Chapter II - b

Raw Mix Knowledge

Objectives and principles
Industrial Examples Tools - Exercises

November 2004
 Learning Objectives

By the end of this presentation you should be

able to :

 Get the knowledge about raw mix chemistry

 Get the link between raw mix and the 10 facts

of clinker

Process Engineering Program – Raw Mix Optimization November 2004 2

 Content

1. Pre-requisites to Raw Mix Knowledge

2. LSF, Deltabc, Sir and AR
3. C3S, C3A, Liquid Phase and Alkalies effect
4. Free lime, C2S and C4AF effects
5. Conclusion

Process Engineering Program – Raw Mix Optimization November 2004 3

 Clinker and Cement Notations

Major oxides Symbol Notation

 Calcium Oxide CaO C
 Silica SiO2 S
 Aluminum Oxide Al2O3 A
 Iron Oxide Fe2O3 F

Example : C4AF means the phase (CaO)4,Al2O3,Fe2O3

Process Engineering Program – Raw Mix Optimization November 2004 4

 Clinker and Cement Notations

Minor oxides Symbol Notation

 Magnesium Oxide MgO M
 Sodium Oxide Na2O N
 Potassium Oxide K2O K
 Phosphore Oxide P2O5 P

Process Engineering Program – Raw Mix Optimization November 2004 5

 Cement Production

 Production Steps :
RAW MATERIALS

80% of limestone (CaCO3)

20% Clay (SiO2-Al2O3)
Crushing and Milling <200 µm
Sweeteners : bauxite, iron oxide, slag,….

KILN FEED

Chemical Composition (weight)

CaO SiO2 Al2O3 Fe2O3
(lime) (Silica) (Alumina) (Iron) Burning 1,450°C

65 to 70% 18 to 24% 4 to 8% 1 to 6%

CLINKER

4 Main Phases
Formula Name Chemical Formula Av. % in weight
Milling <100 µm with gypsum
C3S Alite 3 CaO,SiO2 62
C2S belite 2 CaO, SiO2 22
C3A 3 CaO, Al2O3 8
C4AF 4 CaO, Al2O3,Fe2O3 8 CEMENT

Process Engineering Program – Raw Mix Optimization November 2004 6

 LSF and GSP : Calculation
 Formula :

CaO * 100
LSF 
2.8 * SiO 2  1.2 * Al 2 O 3  0.65 * Fe 2 O 3

 Typical Values : between 90 and 110

Process Engineering Program – Raw Mix Optimization November 2004 7

 2
Δbc : Calculation

 Formula : the sum (SiO2+Al2O3+Fe2O3+CaO) is different from

100 so we need transformed to a % over 100

2.8 * SiO 2  1.65 * Al 2O 3  0.35 * Fe 2O 3  CaO

bc  * 100
SiO 2  Al 2O 3  Fe 2O 3  CaO

 Typical Values : between

 It is to set the value of C2S and then C3S.

 If Deltabc is constant then the kiln feed is constant

Process Engineering Program – Raw Mix Optimization November 2004 8

 Δbc : Concept
 Δbc is the difference between the theoritical CaO required and the real CaO input
to maximise the C3S production through the industrial equipment.

CaO  3 * SiO 2  CaO ,3 SiO 2 ( orC 3 S )

 It is the difference between the thermodynamic and the kinetic CaO transformed
into C3S to minimise the production of free lime. So the CaO input will be less to
guarantee the combination of CaO and SiO2

 Get the maximum proportion of C3S with a raw material containing SiO2, Al2O3,
Fe2O3 and CaO :

 To combine SiO2 into C3S, we need 2.8*SiO2 (1)

 To combine Al2O3 into C3A, we need 1.65*Al2O3 (2)
 To combine Fe2O3 into C4AF, we need 0.35*Fe2O3 (3)
 To get the best cement, we require the CaO theoritical :
CaOth = (1)+(2)+(3)+(4) = 2.8*SiO2+1.65*Al2O3+0.35*Fe2O3 (4)

 Then Δbc = CaOth - CaO real = 2.8*SiO2+1.65*Al2O3+0.35*Fe2O3- CaO

Process Engineering Program – Raw Mix Optimization November 2004 9

 Loss On Ignition (LOI)

 Decarbonation of CaCO3, MgCO3

CaCO 3  CaO  CO 2 MgCO 3  MgO  CO 2
 Combined water in clays and organic matters (TOC)
 Measured with a lab protocol (Temperature 975°C)

 Calculated (estimation)

LOI  0.7857.CaO %  1.089. MgO

 Kiln feed Values LOI= 35.5% on average

 Clinker by definition LOI=0% in theory (0.4% in practice)

Process Engineering Program – Raw Mix Optimization November 2004 10

 Silica Ratio : SiR

 Formula : proportion of SiO2 to the total of Al2O3 and Fe2O3

SiO 2
SiR 
Al 2O3  Fe2O3
 Quality :
 It is to set the proportions of silicates (C3S and C2S) compared
to the aluminates and the aluminoferrites (C3A and C4AF).
 A high value will increase the cement strength but the clinker
reactivity may drop.
 Range :
 Typical Clinker : Average value 2.65

SiR between 2.2 and 3.3
 White Clinker : SiR between 7 and 10

Process Engineering Program – Raw Mix Optimization November 2004 11

 Silica Ratio : SiR

 Production :
 Too high
Liquid phase reduced
Reduce burnability
Risk of over-burnt free lime
No coating (high wall losses
Brick wear

Process Engineering Program – Raw Mix Optimization November 2004 12

 Silica Ratio : SiR
Kiln Feed SiR
2003 Values
3.40

3.20

3.00

2.80
S iR

2.60

2.40

2.20

2.00

Works

Process Engineering Program – Raw Mix Optimization November 2004 13

 Alumina Ratio : AR
 Formula : proportion of Al2O3 to Fe2O3
Al 2O3
A/ F 
Fe2O3
 Quality :
 It is to set the proportions of aluminates (C3A) compared to the
the aluminoferrites (C4AF).
 A high value will increase the C3A and the setting time.
 For 0.63, C3A=0%
 Range :
 Typical Clinker : Average value 1.90

AR between 0.75 and 2.60
 White Clinker : 10

Process Engineering Program – Raw Mix Optimization November 2004 14

 Alumina Ratio : AR

 Production :
 It is linked to the liquid phase composition.
 A high AR will increase the liquid phase viscosity.
 A low AR will increase the liquid phase proportion.

Process Engineering Program – Raw Mix Optimization November 2004 15

 Alumina Ratio : AR
Kiln Feed AR
2003 Values
3,20

2,70

2,20
AR

1,70

1,20

0,70

0,20

Works

Process Engineering Program – Raw Mix Optimization November 2004 16

 Equivalent Alkalies (eqNa2O)

 K2O and Na2O are alkalies

EqNa 2 O  Na 2 O %  O .658 * K 2 O %
 SO3 and EqNa2O molar ratio
SO 3 SO 3%
 x 0.775
EqNa 2 O EqNa 2 O

 SO3 Excess
SO 3 excess  SO 3 clin ker  1.29 * EqNa 2 O

Process Engineering Program – Raw Mix Optimization November 2004 17

 Main Objective

Produce clinker which is a mix of 4 main phases

 C3S (Alite) 3CaO.SiO2 Tricalcium Silicate
 C2S (Belite) 2CaO.SiO2 Dicalcium Silicate
 C3A 3CaO.Al2O3 Tricalcium Aluminate
 C4AF 4CaO.Al2O3.Fe2O3 Tetracalcium Alumino-Ferrite

So we need to input in the kiln CaO, SiO 2, Al2O3 and Fe2O3 in the
right proportions to combine (or react together)

Process Engineering Program – Raw Mix Optimization November 2004 18

 Rankin Diagrams

Process Engineering Program – Raw Mix Optimization November 2004 19

 Study Case : Assumptions

Product team requires from us a clinker with :

C3S Clinker 60-62%
Free Lime Clinker 1.2%
C3A Clinker 8.5%
100 % Pet Coke
Liquid Phase 25%
SO3 Clinker 1.7%
EqNa2O Clinker 0.6%

Process Engineering Program – Raw Mix Optimization November 2004 20

 Clinker C3S (alite)

Alite is the main phase of the clinker which gives strength.

The values are between 58% to 72%.
5th Rule of the « 10 basic Facts on Clinker »

Increasing clinker C3S (to the detriment of C2S) improves

strength at 1, 2, 3 and 7 days.
Key figures :
+10% C3S  +2 to +5 MPa for early strengths

After 28 days, the gain may be less because of the C2S

contribution.

Process Engineering Program – Raw Mix Optimization November 2004 21

 Clinker C3S (Bogue calculation)

Alite % can be estimated as a pure C3S with the following formulas

 From a kiln feed analysis, the chemistry has to be transformed to a clinker analysis (LOI=0%)

 with no free lime 100

Potential SiO 2 Clin ker  SiO 2 ki ln feed .
100  LOI ki ln feed


 With the clinker free lime and SO3t (Kiln feed + combustible effect)

C 3S  4.07.C  7.6.S  6.72. A  1.43.F

 Bogue

C (1)  C  FCaO  0.7.SO3  1.26CO 2

C 3S  4.07.C (1)  7.6.S  6.72. A  1.43.F

Process Engineering Program – Raw Mix Optimization November 2004 22

 Clinker C3S (Example)

Kiln Feed "Potential Clinker" "Bogue clinker" Real Clinker

SiO2 13.49 20.94 20.94 20.69
Al2O3 3.30 5.13 5.13 5.24
Fe2O3 2.21 3.43 3.43 4.09
CaO 41.28 64.08 64.08 64.28
LOI 35.58 0.00 0.00 0.17
CaO(1) - 64.08 61.89 62.08
C3S - 62.28 53.35 54.43
Alite - - - 63.40
FCaO - 0.00 0.71 0.71
SO3 T. - - 2.12 2.12
LSF 95.62 95.62 95.62 96.13
SiR 2.45 2.45 2.45 2.22
AR 1.50 1.50 1.50 1.28

Process Engineering Program – Raw Mix Optimization November 2004 23

 Clinker Alite and C3S

C3S Bogue
C3S and Alite % in Clinker Alite

90.0

80.0

70.0

60.0

50.0
%

40.0

30.0

20.0

10.0

0.0

Works

Process Engineering Program – Raw Mix Optimization November 2004 24

 Clinker C3S Optimisation
CaO  3 * SiO 2  CaO ,3 SiO 2( orC 3 S )
 Get the maximum proportion of C3S with a raw material blend containing CaO
associated with SiO2, Al2O3, Fe2O3 :

CaO (1) + CaO(2) + CaO(3)

Fe2O3 C4AF : 0.35xFe2O3

Al2O3 C3A : 1.65xAl2O3

SiO2 C3S : 2.8xSiO2

CaOth= 2.8xSiO2+1.65*Al2O3+0.35*Fe2O3

Process Engineering Program – Raw Mix Optimization November 2004 25

 Clinker C3S Optimisation
 Assumptions : Input alkalies, Sulfur, Magnesia and iron %
 Step 1. Set desired A/F ratio Oxides
EqNa2O
%
0.6

Calculate Al2O3 SO3
MgO
0.4
2.3
 Step 2. Set desired SR ratio Fe2O3 3.15


Calculate SiO2 A/F 1.77590562

 Step 3. Set desired LSF Al2O3 5.59410269


Calculate CaO SR 2.48560919

 Step 4. Check Sum total all oxides SiO2 21.734422

 Step 5. Check Potential Clinker LSF 95.1234344


C3S CaO 66.22

C3A Sum 100

C2S Sum 100.00

C4AF Compounds Potential Adjusted Target
C3S 62.24 55.00 55
C3A 9.50 9.50 9.5
C2S 15.38 20.84
C4AF 9.58 9.58
Free Lime - 1.50

Process Engineering Program – Raw Mix Optimization November 2004 26

 Clinker Alkalies
Alkalies are important constituents of the clinker.The regularity is getting
more and more important. The values are between 0.3% to 1%. Effect on
Liquid Phase.
N° 7 and 10 Rules of the « 10 basic Facts on Clinker »

• Alkalies, whatever their form, are never favorable to 28-day

compressive strength.
Key figures :
+ 0.1 % Eq Na2O total  -1 N/mm2 @ 28 days

• If clinker SO3 is increased beyond the molar saturation of alkalies, an

increase in both clinker fineness and grinding energy is noted.
Key figures :
+1% Excess SO3 --> + 5 kWh/t @ 350 m2/kg
excess SO3 = SO3 clinker - 1,29 (% Eq. Na2O total)
Process Engineering Program – Raw Mix Optimization November 2004 27
 EqNa2O and SO3 (Example)

Kiln Feed "Potential Clinker" "Bogue clinker" Real Clinker

SiO2 13.49 20.94 20.94 20.69
Al2O3 3.30 5.13 5.13 5.24
Fe2O3 2.21 3.43 3.43 4.09
CaO 41.28 64.08 64.08 64.28
LOI 35.58 0.00 0.00 0.17
SO3 total 1.79 2.78 2.12 2.12
Na2O total 0.03 0.05 0.05 0.07
K2O total 0.33 0.51 0.51 0.49
Eq Na2O 0.25 0.38 0.38 0.39
SO3/EqNa2O 5.61 5.61 4.28 4.19
Na2O Soluble 0.03
K2O Soluble 0.40
Pyritic SO3 0.47 0.74

Process Engineering Program – Raw Mix Optimization November 2004 28

 Clinker EqNa2O (typical values)

Alkalies eqNa2O in Clinker

1.20

1.00
E q N a 2 O in C lin k e r

0.80

0.60

0.40

0.20

0.00

Works

Process Engineering Program – Raw Mix Optimization November 2004 29

 Clinker SO3% (typical values)

SO3t % , Clinker

3.00

2.50

2.00
SO3

1.50

1.00

0.50

0.00

Works

Process Engineering Program – Raw Mix Optimization November 2004 30

 Clinker C3A and Alkalies
C3A is an important phase of the clinker for the obtention
of the liquid phase. It interacts with sulfate addition and
early performances. The values are between 2% to 12%.

8th and 9th Rules of the « 10 basic Facts on Clinker »

• At optimum sulfate addition for early ages, soluble alkalies,
especially alkali sulfates, improve early strength. It is function of
the C3A %.
Key figures :
+ 0.1 % Eq. Na2O soluble --> + 0.5 à 1.5 N/mm2 @1 day
• The molar saturation of alkalies by SO3 in the clinker facilitates
workability control. If there is more alkalies than sulftates the
C3A form is transformed from cubic to orthrhombic. Then there
is a risk of poor workability and ageing.

Process Engineering Program – Raw Mix Optimization November 2004 31

 Clinker C3A (Bogue calculation)

C3A % can be estimated as a pure C3A with the following formulas

 From a kiln feed analysis, the chemistry has to be transformed to a clinker analysis (LOI=0%)
100
SiO 2 Clin ker  SiO 2 ki ln feed .
 with no free lime 100  LOI ki ln feed
 Potential

 Bogue C 3 A  2.65.C  1.69.F

C 3 A  2.65.C  1.69.F

Process Engineering Program – Raw Mix Optimization November 2004 32

 Clinker C3A (Example)

Kiln Feed "Potential Clinker" "Bogue clinker" Real Clinker

SiO2 13.49 20.94 20.94 20.69
Al2O3 3.30 5.13 5.13 5.24
Fe2O3 2.21 3.43 3.43 4.09
CaO 41.28 64.08 64.08 64.28
LOI 35.58 0.00 0.00 0.17
CaO(1) - 64.08 61.89 62.08
C3A - 7.80 7.80 6.96
Rietveld - - - 2.40
FCaO - 0.00 0.71 0.71
SO3 T. - - 2.12 2.12
LSF 95.62 95.62 95.62 96.13
SiR 2.45 2.45 2.45 2.22
AR 1.50 1.50 1.50 1.28

Process Engineering Program – Raw Mix Optimization November 2004 33

 Clinker C3A

C3A Bogue
Bogue C3A and Rietveld C3A % in Clinker C3A tot

14.0

12.0

10.0

8.0
%

6.0

4.0

2.0

0.0

Works

Process Engineering Program – Raw Mix Optimization November 2004 34

 Liquid Phase : LP

 Formula : Al2O3 and Fe2O3 are the main constituents.

@ T  1450 C ; LP  3.0 Al 2 O 3  2.25 Fe 2 O 3  MgO  Na 2 O  K 20

 Optimum : 25%. Viscosity is crucial.
 Too low (<20%)  Too low (>30%)
Hard burning Easy burning
No coating Too much Coating
Risk of brick damage Risk of brick damage
 Other temperatures (T=1338°C and T=1400°C)

Process Engineering Program – Raw Mix Optimization November 2004 35

 Liquid Phase (Example)

Kiln Feed "Potential Clinker" Real Clinker

Al2O3 3.30 5.12 5.24
Fe2O3 2.21 3.43 4.09
MgO 1.69 2.62 3.12
Na2O 0.03 0.05 0.07
K2O 0.33 0.51 0.49
LOI 35.58 0.00 0.17
LP @ 1450°C - 26.27 28.60
LP @ 1338°C - 27.01 28.63
AR 1.49 1.49 1.28

Process Engineering Program – Raw Mix Optimization November 2004 36

 Clinker LP (typical values)

Liquid Phase (@1450°C), Clinker

31.00

29.00

27.00

25.00
LP

23.00

21.00

19.00

17.00

15.00

Works

Process Engineering Program – Raw Mix Optimization November 2004 37

 Clinker Free lime

Kiln feed LSF target below stoechiometric ratio to minimise

clinker free lime. It is the main production parameter to
operate the kiln.
4th Rule of the « 10 basic Facts on Clinker »
Increasing the clinker free lime content reduces both initial
and final setting times in the same proportion.
Key figures :
When free CaO increases from 0.5 to 1.5%, initial set
decreases by about 40 to 50 minutes. This impact may vary
greatly from clinker to clinker (-10 to -100 minutes).

Process Engineering Program – Raw Mix Optimization November 2004 38

 Clinker C2S (belite)

Belite is the second phase which gives long term strength.

The values are between 58% to 72%.

6th Rule of the « 10 basic Facts on Clinker »

For a given Blaine specific surface (SSB), grinding energy
increases with C2S content. Conversely, it decreases with
increasing C3S.

Key figures :
+10% C2S, (or -10% C3S) => +5 kWh/t (@ 3500 cm2/g).
0% C2S, (or -10% C3S) => +5 kWh/t (@ 3500 cm2/g).

Process Engineering Program – Raw Mix Optimization November 2004 39

 Clinker Belite and C2S

Bélite
C2S % in Clinker C2S Bogue

35.0

30.0

25.0

20.0
%

15.0

10.0

5.0

0.0

Works

Process Engineering Program – Raw Mix Optimization November 2004 40

 Clinker C4AF and Color

C4AF is an important phase of the clinker for the obtention

of the liquid phase. It is linked to the color through the iron
addition. The values are between % to %.

No Rules of the « 10 basic Facts on Clinker »

Process Engineering Program – Raw Mix Optimization November 2004 41

 Clinker C4AF

C4AF Bogue
C4AF % in Clinker C4AF

16,0

14,0

12,0

10,0

8,0
%

6,0

4,0

2,0

0,0

Works

Process Engineering Program – Raw Mix Optimization November 2004 42

 Conclusion

 Raw mix control is key on clinker properties

 Minor elements are getting more and more

important to customer (alkalies, MgO, chlorine,
LOI…). Standards have to be met and regularity is
crucial for good relationship with the customer.

Process Engineering Program – Raw Mix Optimization November 2004 43