CEMENT CENTRE TECHNIQUE EUROPE CENTRALE

Day 1 PE Pyroprocessing II
10 rules for clinker quality

A.DEMIRTAS June 2005

PE Pyroprocessing II Training

PE Pyroprocessing II Training

FIRST RULE

Reducing raw mix rejects lowers burning temperature and grinding energy. This is particularly the case with siliceous rejects.
This action is also beneficial to strength properties.

Key Figures:
When the amount of 100 m rejects is reduced from 20 to 10% the global raw mix cement energy consumption is lowered by about 4 kWh per ton of cement at a fineness of 350 m/kg.

Fuel saving for burning & Decrease cement specific griding energy
3

PE Pyroprocessing II Training

Finer raw mix = Saving kW at finish grinding

Month

Raw mix
>100m >200m Blaine t/h mill

CPA HPR
R1 R2 R28

February March April - May

20.0 13.0 13.0

2.0 0.8 0.8

3850 3850 3680

49.0 52.5 55.5

22.5 24.0 22.6

35.7 37.0 37.0

70.0 71.0 70.0

Contes

PE Pyroprocessing II Training

SECOND RULE

Short burning zone promote grindability and strength development.

Key Figures:
The optimum is achieved when the kiln couple is at minimum compatible with steady operations.

Decrease cement specific griding energy

PE Pyroprocessing II Training

Shorter burning zone: better grindability

Grindability and burning zone length

500
450 400 350 300 250 200
30/05/1995 04:00 30/05/1995 12:00 30/05/1995 20:00 31/05/1995 04:00 31/05/1995 12:00

80

Grindability increase

75 70 65

Kiln Amps

Kiln amps decrease

60 55 50

Le Teil
6

PE Pyroprocessing II Training

THIRD RULE

Steady production requires an oxidizing atmosphere because a reducing atmosphere increases volatilization, causing both "cyclical" operations and sulfate and alkali fluctuations, hence producing an irregular clinker.

Stable kiln operation decrease builds-up Uform cement quality

7

PE Pyroprocessing II Training

Reducing atmosphere: enhance volatilization

Combustible

Oxygne kiln outlet (%)

1.8 2.4 1.1 2.1

v SO3 (%)
47.1 59.6 83 67

Clinker SO3 (%)

1.39 1.6 1.2 1.96

Clinker K2O (%)

0.94 1.04 0.98 1.15

Emission SO2 ppmV

2 7 1278 200

Fuel oil 100% Coke 23.8% Coke 47.7% Coke 47.7%

Stack emission in Saint-Constant

Oxydising atmosphere: drop in dust wasting

O2 Kiln outlet (%) Volatilization SO3 (%)

1.9 78 90

3.2

4 32

40

Dust emission ( t/j )

Brookfield Kiln 1

PE Pyroprocessing II Training

FOURTH RULE

Increasing the clinker free lime content reduces both initial and final setting times in the same proportion. Adding lime also accelerates both initial and final setting times.

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). Lime quality (specifically the burning temperature, its hydration level, etc.) and clinker quality have an influence on the results obtained.

Customer satisfaction

PE Pyroprocessing II Training

Free lime and setting time reduction

Initial setting time (mortar)
( min. )

180 160 140 120

100
0.2 0.4 0.6 0.8 1 1.2 1.4 Chaux libre clinker

1.6

St Constant

10

PE Pyroprocessing II Training

Limestone injection at the cooler

Normal +5% Ash Limestone 1 2

Free lime
Blaine Setting time (mn) Strength EN (MPa) Steam cured 80C (MPa)

% cm2 /g initial final 1d 28d 2h30 5h30

1,10
4320 175 245 24,7 69,1 0,5 24,1

2,10
4480 110 180 25,3 67,2 3,8 29,4

2,90
4600 110 170 24,5 66,9 6,0 25,3

2,50
4420 135 255 24,0 67,2 3,8 26,7

Val d'Azergues

11

PE Pyroprocessing II Training

FIFTH RULE

Increasing clinker C3S (to the detriment of C2S) improves strength at 1, 2, 3 and 7 days. After 28 days, the gain may be less because of the C2S contribution.

Key Figures:
+10% C3S +2 to 5 MPa for early strength

Customer satisfaction

12

PE Pyroprocessing II Training

Strength = f (C3S)
60.0 55.0 50.0 45.0

R-28d R-7d

y = 0.4166 x + 32.24 r2 = 0.3117 y = 0.5471x + 15.509 r2 = 0.5785 y = 0.5816x + 1.4245 r2 = 0.6671

N/mm 2

40.0 35.0

R-2d R-1d

30.0
25.0 20.0 15.0 45.0 50.0 55.0 60.0
y = 0.4495x - 2.5851 r2 = 0.4284

C3 S
- Lab grinding - Constant sulfates
Villaluenga

13

PE Pyroprocessing II Training

SIXTH RULE
A "Hard" to grind:

C 2S
+ 10 % C2S

+ 4 kWh/t
( @ 350 m2/kg )

Increase cement specific griding energy

14

PE Pyroprocessing II Training

Karsdorf
KST = 90/92 % C3 S 45 KST = 96/98 55 15 41 D +10

% C2 S
KWh/t BB10 @ 3500 SSB

25
45

-10
-4

MPa

KST = 90
60 50 40 30 24.5 23.5 20 17.3 14.5 10 8.8 9 0 43 41 56 60 54 50 40 SO3 = 2.3 30 SO3 = 2.9 26.5 18.2 20 17.8 11 10 9.8 0 30 44 40

KST = 98
54 50

10

Days

20

30

10

Days

20

30

Lab Cements from Karsdorf s clinkers

15

PE Pyroprocessing II Training

SEVENTH RULE

Alkalies, whatever their form, are never favorable to 28 day mechanical strength.

Key Figures:
+0.1% Eq Na2O total -1 N/mm at 28 days

Customer satisfaction & Increase cement specific griding energy

16

PE Pyroprocessing II Training

Influence of Total Alkalies on 28 day strength

70 65 28 -day Strength (MPa) 60 55 50 45

0.2

0.4

0.6

0.8

1.2

1.4

1.6

1.8

% Total Alcalies

17

PE Pyroprocessing II Training

EIGTH RULE

At optimum sulfate content at an early age, soluble alkalies, especially alkali sulfates, improve early strength.

Key Figures:
+0.1% Eq Na2O soluble +0.5 to 1.5 N/mm @ 1 day

Customer satisfaction

18

PE Pyroprocessing II Training

ALKALIES
Moles 1 K2O + 1 SO3

SULFATES

1 K2SO4

SOLUBLE

These soluble alkalies are

Beneficial
for the 1 and 2 days strength
19

PE Pyroprocessing II Training

Sulfates increase
- Addition in the raw meal
Plant Ranteil Ste As is Gypsum addition As is Gypsum addition % SO3 Clinker 0.2 1.1 0.1 1.3 % K2O Tot 1.15 1.15 0.6 0.6 %Na2O Tot 0.1 0.1 0.2 0.2 SSB (m2/kg) 400 375 402 413 1D (MPa) 11.5 18.0 11.5 17.0

- Increase of fuel sulfur

Plant Martres La Malle Gaz % SO3 Clinker 0.20 % K2O Total 0.40 0.95 % Na2O Total 0.06 0.10 SSB (m2/kg) 370 1D str 12.5

Fuel oil
Fuel BTS Fuel HTS

1.00
0.60 1.00

350
360 340

15.5
18.0 21.0

20

PE Pyroprocessing II Training

NINTH RULE
ALKALIES and C3A
Change of the crystal form of
CUBIC

C3 A

ORTHORHOMBIC

Worse burnability Workability problems Sensitivity to aging Customer satisfaction Drop in 28-days strength
21

PE Pyroprocessing II Training

More alkalies than sulfates

The excess of alkalies goes

in crystals

Na2O + C3A

NC8A3

K2O + C2S

KC23S12

These alkalies, in conjunction with soluble alkalies contribute to a reduction of 28 days strength

22

PE Pyroprocessing II Training

Gypsum addition in raw meal (lab test)

% cru % gypsum Clinker as is 100 0 Gypsum addition 1 97,95 2,05 Gypsum addition 2 96,0 3,95 SO3 kk 0,35 1,40 2,40 SSB 2 ( cm / g ) 3830 3770 3920 SO3 cem. 2,0 2,50 2,90 W/C 28,6 26,0 26,2 Fluidity (%) 88 112 125 1day str MPa 6,5 10,5 12,5

Cristal form As is Gypsed raw mix

C3A

Orthorhombic ( alkalies in cristal ) Cubic ( pure )

Ranteil
23

PE Pyroprocessing II Training

Gypsum addition in raw meal (industrial tests)

SO3kk K20 tot. Na2O tot. SO3 SSB Refus(mm)
Aprs 2 Aprs 30

R 1j
MPa

As is Cement (gypsed kk)

0,1 2,9

0,37 0,56

0,10 0,09

2,80 2,90

3510 3500

14 10

29 19

11,5 16,0

Ste

24

PE Pyroprocessing II Training

TENTH RULE
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 to 350 m/kg excess SO3 = SO3 clinker -1.29 (% Eq. Na2O total)

Kiln stability & Increase cement specific griding energy

25

PE Pyroprocessing II Training

Excess of Sulfates * Finish grind kW increase

coke coal fuel SO3 kk F2 1994 1995 47,37 74,14 51,01 21,30 4,62 3,56 0,45 0,95 F3 0,75 1,18 ~ 0,35 ~ 0,35 #0 #0 1,222 1,237 K2OT Na2OT C/K Mill kW CPJ 45 38,52 40,29

Mekns SO3kk
Industriels tests kk normal Kk (gypsed) Lab.tests kk normal kk (gypsed)

K2OT

Na2OT

SO3cim

Prod

SSB # of mill rev

0,1 2,9 0,1 2,9

0,37 0,56 0,37 0,56

0,10 0,09 0,10 0,09

2,8 2,9 -

21 t/h 17 t/h -

3150 2700 2880 2580

2000 2000

Ste

26

PE Pyroprocessing II Training

Excess of Sulfates * Finish grind kW increase

1991 SO3 kk 0,80 1992 1,45

K2 O

0,89

0,92

Production t / h (B0) CPA 55 (B3) CPA 55 21,6 19,3 20,3 18,2

(B3) CPA HPR

14,2

13,2

La Couronne
27

PE Pyroprocessing II Training

Excess of Sulfates * Finish grind kW increase

4800 4600

Number of turns BB10

4400 4200 4000 3800 3600 3400 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6

y = 1008 x + 3255
R 2 = 0.66

SO3 Clinker

(to reach 350 m2 / kg )

Cantagalo

28

PE Pyroprocessing II Training

Examples

29

CEMENT CENTRE TECHNIQUE EUROPE CENTRALE

Materials for building our world