient alkali input

in raw mix
High
Residence
time
Appropriate
Alk/S ratio High
momentum
burner
Appropriate
O2 at kiln
inlet
Free lime
1-1.5%
Page No. 63 63 25 April 2023

Source of SO2 Emissions
Primary source of SO2 Emissions:

Pyritic Sulfur in Raw Mix
S-- + O2 = SO2
Reaction takes place in the temperature range of 400 - 600ºC
Page No. 64 64 25 April 2023

Sulphur Flow Sheet
Feed (including FeS2)

295°C
Conditioning tower
500°C
Stack
Silo
Gas without SO2
645°C
Gas with SO2
Solid sulfur
780°C
Bag or ESP
890°C 900-1100°C
filter
CaCO3(s)  CaO (s) + CO2(g)
SO2 (g)+ CaO(s) + ½O2 (g)  CaSO4 (s)
Raw mill Fuel 780°C
Bypass
1450°C
Clinker
Fuel
Page No. 65 65 25 April 2023

 Additives
 Raw materials
 Fuel (Main and Alternative)
• References
• Basic Rule
• Proper usage/ Processing
• Benefits
• Maximization/ Technical Solution

Co-processing – Waste to Co-product
 Reference
A). CPCB (Feb’2010) Guidelines on Co‐processing in Cement/Power/Steel Industry
(Ministry of Environment & Forests, Govt. of India)
B). CPHEEO (Oct’ 2018) Guidelines on Usage of RDF in Various Industries

(Ministry of Housing and Urban Affairs); www. swachhbharaturban.gov.in
C). CPCB (Jul’2015) Hazardous And Other Wastes (Management and Transboundary Movement) Rules, 2015,
(Ministry of Environment, Forest and Climate Change vide number G.S.R. 582(E),
Suitability must be checked before use!!!
Page No. 67 67 25 April 2023

Co-processing – Basic Rule
Requirement
 Waste accepted must give an added value for cement kiln
• Calorific value from the organic part
• Material value from the mineral part
 Co-processing can be used
• As raw materials Regulations
 The maximum concentration of various toxic parameters of waste
• As a source of energy
considered for co-processing, is termed as Acceptance Criteria
• Or both
 This is evolved based on the following criteria
• Emission standards
• Pollutants in traditional raw materials
• Treatment alternatives for the available waste
• Trial run conducted in India
Page No. 68 68 25 April 2023

Co-processing – Regulation
Page No. 69 69 25 April 2023

69
Co-processing – Regulation
Page No. 70 70 25 April 2023

70
Alternative Fuel – Availability
Suitability must be checked before use!!!
Page No. 71 71 25 April 2023

Alternative Fuel – Proper usage
Page No. 72 72 25 April 2023

Alternative Fuel – Proper Processing
Page No. 73 73 25 April 2023

Alternative Fuel – Proper Processing… Contd.
Page No. 74 74 25 April 2023

Alternative Fuel – Benefits
Why Alternative Fuels?

• Put waste to good use by turning it into energy
• Co-processing reduces global impact by reducing CO2 emissions
• Affectedly reduce the fuel costs in energy intensive industries
• Achieve Zero fuel costs if feasible
• Convert fuel costs into earnings
• Continuously increasing wastes created by society can be reduced
• Save natural resources and fossil fuels for future
Page No. 75 75 25 April 2023

Alternative Fuel – Benefits… Contd.
“Co-processing is advantageous by capturing energy used during incineration and
utilizing leftover ash, Cement Kiln offers excellent opportunities for safe and sound
recovery of wide variety of Alternative Fuels”
Page No. 76 76 25 April 2023

Alternative Fuel – Benefits… Contd.
General – Guidelines
 Co-processing is a sound alternative that improves ecological footprint
 Diversion from landfill reduces future emissions of methane
 Energy content of used tires 1 ton of used tires = 1.1 tons of coal
 Ash content of used tires is rich in calcium, iron and aluminum
Cement Kiln – Suitable for burning of waste

 High temp, long residence time in oxygen rich atmosphere ensures complete destruction of organic
compounds found in any waste
 Complete scrubbing of exhaust gas due to countercurrent flow of raw material resulting in trapping of
heavy metals, sulphur and other pollutants within clinker
 No “ash” residue; inorganic components are incorporated in clinker
 Process design & operating parameters protect the environment
Page No. 77 77 25 April 2023

Alternative Fuel – Maximization
 Appropriate particle size

AFR Quality  Low and constant H2O content
 Homogenous product mix
 Selection of suitable firing point based upon the waste characteristics

Feeding System  Feeding system sustaining the physical nature of the fuel with full proof system
 Consistent and controlled feed rate with advance automation
 Raw mix based upon the characteristics of waste and % addition

Kiln Process
 Proper residence time in calciner for complete combustion
 Accuracy in feed rate
 Chlorine content in the clinker under permissible limits
Critical Limits
 Alkalis/ Sulfur ratio under permissible limits
 Proper process study on emission to be done.
 Continuous R&D in Alternative process and product technology for 100% substitution
Innovation
 Modification in kiln and calciner system for higher TSR.
Page No. 78 78 25 April 2023

Alternative Fuel – Technical Solution
Technical Solution Benefits Accrued

Retrofit of calciner with low NOx calciner with 85% Fuel substitution without affecting the
Alternative fuel feeding system production rate
Chlorine bypass for calciner retrofit with pneumatic 50% Fuel substitution with emission levels within the
Alternative fuel feeding system. control limits specified by the customer.
Low Nox calciner with mechanical feeding system for 50% Fuel substitution without affecting production
alternative fuels rate.
Page No. 79 79 25 April 2023

Thank You
CONTACT INFORMATION
New Delhi
Corporate Office: 11th & 12th floor,
Hansalaya Building, 15, Barakhamba
Road, New Delhi – 110001
Best Regards,
t: 91 11 23465100
Dr. Alka Mishra f: 91 11 23313303
Contact No.: +91 87545 75186 e: corpcomm@dalmiabharat.com
mishra.alka@dalmiacement.com w: www.dalmiabharat.com
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Portland Clinker - Basic Chemistry

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 Clinker Specifications / Definition/ Composition/ Parameter

Page No. 2 25 April 2023

MANAK BHAVAN, 9 BAHADUR SHAH ZAFAR MARG, NEW DELHI 110002

Table-1 (Clause 5) Chemical Requirements Table-2 (Clause 6.1) Physical Requirements

Page No. 3 25 April 2023

 Dark grey nodular material Table-3 (Clause 6.2) IS 16353 : 2015

Hot Clinker Fresh Clinker Aged Clinker

Page No. 4 25 April 2023

Clinker – Typical Composition

Oxides Notation Desirable range Mineral Desirable range

Page No. 5 25 April 2023

 Free lime >2.0% is indicative of unsound Clinkers.

 fCaO (Free Lime) forms Ca(OH)2(Portlandite);

Page No. 6 25 April 2023

LSF (Clinker) = CaO / CaOmax

CaOmax = 2.80 x SiO2 + 1.18 x Al2O3 + 0.65 x Fe2O3

Typical range for LSF (Clinker) : 0.90 to 0.95 Higher LSF

 Make raw mix difficult to burn

 Trend to produce high free lime

 Increases C3S content, reduces C2S content

 Causes slow setting with high early strength

Page No. 7 25 April 2023

MS/ SR = SiO2 / ( Al2O3 + Fe22O3)

Typical range: 1.8 – 3.2 (Preferred : 2.2) Higher SM

 Results harder burning & high fuel consumption

 Characterizes the ratio of solid to liquid

 Causes difficult in coating formation

 Deteriorates kiln lining

 Results in slow setting & hardening of cement

Page No. 8 25 April 2023

AM/ AR = Al2O3 / Fe22O3

Typical range: 1.3 – 2.5 (Preferred : 1.5) Higher AM

 Increases C3A content and reduces C4AF

 Tends to cement quick setting and high early strength

 Decreases viscosity of liquid phase at fixed temperature

 It determines the role of fluxes in a raw mix

 The lowest temperature is obtained when AM (~1.6)

Page No. 9 25 April 2023

Page No. 10 25 April 2023

 Instrumental Method (Optical Microscopy)

Composition Typical range Desirable range

Page No. 11 11 25 April 2023

Portland Cement Clinker – Microscopic View

Page No. 12 25 April 2023

Portland Cement Clinker – XRD View (Side by side)

Page No. 13 25 April 2023

 C3S = 4.071CaO - 7.602SiO2 - 6.718 Al2O3 - 1.43 Fe2O3

 C2S = 2.867SiO2 – 0.754C3S

Page No. 14 25 April 2023

 Clinker Specifications / Definition/ Composition/ Parameter

Page No. 15 25 April 2023

Hydrogen/carbon ratio can be compared;

Page No. 16 16 25 April 2023

Small quantity of water (H2O)

Page No. 17 25 April 2023

Page No. 18 25 April 2023

Page No. 19 19 25 April 2023

SOx Emission from Kerogen matter

Measured – S Total = 0.30% (Total Sulfur in Kiln Feed)

Measured – S as Sulphide = 0.20% (Whole S-Sulphide Considered as Pyrite FeS2)

Calculated - S as Sulphur trioxide (Except S as sulphide) =0.25%