10

Basic
facts
 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 100µm rejects is reduced from
20 to 10%, the global raw mix cement energy consumption
is lowered by about 4 kWh per tonne of cement at a
fineness of 350 m2/kg.
Grind the raw mix finer

You will save on

• Fuel at burning
• kW at finish grinding
 Finer raw mix = Fuel saving
58.5
Oil
58
(l/t Raw mix)

57.5

57

56.5

56

>100mm residue (%)

55.5
8 12 16 20

CONTES
 Finer raw mix = Fuel saving
8.00
% free CaO
Raw mix
15%>100µm - Industrial as is
6.00
5%>100 µm - lab grinding of residue

5%>100 µ m - complete grinding

4.00

2.00

temperature °C
0.00
1400 1450 1500 1550 1600

MARTRES raw mix ( Lab )

 Finer raw mix = Fuel saving
8.00
% free CaO

6.00

Raw mix

16% > 100mm industrial as is

4.00
8% > 100mm lab re grind

2.00

temperature °C
0.00
1350 1400 1450 1500 1550 1600

KARSDORF raw mix ( Lab )

 Finer raw mix = kw at raw mill
25
kWh/t
y = - 0.42 x + 29.7
y = -0.4267x + 29.759
24 r2 = 0.91

23

22

21

% > 100 µm residue

20
12 14 16 18 20 22

LEXOS raw mix

 Finer raw mix = kW savings at finish grinding
75

kWh/t
y = 1.38 x + 37.8
70
r2 = 0,58

65

60

% > 100 µm residue

55
12 14 16 18 20 22

CPA HPR LEXOS

 Finer raw mix = kW savings at finish
grinding

Raw CPA HPR

Month >100mm >200mm Blaine t/h 1d 2d 28d
cm2/g mill MPa MPa MPa

February 20.0 2.0 3850 49.0 22.5 35.7 70.0

March 13.0 0.8 3850 52.5 24.0 37.0 71.0
April - May 13.0 0.8 3680 55.5 22.6 37.0 70.0

CONTES
 Second rule
A short profile promotes grindability and strength
development.

Key Figures :
The optimum is achieved when the kiln torque is at the minimum
value compatible with stable kiln operation.
A hot and short burning
zone

Gives easy grinding

clinker
 Shorter burning zone: better grindability
Grindability and cooling zone temperature
kWh / t
75

70

65

60

55

50

45
°C
1050 1100 1150 1200 1250 1300 1350 1400 1450
Cooling zone temperature

Port la Nouvelle
 Shorter burning zone: better grindability
Grindability and burning zone length (kiln torque)

75

70

65
BB10 (kWh/t)

60

55

50

45 Nm
600 700 800 900 1000 1100 1200 1300 1400 1500

Kiln drive torque

Port la Nouvelle
 Shorter burning zone: better grindability
Grindability and burning zone length

500 80

450 Grindability 75
improvement
400 70
Kiln Amps

350 65

300 60
Kiln amps decrease
250 55

200 50
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

Le TEIL
 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.
 Give the kiln a breath of fresh
air
A big reduction in volatilization
With, in addition,

* Steady kiln operation

* Stable clinker quality

 Reducing atmosphere : increased volatilization

Kiln exit
Fuel
oxygen (%) v SO3 Clinker Clinker Emissions Emissions
(%) SO3 (%) K2O (%) SO2 ppmV SO3 ppmV
Fuel oil 100% 1.8 47.1 1.39 0.94 2 25
Coke 23.8% 2.4 59.6 1.6 1.04 7 19
Coke 47.7% 1.1 83 1.2 0.98 1278 43
Coke 47.7% 2.1 67 1.96 1.15 200 58

Stack emission in Saint-Constant

Oxydizing atmosphere : drop in dust wasting

Kiln exit oxygen (%) 1.9 3.2 4

Volatilization SO3 (%) 78 - 32
Dust wasting ( t/d) 90 40 -
Brookfield Kiln 1
 Oxygen and Sulfates Volatility
% SO C4 C4
%3 SO3
%
%O 2 Preheater
O2 sortie tourexit %%
SOSO3
3 Clinker
clinker

5,5 4,5

5
3,5

3
4,5 % OO2
2 preheater
sortie tourexit
2,5 % SO 3 C4
SO3 C4
% SO 3 Clinker
SO3 KK
2
4
1,5

1
3,5

0,5

3 0
17/sep 17/sep 17/sep 17/sep 18/sep 18/sep 18/sep 18/sep 18/sep 18/sep
09:00 13:00 17:00 21:00 01:00 05:00 09:00 13:00 17:00 21:00

Le TEIL
 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 degree of
hydration etc.) and clinker quality have an influence on the results
obtained.
Add a pinch of free-lime ...

Your clinker
will be
QUICKER
( Shorter initial setting time )
 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 1.6
Clinker free lime

St CONSTANT
 Limestone injection BATH kiln outlet
Sample SSB CaO l Setting Setting Setting Setting Setting Setting Setting
(m2 / (%) time 23ºC time time time time time
kg) time 23ºC (CTS) Concrete Concrete Concrete Concrete Concrete
(plant) (h:min) 24ºC / 10ºC / 24ºC 10ºC
2%CaCl 2 2%CaCl 2
Reference 360 0.35 165 180 5:45 3:30 4:45 5:10 8:30

Test 1 357 0.7 125 110 4:55

Test 2 371 0.9 120 115 4:40 3:10 4:25 4:30 7:15

Limestone injection WOODSTOCK kiln outlet

- Same objective, same test but less impact
- Clinker chemistry?
 Limestone injection at the cooler

Normal +5% Limestone

Ash 1 2
Free lime % 1,10 2,10 2,90 2,50
Blaine cm2 /g 4320 4480 4600 4420
Setting time initial 175 110 110 135
(min) final 245 180 170 255
Strength EN 1d 24,7 25,3 24,5 24,0
(MPa) 28d 69,1 67,2 66,9 67,2
Heated concrete 2h30 0,5 3,8 6,0 3,8
80°C (MPa) 5h30 24,1 29,4 25,3 26,7

Val d' Azergues

 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 strengths
 GAIN STRENGTH
at 2,7,28 days

Increase C3S by 10 % *
+ 2 to 5 MPa
( * -10% of C2S )
 Strengths = f(C3S)

60.0 y = 0.42 x + 32.24

28d r2 = 0.31
55.0
50.0 y = 0.55 + 15.51
45.0 7d r2 = 0.58
N/mm 2

40.0
y = 0.58x + 1.42
35.0 r2 = 0.67
2d
30.0
25.0 y = 0.45x - 2.59
1d r2 = 0.43
20.0
15.0
45.0 50.0 55.0 60.0

C3 S

- Lab grinding
Villaluenga - Constant total sulfates
 Strengths = f(C3S)
(Villaluenga f1501)

60.00
y = 0.59x + 20.84
55.00 r 2 = 0.59
50.00 28d
45.00 y = 0.68x + 5.61
r 2 = 0.66
N/mm 2

40.00 7d
35.00
y = 0.54x + 0.771
30.00 2d r 2 = 0.59
25.00
y = 0.28x + 4.88
20.00 r 2 = 0.22
1d
15.00
50.0 55.0 60.0 65.0

C3 S

Slight increase in 1 day strength

 WHITEHALL
40

35

30 1 d
3 d
25 7 d
28 d
MPa

20

15

10

0
10 20 30 40 50 60
C3 S

- Industrial clinker
- Lab grinding, constant sulfates
 Sixth Rule
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).
A " tough one " to grind :

C 2S

+ 10 % C2S + 5 kWh/t
( @ 350 m2/kg )
 Grindability = f( chemistry)
% January 1997 February 1997 D Feb. - Jan.
LSF Clinker 94,50 98,60 + 4,10
C3 S 56 64 +8
C2 S 22 15 -7
C3 A 10,20 9,60 =
C4 A F 8,20 8,00 =
Free CaO 1,27 1,30 =

kWh/t BB10 46,70 44,40 - 2,30

SSB BB10 ( cm2/g ) 3680 3710 =
kWh/t Industrial 53,10 51,60 - 1,50
28 d. Industrial 32,0 35,5 + 3,5
(ASTM standards)

OCUMARE
 KARSDORF
KST = 90/92 KST = 96/98 D
% C3 S 45 55 -10
% C2 S 25 15 +10
KWh/t BB10 @ 3500 SSB 45 41 +4

MPa
KST = 90 KST = 98
60 56 60
54 54
50 50 44 50
43
40 41 40 40
30
30 24.5 SO3 = 2.3 30
SO3 = 2.9 26.5
23.5 18.2
20 17.3 20
17.8
14.5 11
10 8.8 9 10 9.8

0 0
0 10 Days 20 30 0 10 Days 20 30

Lab Cements from Karsdorf ‘ s clinkers

 Seventh rule
Alkalies, whatever their form, are never favorable to 28-day
compressive strength.

Key figures :
+ 0.1 % Eq Na2O total  -1 N/mm2 at 28 days
 A pinch of alkalies
and...

...STRENGTH FALLS

@ 28 days
+ 0,1 % alkalies -1,3 MPa
 Influence of Total Alkalies
on 28-day strength
70

65
28 -day Strength (MPa)

60

55

50

45
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2
% Total Alkalies
 Strength = f (alkalies)
80
80 Rc M P a 282d8 j
Rc M P a R
R 28j

70
70
282d8 +
R j +K2O
K2O
R 28j + K2O

60
60
7d7+j +K2O
R K2O
R 7j + K2O

50
50

R 77dj
R 7j
40
40

2 RdR+
2 j K2O
+ K2O
2j + K2O
30
30

R 22dj
R 2j
20
20

1d+K2O
R 1j + K2O
10 R 1j + K2O
10

0 1 Rd 1 j
% C3S 6 56 5
0 R 1j
25 30 35 40 45 50 55 60
25 30 35 40 45 50 55 60
 Eighth rule
At optimum sulfate addition for early ages, soluble alkalies,
especially alkali sulfates, improve early strength.

Key figures :
+ 0.1 % Eq. Na2O soluble --> + 0.5 à 1.5 N/mm2 @1 day
ALKALIES SULFATES

Moles
1 K2O + 1 SO3 1 K2SO4 SOLUBLE
1 Na2O + 1 SO3 1 Na2SO4 SOLUBLE
These Soluble alkalies are

Beneficial
for à 1, 2 day strength
 Sulfate increase
- Addition in the raw meal
Plant % SO3 Clinker % K2O %Na2O SSB (m2/kg) 1d (MPa)
Total Total
Ranteil As is 0.2 1.15 0.1 400 11.5
Gypsum addition 1.1 1.15 0.1 375 18.0
Sète As is 0.1 0.6 0.2 402 11.5
Gypsum addition 1.3 0.6 0.2 413 17.0

- Increase of fuel sulfur

Plant % SO3 Clinker % K2O Total % Na2O Total SSB (m2/kg) 1d (MPa)
Martres Gaz 0.20 0.40 0.06 370 12.5
Fuel oil 1.00 350 15.5
La Malle low-s oil 0.60 0.95 0.10 360 18.0
Hi-s oil 1.00 340 21.0
 Alkalie increase
- Lab addition
term As is 1.85 % K 2 SO 4 clinker 1.85% K 2 SO 4 cement
1 day 20.3 28.1 28.2
7 days 54.3 53.0 53.8
28 days 74.3 66.2 66.3

- Raw mix change

RM eq
Cru NaNa
2O2O==0.45
0.45 %
% RM eq
Cru NaNa
2O2O==0.3
0.3 %
%
Mesured
Measured Calculated at Mesurées
Measured Calculated at
(addition16
(addition %)
16%) 0% addition 1 (addition 20
(addition %)
20%) 0% addition
1 day 17.1 +/- 0.1 21.1 +/- 0.1 13.9 +/-0.12 18.5 +/-0.12
28 days 46.8 +/-0.19 57.8 +/-0.19 47 +/-0.23 62.7 +/-0.23
Number of tests 143 100

( 1 ) FERRET formula
 Ninth rule
The molar saturation of alkalies by SO3 in the clinker
facilitates workability control
 …More alkalies than sulfates
The excess of alkalies goes to
crystal structures

Na2O and C3A NC8A3

K2O and C2S KC23S12

These alkalies, in conjunction with

soluble alkalies contribute to a
reduction in 28 days strength
 ALKALIES and C3A
Change of the crystal form of C3A
CUBIC ORTHORHOMBIC

• Poorer burnability
• Workability problems
• Sensitivity to aging
• Drop in 28-day strength
 Gypsum addition in raw meal (lab test)

% raw mix SSB Fluidity 1d

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

Crystal form C3A

As is Orthorhombic ( alkalies in crystal )

Sulf. raw mix Cubic ( pure )

RANTEIL
 Gypsum addition in raw mix ( Industrial tests)

SO3kk K20 tot. Na2O tot. SO3 SSB Résidue17(mm) 1d

(cm²/g) after 2 min after 30 min MPa

As is 0,1 0,37 0,10 2,80 3510 14 29 11,5

Cement (sulfated kk) 2,9 0,56 0,09 2,90 3500 10 19 16,0

SÈTE
 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 @ 350 m2/kg
excess SO3 = SO3 clinker - 1,29 (% Eq. Na2O total)
 …If

SO3 > Na2O , K2O

* Fine clinker
* Increased kW at finish mill

+ 1% Excess SO3 + 5 kWh / t

( @ 350 m2 / kg )
 EXCESS of Sulfates
* FINER Clinker

100

80
% passing

60 0,1 % S03

40 1,3 % SO3

20

0
0 5 10 15 20 25
mm

RANTEIL 72 - 73
 EXCESS of Sulfates
* Finer Clinker
100

80
% passing

60
0,1 % SO3
40 2,9 % SO3

20

0
0 5 10 15 20 25 30 35
mm

100

80

60
% passing

0,1 % SO3
40 1,2 % SO3

20

0
0 10 20 30 40 50 60
SÈTE
mm
1971
 EXCESS of Sulfates
* Finish grind kW increase
MEKNÈS
coke coal fuel SO3 kk K2OT Na2OT C/K Mill kW
F2 F3 CPJ 45

1994 47,37 51,01 4,62 0,45 0,75 ~ 0,35 #0 1,222 38,52

1995 74,14 21,30 3,56 0,95 1,18 ~ 0,35 #0 1,237 40,29

SO3 kk K2OT Na2OT SO3 cem Prod. SSB # of mill rev

t/h cm²/g
Industrial tests
kk normal 0,1 0,37 0,10 2,8 21 3150 -
kk sulfated 2,9 0,56 0,09 2,9 17 2700 -

Lab.tests
kk normal 0,1 0,37 0,10 - - 2880 2000
kk sulfated 2,9 0,56 0,09 - - 2580 2000
SÈTE
 EXCESS of Sulfates
* Finish grind kW increase

1991 1992

SO3 kk 0,80 1,45

K2 O 0,89 0,92

Production t / h

(B0) CPA 55 21,6 20,3

(B3) CPA 55 19,3 18,2

(B3) CPA HPR 14,2 13,2

La COURONNE
 EXCESS of Sulfates
* Finish grind kW increase

4800

4600

4400
rotations BB10

4200

4000

3800
y = 1008 x + 3255
r 2 = 0.66

3600

3400

0.2 0.4 0.6 0.8 1 1.2 1.4 1.6

SO3 kk

( to obtain 350 m2 / kg)

CANTAGALO