D3P2 - Basic Cement Chemistry PDF

GEOLOGY, RAW MATERIALS AND RAW MIX
Process Engineering Certification Program

April 7 - 11, 2003
Raw Materials Chemistry

Learning Objectives
Understand chemical and mineralogical composition of

cement specific materials
Know the chemical moduli applied for cement specific

materials
Understand the Bogue-calculation for clinker mineral

phases
Understand the factors affecting burnability
2
Holcim (US) Inc. CTS Geology, Raw Materials and Raw Mix 12.12.2005
PECP02-2002
Chemical Composition
Elemental composition in Raw Mix

weight percentage. L.o.I. (Loss on ignition) 35.1
SiO2 14.3
By convention, the Al2O3 3.6
elements are expressed Fe2O3 2.0
in form of their oxides CaO 42.0
(exception; Cl, F). MgO 1.8
SO3 0.25
Usual sequence of K2O 0.63
elements in cement Na2O 0.22

TiO2 0.17
chemistry
Mn2O3 0.10
L.O.I.: e.g. at 1050 °C, P2O5 0.06

Cl 0.01
mainly due to CO2 and F
H2O Total 100.24
3
PECP02-2002
Chemical Formulae
The chemical formula indicates the elements occurring in a
chemical compound:
For a molecular compound, type and absolute number of
elements are given
H 2O O2 C6H6
Water Oxygen Benzene
For a mineralogical compound, type and relative number of

elements are given
SiO2 CaO CaCO3 Ca3SiO5
Quartz Lime Calcite Alite
Note: In mineralogical compounds, the elements need not
necessarily occur in simple numerical ratios (impurities,
solid solution)
4
PECP02-2002
Chemical Formulae
In the cement chemistry, shorthand's are often used:
CaO SiO2 Al2O3 Fe2O3 SO3 H2O

C S A F S H
Examples:
C3S for Ca3SiO5 (Alite)
C2S for Ca2SiO4 (Belite)
C3A for Ca3Al2O6 (Aluminate)
C4AF for Ca4Al2Fe2O10 (Ferrite)
5
PECP02-2002
Mineralogical Composition
Composition of material, expressed in weight-percentage of the

occurring minerals
Examples:
Limestone Calcite CaCO3 90%

Dolomite CaMg(CO3)2 5%
Quartz SiO2 5%
Clinker Alite C 3S 58%

Belite C2S 23%
Aluminate C 3A 9%
Ferrite C4AF 7%
Periclase MgO 1%
Arcanite K2SO4 1%
Free lime CaO 1%
6
PECP02-2002
Lime Saturation
CaO x 100
LS =
2.80 SiO2 + 1.18 Al2O3 + 0.65 Fe2O3
or
CaO
LSF =
2.80 SiO2 + 1.18 Al2O3 + 0.65 Fe2O3
The LS is a measure to which extent the CaO-richest compounds

C3S, C3A and C4AF can be formed without the necessary presence of
free lime. At LS > 100, free lime will unavoidably be present after
burning. 7
PECP02-2002
Saving Potential with Increased Free lime
Thermal Energy
Specific Saving Observed 3 kcal/kg per 0.1%

CaOf increase
Increase CaOf 1.0% - 1.5%
Saving 15 kcal/kg
8
PECP02-2002
Saving Potential with Increased Free lime
Grinding Energy
Specific Saving Observed 1 kWh/t per 0.5%

CaOf increase
Increase CaOf 1.0% - 1.5%
Saving 1 kWh/t
9
PECP02-2002
Lime Saturation
Applied for: Raw meal
Clinker
Cement: neat OPC only
CaO = CaOtotal – 0.7 SO3
Usual range in clinker: 85 – 100
Note: The influence of MgO can be accounted for
(CaO + 0.75 MgO) x 100

LS =
2.80 SiO2 + 1.18 Al2O3 + 0.65 Fe2O3
Max. 2% MgO may be introduced in formula (not applied in cement
specifications)
10
PECP02-2002
Silica Ratio
SiO2
SR =
Al2O3 + Fe2O3
Applied for: Siliceous-argillaceous raw

components
Raw Meal
Clinker
Cement
Usual range in clinker: 1.8 – 3.6
11
PECP02-2002
MgO
Act as a flux at sintering temperature

increase liquid phase
decrease viscosity
reduce burning temperature
Can lead to expansion (unsound) cement
only 2% in solid solution
free MgO causes expansion
Clinker made from magnesia-rich feed must be very
rapidly cooled
12
PECP02-2002
Alumina Ratio
Al2O3
AR =
Fe2O3
Applied for: Siliceous-argillaceous raw

components
Raw Meal
Clinker
Cement
Usual range in clinker: 1 - 3
13
PECP02-2002
Chemical Criteria for Raw Mix
2 .6
C V ,9 4
2 .4
2 .2 M L ,9 7
A T,9 8
D U ,9 1
2
Alumina R atio
1 .8
A D ,9 3
1 .6 P D ,9 5 TR ,9 1
M C ,9 6
1 .4 F C ,9 7
D S ,9 5
H H ,9 6 TH ,9 3
1 .2
1
2 2 .2 2 .4 2 .6 2 .8 3 3 .2 3 .4
S ilic a R a tio
14
PECP02-2002
Content of clinker Minerals according to Bogue
Percentage content of clinker minerals, assuming that

chemical equilibrium is attained, and that no impurities
are present.
C 3S = 4.07 CaO – 7.6 SiO2 – 6.72 Al2O3 – 1.43 Fe2O3
C 2S = 8.6 SiO2 + 5.07 Al2O3 + 2.08 Fe2O3 - 3.07 CaO
or 2.87 SiO2 – 0.754 C3S
C 3A = 2.65 Al2O3 – 1.69 Fe2O3
C4AF = 3.04 Fe2O3
In reality, the mineralogical composition of industrial

clinkers differs to some extent from that calculated
according to Bogue.
15
PECP02-2002
Contents of Clinker Minerals according to Bogue
Applied for Cement - OPC only (excl. blended cements)

- Correction for CaO in CaSO4:
CaO = CaOtot – 0.70 SO3
- For AASHTO: TiO2 and P2O5 to be

added to Al2O3 (no longer for ASTM)
Clinker - CaO can be corrected for free

lime; depending on objective of
calculation
CaO = CaOtot – CaOfree
16
PECP02-2002
Significance of Clinker Minerals for Cement Properties
C3S Contributes to early and late strength (1 d - …)

Increases heat of hydration
C 2S Contributes to late strength (28 d - …)
C 3A Contributes to early strength (1 – 3 d) Increases

heat of hydration
Impairs resistance to sulphate attack
C4AF Little effect
17
PECP02-2002
Significance of Clinker Minerals for ASTM Cement Types
Type I Portland no restrictions regarding clinker

minerals
Type II Portland with moderate sulphate resistance
(and moderate heat of hydration)
C3A max. 8 %
(C3S + C3A max. 58% for moderate
heat of hydration)
Type III Portland with high early strength

C3A max. 15%
(C3A max. 8% for moderate sulphate resist.
C3A max. 5% for high sulphate resist.)
18
PECP02-2002
Significance of Clinker Minerals for ASTM Cement Types
Type IV Portland with low heat of hydration

C3S max. 35%
C2S min. 40%
C3A max. 7%
Type V Portland with high sulphate resistance

C3A max. 5.0 %
C4AF + 2 C3A max. 25%
or
C4AF + 2 C2F max. 25%
19
PECP02-2002
Exercise for Calculation
Raw Mix Potential clinker composition
L.O.I. 35.1 ………
SiO2 14.3 ………
Al2O3 3.6 ………
Fe2O3 2.0 ………
CaO 42.0 ………
MgO 1.8 ………
SO3 0.25 ………
K2O 0.63 ………
Na2O 0.22 ………
TiO2 0.17 ………
Mn2O3 0.10 ………
P2O5 0.06 ………
Cl 0.01 ………
20
PECP02-2002
Exercise for Calculation
Raw Mix Potential clinker composition

LS ……… ………
SR ……… ………
AR ……… ………
Na2O-equiv. ………
C3S ………
C2S ………
C3A ………
C4AF ………
21
PECP02-2002
The affinity of the elements is
Cl
Alkali
Chlorides These are formed first
Alk
Alkali If both alkalis and sulfur are
Sulfates available, these formed next
SO3
Calcium Only if excess sulfates are
Sulfates
present, these are formed
Ca
22
PECP02-2002
Na2O-equivalent
Total alkali content, expressed as Na2O

Na2O-equivalent = Na2O + 0.658 K2O
Note: Limit for low alkali cement

Na2O-equivalent < 0.6 %
Applied for: Clinker

Cement
23
PECP02-2002
Molar Alkali/SO3 Ratio
K2O Na2O Cl
+ +
Alk 94 62 71
=
SO3 SO3
80
Desirable value: 1 - 1.2
24
PECP02-2002
Burnability
The amount of mass transfer of its constituents with ease
or difficulty to the clinker phases.
CaOf = f (θ, T)
where: θ - Burning time
T - Temperature
25
PECP02-2002
Factors Affecting Burnability
Raw mix
Mineralogical composition (lime, clay, corrective, and modifies)
Chemical composition (main component relations, minor volatile and non-volatile
components)
Granulometric composition (fineness, particle-size distribution, homogeneity, and
compaction
Thermal treatment (firing temperature, heating rate, burning period, and burning activation)
Liquid phase formation (appearance temperature, amount, viscosity, and surface tension)
Coal ash (amount absorbed, composition, and fineness)
26
PECP02-2002
Belite Formation
700 - 1200oC
2CaCO3 + SiO2 => C2S + CO2
Calcite Quartz Belite
Rapid Reaction Slow Reaction

Particle size not Particle size
limiting factor important
27
PECP02-2002
Burnability Test
Rating in test
Conditions
CaOf % Evaluation
1400C
0-2 very good
15 min.
2-4 good
10g material 4-6 moderate
Determined 6-8 poor
CaOf >8 very poor
28
PECP02-2002
Quartz: 32 micron
Calcite: 90 micron
CaOf = 0.60 Q>32 µm + 0.17 Cc>90 µm + 0.33 LS + 1.56 SR - 33.07

29
PECP02-2002
Grinding the raw materials finer leads to:
Faster reaction from raw meal to clinker in the kiln
Increased electrical consumption of the raw mills
30
PECP02-2002
Grinding raw materials too fine may lead to
generate more CKD.
Please discuss with people from Holly Hill,

Dundee and Ada.
31
PECP02-2002
If any of the following factors change, the raw materials set-point has to
be adjusted accordingly
The coal ash incorporation in clinker

The discarding of kiln dust
32
PECP02-2002
Coal Ash
In coal-fired kiln, the ash from the combustion of coal must

be considered!!!
For example:
If a kiln fires 25 tons/hour of coal having an ash content of
17%, there will be 4250 kg of coal ash added hourly to the
system.
33
PECP02-2002
Effect of Coal Ash on Clinker
Potential
Kiln Feed Coal Ash Clinker
SiO2 20.71 47.00 21.50
Al2O3 4.84 27.00 5.50
Fe2O3 2.78 20.00 3.30
CaO 67.43 3.00 65.50
MgO 2.58 0.00 2.50
SO3 0.15 1.5 0.15
Na2O
34
PECP02-2002
Effect of Coal Ash on LSF &SR
102 2.5
100
2.4
L S F o f C lin k e r
S R o f C lin k e r
98
96
2.3
94
92 2.2
0 10 20 30 0 10 20 30
Coal Ash Content (%) Coal Ash Content (%)
35
PECP02-2002
Changing from natural gas to coal firing
will alter the resultant clinker in
1. Chemical Composition
2. Alkali/SO3 Ratio
3. Burnability
36
PECP02-2002
The set points of the raw meal composition have to be such
that the target composition of the clinker is being obtained.
The primary target is the clinker

composition
37
PECP02-2002

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GEOLOGY, RAW MATERIALS AND RAW MIX

Process Engineering Certification Program

Raw Materials Chemistry

 Understand chemical and mineralogical composition of

 Know the chemical moduli applied for cement specific

 Understand the Bogue-calculation for clinker mineral

 Elemental composition in Raw Mix

elements in cement Na2O 0.22

 L.O.I.: e.g. at 1050 °C, P2O5 0.06

 For a mineralogical compound, type and relative number of

 In the cement chemistry, shorthand's are often used:

CaO SiO2 Al2O3 Fe2O3 SO3 H2O

Composition of material, expressed in weight-percentage of the

Limestone Calcite CaCO3 90%

Clinker Alite C 3S 58%

The LS is a measure to which extent the CaO-richest compounds

Specific Saving Observed 3 kcal/kg per 0.1%

Increase CaOf 1.0% - 1.5%

Specific Saving Observed 1 kWh/t per 0.5%

Increase CaOf 1.0% - 1.5%

(CaO + 0.75 MgO) x 100

Applied for: Siliceous-argillaceous raw

 Act as a flux at sintering temperature

Applied for: Siliceous-argillaceous raw

 Percentage content of clinker minerals, assuming that

In reality, the mineralogical composition of industrial

Applied for Cement - OPC only (excl. blended cements)

- For AASHTO: TiO2 and P2O5 to be

Clinker - CaO can be corrected for free

 C3S Contributes to early and late strength (1 d - …)

 C 2S Contributes to late strength (28 d - …)

 C 3A Contributes to early strength (1 – 3 d) Increases

 C4AF Little effect

 Type I Portland no restrictions regarding clinker

 Type III Portland with high early strength

 Type IV Portland with low heat of hydration

 Type V Portland with high sulphate resistance

Raw Mix Potential clinker composition

Total alkali content, expressed as Na2O

Note: Limit for low alkali cement

Applied for: Clinker

Desirable value: 1 - 1.2

 Coal ash (amount absorbed, composition, and fineness)

Rapid Reaction Slow Reaction

CaOf >8 very poor

CaOf = 0.60 Q>32 µm + 0.17 Cc>90 µm + 0.33 LS + 1.56 SR - 33.07

Increased electrical consumption of the raw mills

Please discuss with people from Holly Hill,

 The coal ash incorporation in clinker

In coal-fired kiln, the ash from the combustion of coal must

The primary target is the clinker

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Understand chemical and mineralogical composition of

Know the chemical moduli applied for cement specific

Understand the Bogue-calculation for clinker mineral

Elemental composition in Raw Mix

L.O.I.: e.g. at 1050 °C, P2O5 0.06

For a mineralogical compound, type and relative number of

In the cement chemistry, shorthand's are often used:

Act as a flux at sintering temperature

Percentage content of clinker minerals, assuming that

C3S Contributes to early and late strength (1 d - …)

C 2S Contributes to late strength (28 d - …)

C 3A Contributes to early strength (1 – 3 d) Increases

C4AF Little effect

Type I Portland no restrictions regarding clinker

Type III Portland with high early strength

Type IV Portland with low heat of hydration

Type V Portland with high sulphate resistance

Coal ash (amount absorbed, composition, and fineness)

The coal ash incorporation in clinker