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CEMENT PROCESS ENGINEERING

VADE-MECUM

6. PYROPROCESSING

Rev. 2002

CEMENT PROCESS ENGINEERING


VADE-MECUM

SECTION 6 PYROPROCESSING

Table of Contents
1.
2.

3.

4.

5.

6.

7.

8.

9.
10.

Kiln Typical Values .............................................................................. 6.1


Quick Overview Kiln Exit Gas Calculation ......................................... 6.1
2.1 Calculation of Various Components .............................................. 6.1
2.2 Typical Fuels Composition............................................................ 6.2
2.3 Kiln Exit Gases for Different Fuels ............................................... 6.2
Pyroprocessing Reactions by Zone....................................................... 6.3
3.1 Evaporation Zone ......................................................................... 6.3
3.2 Dehydration Zone ......................................................................... 6.3
3.3 Decarbonation Zone...................................................................... 6.3
3.4 Clinkering Zone ............................................................................ 6.4
3.5 Cooling Zone................................................................................ 6.4
Cyclone................................................................................................. 6.4
4.1 Pressure Drop............................................................................... 6.4
4.2 Thermal Efficiency ....................................................................... 6.5
4.3 Trapping Efficiency ...................................................................... 6.5
4.4 Calculation of Material Flow ........................................................ 6.5
Chains................................................................................................... 6.5
5.1 Guideline...................................................................................... 6.5
5.2 Lafarge Corp Data........................................................................ 6.6
Cooler................................................................................................... 6.8
6.1 Compartments .............................................................................. 6.8
6.2 Fans ............................................................................................. 6.8
6.3 Cooler Efficiency Coefficients....................................................... 6.9
6.4 Typical Heat Balance Davenport Cooler...................................... 6.11
Kiln Heat Balance............................................................................... 6.12
7.1 Theoretical Heat for Clinker Formation ....................................... 6.12
7.2 Wall Losses ................................................................................ 6.12
7.3 Kiln Residence Time................................................................... 6.13
7.4 Water Spray ............................................................................... 6.15
7.5 Heat Balance Example................................................................ 6.15
Volatile ............................................................................................... 6.17
8.1 Properties of Volatile Elements ................................................... 6.17
8.2 Volatilization Process ................................................................. 6.19
8.3 SO2 - SO3.................................................................................. 6.20
8.4 Build-up and Rings ..................................................................... 6.22
8.5 Volatile Balance Example : Davenport 1997................................ 6.23
8.6 Circulation in Preheater (Port-la-Nouvelle).................................. 6.25
Lafarge Corp Typical Ratios ............................................................. 6.26
57 Clinker Reactivity Study (P. Barriac) ........................................... 6.27

Index - i
Rev. 2002

CEMENT PROCESS ENGINEERING


VADE-MECUM

SECTION 6 PYROPROCESSING

1. Kiln Typical Values


Process Type
Wet

Long Dry
<1000 T/D

Long Dry
>1000 T/D

0.6
0.5
8.1
1.3
0.1
37
0
1
12
231

0.9
0.7
113
1.8
0.12
38
0-20
1.4
15
123

0.6
0.7
108
2.2
0.12
37
25
1.4
20
96

0.6
0.7
104
1.7
0.06
33
25
1.5
22
102

1.9
1.8
132
2.3

2.3
2.6
166
2.3

2.9
3.1
172
2.3

17

15

13

2.5
32
24

3
32
17

3
40
15

1250
1.7
2.0
2.8

1000
1.2
1.4
1.8

950
1.1
1.4
1.7

4.0
1.22
4.2

0.1
2.5
1.30
4.7

0.1
2.4
1.30
4.3

900
1.0
1.3
1.4
1.4
0.2
2.3
1.37
3.9

800
0.9
N/A
1.2
1.3
0.2
2.1
1.39
4.4

775
0.7
N/A
1.0
1.2
0.2
1.9
1.39
4.3

750
0.3
N/A
0.5
1.1
0.2
1.8
1.50
2.2

2.0
3.0
14.0
10.0

12.0
2.0
29.0
11.6

12.0
2.0
27.0
12.2

33.0
36.0
1.0
1.0
100.0

41.8
1.2
1.5
0.9
100.0

44.0
1.3
1.6
0.0
100.0

12.0
2.0
25.0
10.0
1.0
46.4
1.3
1.7
0.6
100.0

15.0
2.0
20.0
6.0
2.0
52.3
1.5
1.9
-0.6
100.0

13.0
2.0
19.0
6.0
2.0
53.9
1.5
1.9
0.6
100.0

13.0
2.0
18.0
5.0
2.0
55.7
1.6
2.0
0.7
100.0

20

4
4

3.6

Units
Ratios to Kiln Dimensions
Production per unit volume
MTPD/m3
Production per unit brick surface
MTPD/m2
Production per unit BZ c/section
MTPD/m2
Kiln slope
degrees
Chain load
T/MTPD
Length/diameter
ratio
Enlarged section vs total length
percent
Kiln speed
rpm
Shell circumferential speed
m/min
Total material retention time
min
Fuel and Gas Flow
Specific heat consumption - base
kcal/kg
Burning zone gas flow
Nm3/kg
Calcining zone gas flow
Nm3/kg
Kiln exit gas flow
Nm3/kg
Preheater exit gas flow
Conditioning water flow
Nm3/kg
Stack gas flow @ 7% O2
Nm3/kg
Stack gas density
kg/Nm3
Burning zone thermal load
Gcal/m2/hr
Heat Outputs from Kiln/Cooler/Preheater
Cooler vent gas
%SHC
Solid fuel drying gas
%SHC
Kiln/preheater exhaust gas
%SHC
Shell radiation
%SHC
Preheater vessel radiation
%SHC
Heat of formation of clinker
%SHC
Drying of raw meal or slurry
%SHC
Clinker sensible heat exit cooler
%SHC
Unaccounted
Total
%SHC
Incremental loss per % dust wasted
Incremental loss per % bypass

kcal/kg
kcal/kg

1-stage
4-stage
4-stage
4-stage
Preheater Preheater Precal AT Precal AS

2. Quick Overview Kiln Exit Gas Calculation


2.1 Calculation of Various Components
a. CO2 from Calcination (LOI)
0.786 C + 1.092 M
LOI =
kg / kg dry RM
100
=

0.786 C + 1.092 M
100
*
kg / kgkk
100
100 LOI

Typical value:

0.533 kg/kgkk
0.35 kg/kg RM
0.272 Nm3/kgkk

b. H2O from Slurry Moisture


SM
H2O =
kg / kg dry RM
100 SM
SM
100
*
kg / kgkk
100 SM 100 LOI
Typical value:
0.865 kg/kgkk
1.08 Nm3/kgkk

6.1
Rev. 2002

CEMENT PROCESS ENGINEERING


VADE-MECUM

SECTION 6 PYROPROCESSING

d. Excess Air
KEGN * OXY
EA =
21 OXY

c. H2O from Water Spray


WS liters/kgkk = WS kg/kgkk

Typical value:

0.10 kg/kgkk
0.124 Nm3/kgkk

Typical value:

0.105*KEGN Nm3/kgkk

2.2 Typical Fuels Composition


Coal
C
H
O
S
Ash
LHV

Mass% (dry basis)


65.0
5.0
5.0
2.0
23.0
27214 MJ/t

Oil
C
H
O
S
N
LHV

Mass%
86.0
11.0
0.5
2.0
0.5
41320 MJ/t

Gas
CH4
C2H6
C3H8
N2
CO2
LHV

Volume%
97.25
0.98
0.03
1.33
0.4
35.51 MJ/Nm3

2.3 Kiln Exit Gases for Different Fuels


Coal
Preca
Long dry
Wet
Oil
Preca
Long dry
Wet
Natural Gas
Precal
Long dry
Wet

Nm3/kgkk
1.37
1.47
3.06

CO2
31
30
17

% volume
H2O
N2
5
61
6
61
39
42

CO2
30
29
16

% volume
H2O
N2
7
60
8
61
49
42

Nm3/kgkk
1.38
1.48
3.07
Nm3/kgkk
1.45
1.57
3.2

Oxygen vs. Excess Air


%O2 in KEG
Process
1.0
Precal
Long dry
Wet
2.0
Precal
Long dry
Wet
3.0
Precal
Long dry
Wet
4.0
Precal
Long dry
Wet

CO2
25
24
13

% volume
H2O
N2
13
59
14
59
44
41

O2
2.8
1.9
1.2

O2
2.8
1.8
1.2

O2
2.6
1.7
1.1

Excess at (% of neutral comb gas)


Coal
Oil
Gas
6.4
6.3
6.0
6.1
6.0
5.8
5.7
5.6
5.4
13.4
13.2
12.6
12.9
12.7
12.1
12.1
11.9
11.3
21.2
20.8
19.9
20.4
20.1
19.2
19.1
18.8
17.9
29.9
29.4
28.1
28.8
28.4
27.1
26.9
26.5
25.2

6.2
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CEMENT PROCESS ENGINEERING


VADE-MECUM

SECTION 6 PYROPROCESSING

3. Pyroprocessing Reactions by Zone1


100

80

60

40

20

00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00
00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00
00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00
00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00
00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00
H2O clays

masses

CO2

%
100

Ca CO3

Quartz

Quartz

CaO
C33S

60
C2S

40
20

Cristob.

Clays
0

200

80

Liqu.
400

Fe2O3

600

800

C2(A,F)

1000

C12A7

1200

C4AF

1400

T C

C 3A

3.1 Evaporation Zone

Between 100 and 400C: H2O (l) + heat H2O (g), H = 44.2 kJ/mol

3.2 Dehydration Zone


Between 350C and 650C
Clay starts to lose its water of crystallization:
2 SiO2 . Al 2 O3 . 2 H 2 O Heat 2 SiO 2 . Al 2 O3 + 2 H 2 O , H = + 202 kJ/mol
At 400C
Magnesium carbonates decomposition pressure reaches atmospheric pressure at this temperature:
MgCO3 + Heat MgO + CO2 , H = + 117 kJ/mol
Vaporization and oxidation of organic compounds and sulfides:
7
2 FeS 2 + O2 Fe2O3 + 4 SO3
2

At 550 C
CaCO3 starts to decompose at this temperature. However, acidic environment favours the deformation of the
molecules of CaCO3.

3.3 Decarbonation Zone


At 900C
This is the zone where CaCO3 decomposes rapidly into CaO and CO2 because of its decomposition pressure
at this temperature:
CaCO3 CaO + CO2 , H = + 178.2 kJ/mol

Much free lime is produced and starts to react:


2CaO + SiO 2 2CaO . SiO 2 , H = -125.9 kJ/mol
2CaO + Al 2 O3 2CaO . Al 2 O3 ,

1 Each enthalpy of reaction is given @25C, according to G.Seidel, H.Huckauf and J.Stark: Technologie des Bindebaustoffe Brennprozess und Brennanlagen

6.3
Rev. 2002

CEMENT PROCESS ENGINEERING


VADE-MECUM

SECTION 6 PYROPROCESSING

2CaO + Fe 2 O3 2CaO . Fe 2 O3 , H = -31 kJ/mol

Free CaO combines with SO3 to give anhydrite:


CaO + SO3 CaSO4
This anhydrite reacts with the alkalies from clay to give alkali sulphates:
CaSO4 + Na 2 O CaO + Na 2 SO4
CaSO4 + K 2 O CaO + K 2 SO4 or 3 K 2 SO4 . Na2 SO

The quantity of SO3 is generally insufficient to combine with the alkalies:


Na 2 O + C 3 A NaC 8 A3

K 2 O + C 2 S KC 23 S 12

3.4 Clinkering Zone


At 1200C
Belite ( C 2 S ) formation completed: 2CaO + SiO2 2CaO . SiO2 , H = -125.9 kJ/mol.
C12 A7 becomes enriched in lime and changes to C 3 A

C 2 A and C2 F form a solid solution : C4 AF , H = -50.4 kJ/mol


Between 1250C and 1450C
C 3 A and C4 AF liquefy and constitute the flux. C 2 S combines with free CaO to form C 3 S in the presence
of flux, forming nodules: CaO + C 2 S C 3 S , H = +8 kJ/mol.

The alkali sulfates decompose, liberating alkalies and SO2 :


R2 SO4 + Heat R 2 O + SO 2 + 1 / 2 O 2

Anhydrite decomposes into CaO and SO2 :


CaSO4 + Heat CaO + SO2 + 1 / 2 O2 , H = +490 kJ/mol.
Ferric oxide, in a reducing atmosphere, changes to ferrous oxide:
Fe 2 O3 2 FeO + 1 / 2 O2

3.5 Cooling Zone


At 1400C to 1250C,

The 1 form C 2 S crystallizes to the more hydrolizable C 2 S form.


The C 3 A and C 4 AF crystallize and finally the molten sulfates crystallize.

4. Cyclone
4.1 Pressure Drop

The Dp through a cyclone for a family of


similar cyclones:
Dp = cst r

Q2
D4

where:
- Dp is the pressure drop through the cyclone
- r is the fluid density
- Q is the gas flow
- D is the diameter of the cyclone

6.4
Rev. 2002

CEMENT PROCESS ENGINEERING


VADE-MECUM

SECTION 6 PYROPROCESSING

4.2 Thermal Efficiency

hth= 1

where:
- T go is the temperature of gas at cyclone outlet

T go Tmo
T go

T go is the temperature of material at cyclone discharge

A normal value for thermal cyclone efficiency is above 95%. This definition is commonly used but the name
"Thermal efficiency" can be considered misleading because the useful heat gained by the material at the
cyclone discharge is also related to the cyclone trapping efficiency.

4.3 Trapping Efficiency

Di Do
Di

where:
- Di is the dust load of gas at cyclone inlet
- Do is the dust load of gas at cyclone outlet
The current value for the trapping efficiency of the top cyclone is around 95%. It was commonly accepted in
the past that the bottom cyclones had a lower efficiency (75-85%) but series of measurements and tower
simulation showed a higher efficiency for these cyclones (around 90%).
ht =

4.4 Calculation of Material Flow

With the two following equations expressing


the total flow conservation and the tracer
flow (i.e. K2O), the recirculation level can be
assessed.
- Fkk + FKD = FKL + FCA
- Fkk K kk + FKD = FKL K kk + FCA KCA

where:
- FKD :
- FKL :
- Fkk :
- FCA :
- K kk :
- K KD :
- K KL :
- K CA :

The kiln dust flow (LOI=0)


The kiln load flow (LOI=0)
The clinker flow (LOI=0)
The coal ash flow (LOI=0)
Tracer concentration in clinker
Tracer concentration in kiln dust
Tracer concentration in kiln inlet
Tracer concentration in coal ash
(if ash has to be added)

5. Chains
5.1 Guideline
Zone
Free
Dust
Plastic

Preheat lower section

Preheat upper section

zone length (ratio to kiln diameter)


M2/m3
Chain length (% of kiln diameter)
zone length (ratio to kiln diameter)
M2/m3
Chain length (% of kiln diameter)
zone length (ratio to kiln diameter)
M2/m3
Chain length (% of kiln diameter)
zone length (ratio to kiln diameter)
M2/m3
Chain length (% of kiln diameter)

Target (wet)
1.0 to 1.5
11.0 to 15.0
<75%
1.0 to 4.0
5.0 to 8.0
60% to 70%
0.5 to 2.5
7.0 to 10.0
70%
0.5 to 2.5
6.0 to 8.5
70%

Dry kiln
1.0 to 1.5
11.0 to 15.0
<75%
N/A
N/A
N/A
0.5 to 2.5
7.0 to 10.0
70%
0.5 to 2.5
6.0 to 8.5
70%
6.5
Rev. 2002

CEMENT PROCESS ENGINEERING


VADE-MECUM

Zone
Radiation

SECTION 6 PYROPROCESSING

Target (wet)
1
8.5 to 11.0
70%
2.5-2.8
110-130
6-10
18-25%

zone length (ratio to kiln diameter)


M2/m3
Chain length (% of kiln diameter)

Global m2/mtpd
Global kg/mtpd
Global length
Global length

Ratio to kiln diameter


% kiln length

Dry kiln
1
8.5 to 11.0
70%
2.3 2.6
105-110
58
17 22%

(sources: Marc Brunelle)

Chain surface: 19m2/t for oval chains vs. 22-25 m2/t for round chains.
For small kilns, ratios are always lower than for larger kilns.
Ratios are higher for dry kiln compared to wet kiln.
Chainless sections are applied along chain zone aiming to:
- equalize gas temperatures
- serve as a buffer area to equalize varying rates of material transportation
- precipitate kiln dust
- allow for installation of thermocouples
Other Rules of Thumb
1500 m of installed chains reduces the exit chain gas temperature by 100oC.
A properly designed chain system can lower the SHC by 300 kcal/kg ck.
heat exchange rate: 8.75 kcal/h/m2/C.
pressure per one meter of chain: 1-2 mm H2O for curtain chain and 2-3 for Gartand chain (note: Garland
chains are abandoned due to practical considerations in maintaining hanging pattern).
For Gartand chain, the thermal effect is 1.5 time higher than curtain chain.
Wear rate: 80-120 g/t ck for wet kiln and 100-150 for dry kiln.

5.2 Lafarge Corp Data


Kiln
updated Feb 99
M.Brunelle (CTS)

Type

Impact Chain densities


Specific Area
plates
m2/m3
C1-C2
(less FE void)

Gross Area
m2/m3
C2
(plus all voids)

BTH K1(1999)
1SPH
BTH K1(1998)
1SPH
JPA K2 (1998)
1SPH
Averages

6.46
6.44
6.33
6.39

STC K1

Dry
(cros)
Dry
Dry
Dry
Dry
Dry
Dry

BFD K2 (1998)
ESW K4 (1999)
ESW K4 (1998)
STC K2 (1998)
SCK K1(1998)
SCK K2 (1998)
Averages

yes X1

Area Ratio
m2/mtpd
Nominal Prod.

Specific Weight
kg/m3
C1-C2
(less FE void)

Gross Weight
kg/m3
C2
(pluss all voids)

Weight Ratio
kg/mtpd
(Nominal Prod.)

4.39
4.38
4.93
4.65

1.36
1.17
2.57
1.87

260.12
260.26
242.82
251.54

176.77
176.77
189.32
183.05

54.79
47.14
98.46
72.80

4.90

4.18

1.76

303.00

258.57

109.18

5.70
7.46
7.42
6.96
8.21
7.79
7.26

4.70
5.44
5.36
6.48
6.34
6.16
5.75

1.50
2.96
3.08
2.44
2.10
2.21
2.38

269.30
303.21
301.27
317.93
309.56
274.44
295.95

221.90
220.92
217.89
296.23
238.92
216.96
235.47

71.00
120.37
125.02
111.57
79.14
77.90
97.50

6.6
Rev. 2002

CEMENT PROCESS ENGINEERING


VADE-MECUM
Kiln
updated Feb 99
M.Brunelle (CTS)

Type

FDA K1(1998)
FDA K2 (1998)
RMD K1(1998)
RMD K2 (1998)
SEA (1998)
Averages

Wet
Wet
Wet
Wet
Wet

Impact Chain densities


Specific Area
plates

yes X2
yes X1
yes X1

SECTION 6 PYROPROCESSING

m2/m3
C1-C2
(less FE void)

Gross Area
m2/m3
C2
(plus all voids)

4.95
5.90
7.16
6.54
4.82
5.88

4.36
5.13
6.23
5.28
4.07
5.01

Area Ratio
m2/mtpd
Nominal Prod.

Specific Weight
kg/m3
C1-C2
(less FE void)

Gross Weight
kg/m3
C2
(pluss all voids)

Weight Ratio
kg/mtpd
(Nominal Prod.)

2.72
3.00
2.68
2.62
2.72
2.75

280.57
333.31
283.75
291.05
189.23
275.58

246.86
289.84
247.01
234.90
159.84
235.69

154.36
169.66
106.16
116.66
106.76
130.72

6.7
Rev. 2002

CEMENT PROCESS ENGINEERING


VADE-MECUM

SECTION 6 PYROPROCESSING

6. Cooler
6.1 Compartments
Compartments number
<800 tpd:
4 compartments
2000-3000 tpd:
7 compartments
800-1200 tpd:
5 compartments
3000-4000 tpd:
8 compartments
1200-2000 tpd:
6 compartments
>4000 tpd:
9 compartments
To the middle of the cooling zone, the ratio between compartment area will be 1.4 (except for the #2).
Recuperation zone
Q
I=
.
1440 H k N C
where:
- l:
cooler width
clinker flow (t/day)
- Q:
:
Clinker apparent density (t/m3) generally 1.25
bed depth (m)
- H:
grate efficiency (0.70 for flat grates)
- k:
number of stroke per minute (usually 10 to 14spm)
- N:
the grate course (m)
- c:
N has to be chosen to allow 1.6 * N in case of push.
The length of the recuperation zone will be set with an air density between 1.45 Nm3/m2*s (Fuller) and 1.55
(IKN) and a heat consumption 800 kcal/kg and 0.85 Nm3/kgkk for the combustion air.
Cooling zone
The cooler loading will be the factor determining the cooling zone length:
- 40 t/m2/day dry process (high pressure fans thick bed depth (60 cm))
- 35t/m2/day wet process (high pressure fans)
- 28 t/m2/day all processes (low pressure fans, thin bed depth (30 cm))
Rules of thumb
Air velocity above clinker bed: 5 to 7m/s.
6 to 10 strokes per minute, cooler stroke length around 5, clinker speed around 1 to 1.2 m/min.
Clinker granulometry: passing 0.5mm:<15% , remaining at 25mm<10%.
Void volume: about 0.4 to 0.5.
Clinker bulk density: 89 to 120 lb/ft3.
Grate cooler: 5-10 kWh/ t, target should be below 5 kWh/t w/o vent air fan.

6.2 Fans
Recuperation zone
Maintain the flow during a kiln push: the fan maximum pressure has to be 30% higher than the nominal. At
constant flow, 15% of security to absorb the pressure variation. It is also a good security to keep 30% of flow
reserve between the peak of the curve and the nominal.
In the kiln, minimum cooling rate between 1450 and 1300C: 20C/min.

6.8
Rev. 2002

CEMENT PROCESS ENGINEERING


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SECTION 6 PYROPROCESSING

Cooling zone
They should be able to go from 2.5 to 3 Nm3/kg during a push. Their curve should be flatter and their
maximum pressure 30% above the functioning point. 20% increase in flow has to keep 15% safety margin on
pressure. Minimum is 30 mbar for single-stage cooler.
Rules of thumb
Grate plate resistance is directly related to the air flow and represents about 15% of total air resistance.
Basic operating principles:
- Maintain a constant air to clinker ratio
- Maintain a constant bed depth
- Remove all excess cooling (vent) air
The longer the air/clinker contact time, the cooler the clinker.
The higher the velocity air, the colder the clinker surface, the higher the heat transfer rate from center to edge
of the clinker but the lower the between air and clinker edge.
Average cooling air flow (Lafarge Corp): 3.7 kg/kg kk, 2.9Nm3/kg kk.
Average grate loading: 30 mt/m2/d (the older the lower usually).
3250.( 347 K )
Secondary air temperature: T =
.
SHC .n
where: K: heat loss of the cooler in kcal/kgck, SHC in kcal/kgck, n: excess air (ex:1.1)
Airflow:
Chamber #
1
2
3
>=4
Nm3/(m2.s)
2.0-3.5
1.2-1.8
1
<1

6.3 Cooler Efficiency Coefficients


a. Recovery Efficiency ():
= heat gained by recovered gases =
total usable heat input

hsa + hta
m + mta
hck ,in + hca sa
mca

where :
- msa=mass of secundary air in kg/h and hsa is the enthalpy of secondary air in kcal/h
- mta=mass of tertiary air in kg/h and hta is the enthalpy of tertiary air in kcal/h
- mca=mass of cooling air in kg/h and hca is the enthalpy of cooling air in kcal/h

This efficiency depends highly on the quantity of air recovered by combustion. It is higher for wet kilns
(90%) than for dry kilns (70%).

b. Cooling Efficiency
heat lost by clinker hck,in - hck,out
=
=
heat input in clinker
hck,in
c. Recovery Factor (k)

k=

ln (1 )
or = 1 - e -k ( m sa + mta )
m sa + mta

k = 0.9
k = 1.1

bad cooler
poor cooler

k = 1.3
k = 1.6

good cooler
excellent cooler

6.9
Rev. 2002

CEMENT PROCESS ENGINEERING


VADE-MECUM

SECTION 6 PYROPROCESSING

d. Cooler Loss
Cooler loss = all heat not recovered by combustion air.
Cooler loss = heat content of clinker leaving cooler ( hck ,out ) :
+ heat content of vent air + heat content of coal mill air
+ heat content of raw mill air + wall heat losses
e. Typical Values
(Lafarge Corp data)
k
Cooler loss (kcal/kgkk)

min
0.83
60

max
1.67
180

Av.
1.25
120

min
92%
51%

max
97.2%
85.7%

Av.
95%
70%

6.10
Rev. 2002

CEMENT PROCESS ENGINEERING


VADE-MECUM

SECTION 6 PYROPROCESSING

6.4 Typical Heat Balance Davenport Cooler


Cooler heat & mass balance
Clinker (T/d):
Clinker (kg/h):
IN

Davenport cooler

2537
105725

Final balance
Date:Sept 16 to 18, 97

Ref. temperature:

0C

volume

volume

mass

mass

Temp.

Heat

Nm/h

Nm/kg ck

kg/kg ck

kg/h

kcal/h

Cooling air
Hot clinker
Total
OUT
Secondary air
Tertiary air
Raw mill take-off
Coal mill take-off
Vent air
Cold clinker
Wall loss
Total
Difference:

225671

2.13

225671

291643
105725
397368

37
1350

2.13

2.76
1.00
3.76

2613673
36638913
39252586

24.7
346.5
371.3

23016
71770

0.22
0.68

0.28
0.88

29745
92751

974
874

7540626
20901034

71.3
197.7

16232
114652

0.15
1.08

0.20
1.40
1.00

20978
148170
105725

317
167
143

225671

2.13

3.76

397368

1623430
5976961
2916855
293680
39252586

15.4
56.5
27.6
2.8
371.3

0.00
0.00%

0.00
0.00%

0
0.00%

0
0.00%

0.0
0.00%

0
0.00%

:
:

75.37%(recovery ratio)
92.04%(cooling efficiency)

k:
Cooler loss:

Tertiary air
0.68 Nm/kg ck
0.22 Nm/kg ck
974C
Secondary air

Heat
kcal/kg ck

874C

1.56
102.26kcal/kgck
Vent
1.08 Nm/kg ck

Coal mill
0.15 Nm/kg ck
317C

167C

Clinker
105725 kg/h
1350C

Cooling air
2.13 Nm/kg ck
37C

Clinker
105725 kg/h
143C

6.11
Rev. 2002

CEMENT PROCESS ENGINEERING


VADE-MECUM

SECTION 6 PYROPROCESSING

7. Kiln Heat Balance


7.1 Theoretical Heat for Clinker Formation
Perray
From clinker analysis:

Q (kcal / kg ck ) = 4.11 Al 2 O3 + 6.47 MgO + 7.64 CaO 5.11 SiO2 0.60 Fe 2 O3

Lafarge Model

172 160

228 100

Exothermic reaction

Decarbonization
QD = 437.5 + 0.66 10 2 T 0.22 10 4 T 2
where:
- QE in kcal/kgkk
- QD in kcal/kg CaCO3
- T is the decarbonatation temp (K)

Qtheo = QD - QE

QE = C 2 S + C 3 S

7.2 Wall Losses


a. General Formula
WL = S ( T 2 T 1 )
where:
- WL is the losses in kcal/h
- S is the area in m2
- T2 is the wall temperature (C)
- T1 is the ambient temperature (C)
- is defined in the following graph
65

60
55
50
45

W/M2C

40

v = 14 m/s wind
13
12
11

35

10
9

30

8
7

25

6
5

20
15

4
v =3 0 m/s (free convection)
2
1

S = 0.9

Wind:0m/s

10

Ambient T - 20C

5
0

100

200

300

400

500

600

T - T (C)

6.12
Rev. 2002

CEMENT PROCESS ENGINEERING


VADE-MECUM

SECTION 6 PYROPROCESSING

b. Radiation

tp + 273 4

100

Loss = *4.96 *

Emissivity:
material
bricks
steel
For oxidized steel
For dusty kiln shell
For silica bricks

4
te + 273
kcal /
100

m2 h with: tp: wall temperature, te: external temp. (in C)

0.8
0.95
=0.996-2.88*10-4.(tp-100)
=0.96-5.2*10-4.(tp-100)
=0.81-6.08*10-4.(tp-200)

Other data
tp

Iron oxide
500C
0.78
Steel oxide
Zinc galvanized sheet bright
28C
0.23
Steel oxide
Iron polished
425C
0.144
Steel polished
Steel dense shinny oxide layer
25C
0.82
Steel pipe
Emissivity Error measurement: Example
Read temperature=65C, emissivity choosen: 1 instead of actual: 0.4

tp
40C
370C
770C
200

0.94
0.97
0.52
0.8

True temperature= t = ( 273 + 65 ).4 1 / 0.4 = 425 K = 152C


Loss calculated with read temperature=290kcal/h/m2, Loss with true temperature=510 kcal/h/m2
c. Convection

Loss = * ( tp te )1.25 kcal / m2 h


: coef exchange
2.6 for vaults
2.2 vertical surfaces

7.3 Kiln Residence Time


Rules of thumb:
Long kiln: 2-4 hours (Lafarge Corp. average: 155 min), short kiln:40 to 60 minutes.
RPM from 1.5 to 2.5 (short kiln), Long Kiln: 1.2 to 1.8, Lafarge Corp. average: 1.34.
Le Teil (1998): 1.5 to 2.3RPM improved clinker granulometry: Retained at 20mm: 7.2 to 13.5%, R10mm:
25to 37%
with:
Perray
- L Kiln length (m)
0.19 L
T=
- N Kiln speed (rpm)
N d S
- d kiln diameter (m)
- S Kiln slope (m/m)
Material speed
with:
Lafarge model in calcination zone:
- Vm: the speed at m
Ts + Tf
Tm
Tm: mat temp at m
N d S
2
Vm =

- Ts: temp where calcination begins


0.19
Tf Ts
- Tf: temp where calcination ends

6.13
Rev. 2002

CEMENT PROCESS ENGINEERING


VADE-MECUM

SECTION 6 PYROPROCESSING

6.14
Rev. 2002

CEMENT PROCESS ENGINEERING


VADE-MECUM

7.4 Water Spray

SECTION 6 PYROPROCESSING

w.s.(T1 T2 )
where: T1 and T2: uncooled and cooled temp (C) of the gas, w:
(100 t2 ) + 538.9. f

Flow needed = kg / h =

gas rate (kg/h), s: specific heat of gas (kcal/kg), t2:water temp. (in C), f :% water evaporated (decimal).
Lafarge corp : from 0 to 0.26kg water/kg clinker, average: 0.14.

7.5 Heat Balance Example


a. Davenport 1997 Flow Sheet

6.15
Rev. 2002

CEMENT PROCESS ENGINEERING


VADE-MECUM

SECTION 6 PYROPROCESSING

b. Precalciner Heat Balance


plant

Davenport

kiln

date

Kiln 1

13/11/97

Precalciner specific heat consumption


584 kcal/kg ck
heat in
%mass kg/hr
Air
99617
Primary air 1
2.00%
1992
Primary air 2
2.00%
1992
Inleakage 1
10.00%
9962
Inleakage 2
0.00%
0
Tertiary air
86.00%
85670
Preheater feed
190500
H2O
0.00%
0
Kiln Dust
0
Return Dust
0
Coal/Coke
8334
Combustion
H2O
1.34%
112
Natural Gas
0
Combustion
H2O
0.00%
0
WDF
0
Combustion
H2O
0.00%
0
Kiln Gases
49672
total in

Temp
(C)
kcal/kg
712 181.98
10
2.40
10
2.40
10
2.40
10
2.40
823 211.21
61
11.84
61.04
300
68.65
350
81.80
60
16.57
7361.60
60.04
80
43.21
0
80.15
80
44.98
0.00
80.15
904 258.36

348122

kcal/hr kcal/kg ck
18127832
172.52
4788
0.05
4788
0.05
23938
0.23
0
0.00
18094318
172.20
2256252
21.47
0
0.00
0
0.00
0
0.00
138056
1.31
61349445
583.86
6705
0.06
0
0.00
0
0.00
0
0.00
0.00
0.00
0.00
0.00
0
0.00
12833217
122.13
94711507

heat out
%mass kg/hr
Tower Exit Gas
188391
O2
2.13%
4013
CO2
45.82%
86313
H2O
2.18%
4103
SO2
0.18%
338
N2
48.87%
92067
Ar
0.83%
1558
Bypass Gas
21000
O2
2.00%
420
CO2
32.14%
6749
2.84%
596
H2O
SO2
3.77%
791
N2
58.27%
12237
Ar
0.99%
207
Bypass Dust
3810
Kiln Feed
112921
Heat of Formation
Tower Exit dust
22000
Wall Losses

901.37 total out

difference

Temp
(C)
kcal/kg
kcal/hr kcal/kg ck
358 100.84 18997182
180.80
81.97
328920
3.13
83.08 7170647
68.24
759.59 3116709
29.66
59.90
20229
0.19
90.06 8291338
78.91
44.51
69337
0.66
440 126.82 2663285
25.35
102.07
42869
0.41
104.95
708259
6.74
800.12
476879
4.54
75.39
59662
0.57
111.49 1364285
12.98
54.74
11332
0.11
400
85.46
325607
3.10
850 197.04 22249876
211.75
412.02 46526066
442.79
340
79.13 1740957
16.57
22.00 2484260
23.64

348122

94987233

904.00

0
0.00%

275726
0.29%

2.62
0.29%

c. Kiln Heat Balance


plant

kiln

Davenport

fuel
Coke/Coal
Natural Gas
Waste Derived Fuel

kg/hr
Temp (C) LHV (kcal/kg) Tot. kcal/kg
3572
60
7362 26354660
0
15
0
0.00
0
0
0
0.00

total combustion air


Total Combustion Air

%vol

Primary Air 1
Primary Air 2
Inleakage 1
Inleakage 2
Secondary Air

4.78%
6.21%
10.00%
0.00%
79.01%

total kiln gas


Total Kiln Gas
O2
CO2
H2O
SO2
N2
Ar

%vol

excess air
Excess Air

kg/hr
2402

2.01%
23.45%
5.06%
1.89%
66.80%
0.79%

Nm3/hr
29600
1415
1837
2960
0
23388
Nm3/hr
34667
696
8130
1754
655
23158
275

%mass

4.78%
6.21%
10.00%
0.00%
79.01%
%mass
2.00%
32.14%
2.84%
3.77%
58.27%
0.99%

Kiln 1
Clinker
Kiln Feed
Return Dust
Waste Dust

Date

kg/hr
Temp (C) neutral combustion air
38254
Neutral Combustion Air
O2
1828
27 CO2
2374
25 H2O
3825
25 SO2
0
25 N2
30226
1065 Ar

%mass

kg/hr
Temp (C) neutral combustion gas
49672
904 Neutral Combustion Gas
993
O2
15963
CO2
1410
H2O
1872
SO2
28944
N2
490
Ar

%mass

water spray
H2O spray

13/11/97

kg/hr
105075
112921
0
0

23.15%
0.04%
0.00%
0.00%
75.53%
1.28%

0.00%
25.71%
3.60%
0.31%
69.22%
1.17%
kg/hr
0

kg/kg ck
1.00
1.07
0.00
0.00
kg/hr
35852
8300
14
0
0
27079
459
kg/hr
39195
0
10076
1410
121
27130
459
Temp (C)
10

6.16
Rev. 2002

CEMENT PROCESS ENGINEERING


VADE-MECUM

SECTION 6 PYROPROCESSING

d. Kiln Summary
plant

Davenport

kiln

date

Kiln 1

13/11/97

Kiln specific heat consumption


250 kcal/kg ck
heat in
%mass kg/hr
Air
38254
Primary air 1
4.78%
1828
Primary air 2
6.21%
2374
Inleakage 1
10.00%
3825
Inleakage 2
0.00%
0
Secondary Air 79.01%
30226
Kiln Feed
112921
H2O
0.00%
0
H2O Spray
0
Return Dust
0
Coal/Coke
3572
Combustion
H2O
1.34%
48
Natural Gas
0
Combustion
H2O
0.00%
0
WDF
0
Combustion
H2O
0.00%
0
total in

Temp
(C)
kcal/kg
kcal/hr kcal/kg ck
846 221.92 8489285
80.79
27
6.50
11884
0.11
25
6.01
14256
0.14
25
6.01
22974
0.22
25
6.01
0
0.00
1065 279.23 8440171
80.33
850 609.06 68775942
654.54
0.00
0
0.00
10
9.97
0
0.00
300
68.65
0
0.00
60
16.57
59167
0.56
7362 26292619
250.23
60.04
2873
0.03
15
7.70
0
0.00
0
0
0.00
14.97
0
0.00
0
0.00
0.00
0.00
0
0.00
0.00
0.00
0
0.00

154747

103619887

heat out
%mass kg/hr
Total Gas
49672
O2
2.00%
993
CO2
32.14%
15963
H2O
2.84%
1410
SO2
3.77%
1872
N2
58.27%
28944
Ar
0.99%
490
Clinker
105075
Heat of Formation
Exit dust
0
Wall Losses

986.15 total out

difference

Temp
(C)
kcal/kg
kcal/hr kcal/kg ck
904 258.36 12833217
122.13
221.81
220355
2.10
239.69 3826133
36.41
1049.74 1479875
14.08
168.70
315788
3.01
239.63 6935970
66.01
112.52
55097
0.52
1358 349.49 36723000
349.49
420.00 44131394
420.00
400
95.32
0
0.00
75.00 7880606
75.00

154747

101568217

966.63

0.00
0.00%

-2051671
-2.02%

-19.53
-2.02%

8. Volatile
8.1 Properties of Volatile Elements
a. Basic Volatile Properties
The raw mix comes with some minor elements (potassium, sodium, sulphur and chlorides) called volatiles.
Element

Compound
Oxide
Hydroxide
Carbonate
Sulfate
Chloride

Formula

Na2O
NaOH
Na
Na2CO3
Na2SO4
NaCl
Oxide
K 2O
Hydroxide
KOH
K
Carbonate
K2CO3
Sulfate
K2SO4
Chloride
KCl
Oxide
CaO
Hydroxide Ca (OH)2
Ca
Carbonate
CaCO3
Sulfate
CaSO4
Chloride
CaC12
Fluoride
CaF2
d=Decomposes, s=Sublimates

Molecular
Weight
62.0
40.0
106.0
142.0
58.4

Melting
Point C
820
322
851
884
801

Boiling
Point C
d
1390
d

1465

94.2
56.1
138.2
147.3
74.6

887
410
891
1069
776

d
1327
d
1689
1410

362
426
1146
1434
1436

2850

1600

636
987
288
1430
795

56.1
74.1
100.1
136.1
111.0
78.1

2580
d
d
d 1280 (1450)
772
1380

Heat of Formation
- Hf kJ/mol
416
427
1131
1385
411

6.17
Rev. 2002

CEMENT PROCESS ENGINEERING


VADE-MECUM

SECTION 6 PYROPROCESSING

b. Eutectic
In a multicomponent-system the melt formation is governed by eutectics. Eutectic is a mixture of two or more
substances that have a melting point lower than any of the substances of the mixture.

Eutectic Melting
System

Concentration
(% mole)
52 48
58 42
23 77
60 40
42 58
40 60
68 32
50 50
65 35
25 75
50 50

Na2SO4 CaSO4
K2SO4 CaSO4
K2SO4 Na2SO4
K2CO3 CaCO3
K2CO3 Na2CO3
K2SO4 KCl
KCl CaSO4
KCl NaCl
NaCl Na2SO4
KCl CaCl2
NaCl CaCl2

Melting point
(C)
900
867
823
750
710
690
688
640
630
600
500

c. Vapor Pressure
Vapor Pressure for Volatile Compounds at Different Temperatures
mm Hg
760
700

NaOH

KCl

KOH

600

NaCl
500
Na 2CO3

400

Na 2SO4

300
200

Caution: This graphic is for trend indication only.


We have no indication of the precision of the
curves. Do not use for calculation.
Thus, for instance, K is more volatile than Na.

K2 SO4

K2 CO3

100

700

800

900

1000 1100 1200 1300 1400 1500 C

d. Typical Chemical Reaction

Me n (SO4 )m n MeO + m SO2 +

The equilibrium constant of that reaction has this formula: K =

m
O2
2

where: Men can be: Ca, K2,Na2

[MeO]n [SO2 ]m [O2 ]m / 2


Men (SO4 )m

6.18
Rev. 2002

CEMENT PROCESS ENGINEERING


VADE-MECUM

SECTION 6 PYROPROCESSING

e. Parameters Influencing the Volatilisation Process


Influence of kiln gases on the volatility of the circulating elements

Kiln atmosphere
vapor pressure
CO2
H2O
O2

Sodium
v

Potassium
v

Sulphur
v

Chloride
v

SO2

Effect of fineness on v at 1300C

1.7% > 200 m


21.8 % > 90 m
< 90 m
< 60 m

K2O
v
0.89

Na2O
v
0.42

SO3
v
0.63

0.89
0.93

0.46
0.45

0.63
0.65

8.2 Volatilization Process

Volatiles will start to volatilize (evaporate) from the liquid phase as soon as the temperature increases.
A fraction of those elements (or compounds) will be vaporized in the burning zone and get entrained with the
gases toward the back of the kiln. The vapors will cool down together with the gas stream and recondense
before leaving the kiln or in the dust collector. The condensation takes place on any cool surface, mostly on
the dust carried by the gas.
:
flux of volatile component i brought by fuel (g/kg ck)
- Fi
- Mi
:
flux of volatile component i brought by raw mix (g/kg ck)
:
flux of volatile component i going out with the clinker (g/kg ck)
- Ci
- Li
:
flux of volatile component i lost with gas and dust (g/kg ck) ( loss)
:
flux of volatile component i in the kiln load (g/kg ck)
- Ki
:
flux of volatile component i in the gas stream (g/kg ck)
- Gi

a. Volatile Recirculation Model


Exit gas
& dust

Gas & dust

Trapping
Raw mix

Fuel

Volatilization
Kiln load

Kiln load: K =
Clinker: C =

tF +M
1 vt

1v
(tF + M )
1 vt

Clinker

Gas stream: G =
Losses: L =

vM +F
1 vt

1t
(vM + F )
1 vt

6.19
Rev. 2002

CEMENT PROCESS ENGINEERING


VADE-MECUM

Typical volatilization and trapping coefficients


Type of kiln
SO3
K2O
v
t
v
Wet kiln without dust wasting
0.59
0.76
0.45
Wet kiln with dust wasting
0.72
0.63
0.53
Long dry kiln
0.65
0.87
0.65
Preheater kiln
0.80
0.90
0.69
Precalciner kiln
0.55
0.96
0.49
(Prepared from average volatile balances made within Lafarge)
Typical concentration factors of volatiles in the kiln load
(kiln load / raw mix ratio)
Na2O and K2O
2 to 10
SO3
4 to 20
20
to 100
Cl

SECTION 6 PYROPROCESSING

Na2O
t
0.81
0.51
0.81
0.96
0.98

v
0.12
0.24
0.21
0.26
0.55

Clt
0.68
0.45
0.79
0.60

v
0.99
0.99
0.99
0.99
0.99

t
0.99
0.99

b. Evolution of Volatiles During Transitions


If M() is a step at = 1 then:
K ( ) = K + (K K )(vt ) / T
1

where:
- K0 : previous kiln load composition
- K1 : new kiln load composition
- :
time (to avoid confusion with t, the trapping coefficient)
the time required by a given mass of volatile to complete a cycle
- T :
flux of volatile from the raw mix at time
- M() :
- F() :
flux of volatile from the fuel at time
- K() :
flux of volatile in the kiln load at time
Rules of thumb
Circulating kiln load : 1.7 to 2.1 kgload/kg clinker.
Generated dust: Lafarge Corp average for LD kilns:0.6, from 0.2 to 1.34 (BFD).
Generated dust: short kiln: 100 to 150g/kgck, Lepol Grate: 50g/kgck.
c. Volatile Cycle
t
C=
1v
- t is the time between the trapping and the
burning zone
- v is the volatilization coefficient
- C is the cycling time

Chlorine:
SO3 :

v = .99
v = .6

5-6 days
5-7 hours

8.3 SO2 - SO3


a. General
Sulfur is found in:
- Clinker raw material (combined form of sulfur or sulfate).
- Combustibles (S in the form of organic components).

6.20
Rev. 2002

CEMENT PROCESS ENGINEERING


VADE-MECUM

SECTION 6 PYROPROCESSING

Sulfur Behaviour
Sulfur Input Locations to Precalciner
Feed: as SO4 , 90-95% capture
as FeS 2 , 35-60% capture

30-40%
capture

Fuel

RM

Fuel: as SO 4 or S,
90-95% capt
100
80
% of total sulphur

Formation in the Burning zone


The following is the thermodynamic
equilibrium of sulfur species in a 10% excess
air flue gas. The principal product formed in
the burning zone will be SO2 .

60
40
20
0

0 0 0 0 0 0 0 0 0 000 0 0 0 0 0 0 0 0000 0 0 0 0 0 0 0 0000 0 0 0 0 0 0 0 000 0 0 0 0 0 0 0 0


00 00 00 00 00 00 00 00 00 0 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 0 00 00 00 00 00 00 00 00 0
0 0 0 0 0 0 0 0 0 00 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 00 0 0 0 0 0 0 0 0 0
0 0 0 0 0 0 0 0 0 00 0 0 0 0 0 0 0 000 0 0 0 0 0 0 0 000 0 0 0 0 0 0 0 00 0 0 0 0 0 0 0 0 0
0 0 0 0
H2SO4

400

SO2

SO3

600

800

1000

1200

1400

Temperature (K)

b. What Affects the SO2 Generation in the Burning Zone?

The composition of the kiln load


Sulfur is preferably linked with alkalies which have a higher stability and a greater chance of being found as
alkali sulfate in the clinker ( K 2 SO4 , Na2 SO4 ) themselves being part of bigger compounds. So if the kiln load
composition has a molar excess of K 2O Na2O available (not combined with chlorine) vs SO3 , the SO 2
generated from the load will be lower (sulfur, alkali, molar ratio < 1.2).
The burning zone temperature
At lower temperature, less CaSO4 or alkali sulfates will decompose to form SO 2 and the SO3 level in the
clinker will be higher.
The O2 level
2000

SO 3

1.0

S
O2 1500
pp
m 1000

1400C

0.8
0.6

500

0.4

0.2
0.0

0.5

1.0

1.5
2.0
Oxygen %

2.5

3.0

0
0

1.0

2.5

1200C
1000C
%O 2
5.0

The residence time in the burning zone


The longer the time the material stays in the burning zone, the higher the chance for SO 2 to volatilize.
Back-end
If the raw mix contains sulfur compounds (i.e. FeS 2 = pyrite), the combustion of these compounds generates
SO 2 .

6.21
Rev. 2002

CEMENT PROCESS ENGINEERING


VADE-MECUM

SECTION 6 PYROPROCESSING

00 00 00 00 00 00 00 00 00
0 0 0 0 00 0 0 000 0 0 00 0 0 0 00 0 0 0 00 0 0 0 00 0 0 000 0 0 00 0 0 0 00 0 0 0 0
00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00
0 0 0 0 00 0 0 000 0 0 00 0 0 0 00 0 0 0 00 0 0 0 00 0 0 000 0 0 00 0 0 0 00 0 0 0 0
00 00 00 00 00 00 00 00 00

c. SO3 Volatilization in Calciner


SO3 volatilization (%)

90
80
70
60
50
40

90

91

92

93

94

95

96

97

98

99 100

Combustion efficiency (%)

trapped by CaCO 3 and CaO at lower


temperatures. There is a large excess of
CaCO 3 in the preheater, which explains a
high trapping coefficient (95% "dry"
scrubbing).

00 00 00 00 00
0 0 0 0 0 000 0 0 0 0 000 0 0 0 0 00 0 0 0 0 0 00 0 0 0 0 0 00 0 0 0 0 0 0
0 0 0 0 0 000 0 0 0 0 000 0 0 0 0 00 0 0 0 0 0 00 0 0 0 0 0 00 0 0 0 0 0 0
0 0 0 0 0 0000 0 0 0 0 0000 0 0 0 0 000 0 0 0 0 0 000 0 0 0 0 0 000 0 0 0 0 0 0
0 0 0 0 0

Lab experience (H. Ritzmann, Neubeckum).


80

SO2 trapped (% of total)

d. Trapping
SO2 is stable above 900C but starts to be

60

40

20

400

500

600

700

800

900

1000

Temperature (C)

CaCO3 + SO 2 + 1 / 2 O2 CaSO4 + CO2 .


In a precalciner kiln, the decarbonated limestone captures more actively SO 2 , especially with a high level of
Oxygen and the following equilibrium is shifted to the left: CaSO4 CaO + SO2 + 1 / 2 O2 .
For this reason, precalciner kilns are able to absorb rather high concentrations of SO 2 in the gas coming from
the kiln.

8.4 Build-up and Rings

After condensation and before solidification of the volatiles, the dust particles will be sticky and tend to
agglomerate on solid objects: kiln walls, chains or lower cyclones of preheater tower.
The sulphur build-up usually occurs where the temperature is between 800C and 1100C: kiln walls and
chains for a long kiln, smoke chamber and lower cyclone for a preheater kiln. In those build-ups, the following
sulfates are most commonly found: Arcanite (K2SO4), Anhydrite (CaSO4), Glaserite (K3Na (SO4)2), CaLangbeinite (K2Ca2 (SO4)3) and sulfate spurrite (Ca2 (SiO4)3 CaSO4).
In a long kiln, the build-ups are formed below the internal exchanger. This takes place in the kiln load so the
build-ups formed this way are naturally destroyed in the majority of the cases. In small diameter kiln,
however, a sulfate ring can appear.
Chlorine will condense in the 600C to 700C zones, that is in the chains for a long kiln.
Operational difficulties when the concentration of circulating elements in the load material exceeds the
following levels (on clinker basis):
- Na2O + K2O = 35 %, SO3 =35 %, Cl- =1.21.6 %

6.22
Rev. 2002

CEMENT PROCESS ENGINEERING


VADE-MECUM

SECTION 6 PYROPROCESSING

8.5 Volatile Balance Example : Davenport 1997


Flow
t/h
168.500
105.075
22.000
0.000
3.810

Loss of ign
%
*
35.410
0.000
5.210
5.000
0.000
5.200

Moisture
%
0.000
0.000
0.000
0.000
0.000
0.000

SO3
%
0.897
0.610
2.450
1.440
0.000
11.230

Coal
Coke

Flow
t/h
8.680
3.720

Ash
(as rec) %
10.460
0.510

Moisture
(as rec) %
5.570
4.590

S
(as rec) %
1.020
3.040

K2O (ash) Na2O (ash)


Cl
%
%
(as rec) %
2.100
0.290
0.000
1.100
2.780
0.000

Stack

Flow SO2
kg/h
908.18

Dust (dry)
kg/h
0.00

Dust SO3
%
0.00

Dust K2O
%
0.00

Dust Na2O
%
0.00

Flow
dry t/h
168.5
22.0
8.2
3.55
0.00
105.08
22.00
3.81
1.14
-

CO2
%
35.4
5.0
0.00
0.00
5.00
5.20
0.00
-

Flow CO2=0
t/h
108.83
20.90
1.13
0.30
0.00
131.17
105.08
20.90
3.61
1.135
130.72

Flow
t/h
168.2
22.0
8.7
3.7
.0
105.3
22.0
3.8
1.1
-

Flow dry
kg/kgkk
1.60
0.21
0.08
0.03
0.00
1.00
0.21
0.04
0.01
-

Raw mix
Clinker
Kiln load
Recirculated dust
Injected prod
Waste dust

K2O
%
0.500
0.710
1.099
0.580
0.000
2.073

Na2O
%
0.090
0.130
0.760
0.100
0.000
0.493

Dust Cl
%
0.00

Cl
%
0.001
0.010
0.101
0.001
0.000
0.255

Loss of ign
% *
0.00

Mass Balance

Raw mix
Recirculated dust
Coal
Coke
Injected prod
Total inlet
Clinker
Recirculated dust
Waste dust
Stack
Total outlet

| (Coal; Flow CO2=0: Ash + S converted to SO3 + Cl)


| (LWF; Flow CO2=0: Ash + S converted to SO3 + Cl)

(Stack; Flow CO2=0: Dust + SO2 converted to SO3 + Cl)


Inlet-outlet:
0.44
(st/h LOI=0)

Flow Rate Adjustment


Weighting
Raw mix
Recirculated dust
Coal
Coke
Injected prod
Total inlet
Clinker
Recirculated dust
Waste dust
Stack
Total outlet

*Ignition loss at:

0.50
0.00
0.00
0.00
0.00
0.50
0.00
0.00
0.00
1.0

%CO2 C

Flow CO2=0 Flow CO2=0


t/h
kg/kg kk
108.61
1.03
20.90
0.20
1.13
0.01
0.30
0.00
0.00
.000
130.94
1.24
105.30
1.00
20.90
0.20
3.61
0.03
1.14
0.011
130.94
1.24

note - data entry


Enter weighting factors
in boldface
total must equal 1.0
all positive values 0-1

note - data entry on "Ignition loss"


Concerns LOI determination; impacts the CO2=0 mass balance
if %CO2; LOI is only CO2 loss
if 1050; LOI is CO2 & moisture loss
if 1400; LOI is CO2 & moisture & volatile loss

6.23
Rev. 2002

CEMENT PROCESS ENGINEERING


VADE-MECUM

SECTION 6 PYROPROCESSING

Kiln Audit November 1997


Volatile Balance
kiln load
hypothesis

Waste Dust 4.063


=
Stack = 10.231

17.304

Return Dust
=
3.009

Raw Mix = 14.783

1.30

SO3
31.362

kg/kg
clinker

Combustible
=

Volatilization =
26.208

Trapping =
14.058

Clinker = 5.642

Kiln Load =31.850

17.792

Volatile Coefficient =

Total Trapping Coefficient 0.544


=

5.154

0.823

K2O
Waste Dust
=

0.750

1.962

Combustible
=

7.202

0.173

Stack = 0.000
Return Dust
=
1.212

Raw Mix = 7.831

Volatile Coefficient =

Total Trapping Coefficient 0.896


=

kiln load
hypothesis

Raw Mix = 1.444

1.30

Na2O

0.387

Return Dust
=
0.209

Clinker = 7.254

Kiln Load =14.283

9.043

Waste Dust 0.178


=
Stack = 0.000

Volatilization =
7.029

Trapping =
5.240

8.615

0.492

kg/kg
clinker

Combustible
=

Volatilization =
8.586

Trapping =
8.228

Clinker = 1.294

Kiln Load =9.880

1.652

Volatile Coefficient =

Total Trapping Coefficient 0.979


=

0.028

0.869

Chlorine
Waste Dust 0.057
=
Stack = 0.000

0.059

Return Dust
=
0.002

Raw Mix = 0.095

1.275

Total Trapping Coefficient 0.955


=

0.018

Volatilization =
1.257

Trapping =
1.216

0.097

Combustible
=

Clinker = 0.056

Kiln Load =1.313


Volatile Coefficient =

0.957

6.24
Rev. 2002

CEMENT PROCESS ENGINEERING


VADE-MECUM

SECTION 6 PYROPROCESSING

8.6 Circulation in Preheater (Port-la-Nouvelle)


a. Kiln Parameters
- Clinker production:
- Raw mix:
- Coal:
- Heat consumption:
- O2 kiln out:
-

O2 tower out:

58.33 tph
88.4 tph
8.035 tph
833 kcal/kk
2.5%

3.5%

Kiln exit gas:


C1 exit gas:
Tower exit gas:
Dust tower exit:
Kiln exit temp:
C1 exit temp:

1.286 Nm3/kk
1.412 Nm3/kk
1.505 Nm3/kk
4.2 tph
1200 C
835 C

The dust from ESP and conditioning tower are mixed after the raw mix feeder.
In the following diagrams, the ESP dust + conditioning tower dust are called E-P dust.

b. Kiln Volatile Balance


Volatilization (%)
Trapping (%)

SO3

K2O

Na2O

Cl

68.5
100

77.5
100

18.4
100

99.0
100

c. Flow Calculation in Exchanger


Equation 1: @LOI=0
Mat C2 + Kiln dust = Mat C1 + C1 dust
Equation 2:
[K 2 O]C 2 + [K 2 O]Kdust = [K 2 O]C1 + [K 2 O]dustC1

Cyclone

Efficiency

C4
C3
C2
C1

95%
94%
94%
89%

d. Flux per Cyclone

Cl
SO3
Na2O
24.15
22.2
C1
Inlets
2.78
25.61
21.5
Outlets
2.84
-6%
+3%
-2%
rel
11.92
C2
Inlets
8.02
2.27
11.4
Outlets
16.97
2.58
+4.4%
-112%
-14%
rel
3.32
C3 + C4
Inlets
4.59
1.51
2.45
Outlets
5.54
1.74
+23%
-21%
-15%
rel
The relative difference inlet/outlet is higher for the top stage:
- only 1 measurement
- smaller volatile content
The SO3 balance for stage 2 is explained by the SO2 trapping in material (lower in C1) SO 2 is stable above
700. The volatile elements are trapped principally in the 2 bottom stages (75%).

6.25
Rev. 2002

CEMENT PROCESS ENGINEERING


VADE-MECUM

SECTION 6 PYROPROCESSING

9. Lafarge Corp Typical Ratios


1998 data
Kiln by plant
Process

Long wet

Long dry

Rated Capacity Thermal load Specific loading Cooler loading


Metric tonnes
Gcal/hm2
MTPD/M3
MTPD/m2

Richmond 1
Richmond 2

830
823

5.7
6.0

0.6
0.6

Woodstock 1
Woodstock 2

794
839

4.1
4.4

0.6
0.6

Fredonia 1
Fredonia 2

446
650

3.4
5.7

0.5
0.5

22.3
31.7

Paulding 1
Paulding 2

687
687

6.1
6.1

0.6
0.6

22.8
22.8

Brookfield 1
Brookfield 2

650
855

4.1
4.4

0.5
0.8

25.1
35.8

Exshaw 4

1272

3.5

0.5

34.6

Kamloops

617

4.0

0.6

23.8

St-Constant 1
St-Constant 2

1510
1540

3.9
4.0

0.6
0.6

33.8
37.5

Alpena 19
Alpena 20
Alpena 21
Alpena 22
Alpena 23

1119
1105
1102
1649
1657

6.2
6.1
5.8
5.1
5.6

0.7
0.6
0.6
0.5
0.5

47.1
32.2
32.1
34.0
34.2

Joppa 1

1574

6.2

0.6

28.9

Sugar Creek 1
Sugar Creek 2

705
804

4.6
4.7

0.7
0.7

23.4
22.3

Single stage Bath


Preheater
Joppa 2

3267

4.6

0.6

41.1

1845

5.4

0.6

29.4

S Preheater Whitehall 1
Whitehall 2

1344
947

4.3
3.7

1.7
1.8

57.7
52.4

AS Preca

Exshaw 5

2459

5.3

4.1

57.0

Davenport

2751

2.7

3.4

40.0

Richmond 3

3000

3.1

4.7

38.9

6.26
Rev. 2002

CEMENT PROCESS ENGINEERING


VADE-MECUM

SECTION 6 PYROPROCESSING

10. 57 Clinker Reactivity Study (P. Barriac)


Ranges studied:

If we want:

Free CaO Underburning


R. quartz on Sol. Na2O eq.: Ex. SO3/tot. alk.: - C3A perc.: 0% to C3S perc.: 43% to C2S perc.:
0.6% to +1.7%
12.6%
76%
2% to 31.5% perc.: 0.05%
to
63: 0.5% to 0.1% to 0.9%
to 2.2%
overburning
5.3%
Siliceous raw % of soluble
Excess SO3/tot.
% of C3A
% of C3S
% of C2S
% of free
Moderate
mix reject
alkalies
alkalies
CaO
burning with:




burning
(easier
% alkalies (with Ex. SO3/total at the expense of at the expense of in favour of with lime zone length
(in particular
combination and/or clinker alk. 1% to limit %C4AF (strong %C2S (and/or with
%C3S
saturation
rate of
%C4AF and
impact if high %
factor to keep
: small alite % SO3 (to have
alite size)
temperature
%MgO)
sol. alk.)
C3S = Ct
and belite size) a molar ratio
rise)
1)
burning
zone
length
R.28-d.
(easier
% total alkalies (with Ex. SO3/total at the expense of with %C4AF
with
(we can
( rates of
%C4AF and free CaO to
combination
(almost of all alk. 1% to limit
%C4AF
and %MgO
temperature
%MgO
%C3S)
: small alite alkalies are
alite size)
rise and
and belite size) soluble at 28 d)
cooling)
burning
zone
length
(easier
(with
Ex.
SO
/total
at
the
expense
of
with
%C
AF
with
R. 1, 2 and 28-d.
3
4
rates
of
(
AF
%C
AF
and
combination
%C
and
%MgO
alk. 1% to limit
4
4
temperature
%MgO
: small alite
alite size)
rise and
and belite size)
cooling)
burning
zone length
(easier
(keeping a molar at the expense of at the expense of in favour of
kWh/t
(in
combination
ratio at least equal
%C4AF
%C2S (and/or with
%C3S
particular
%C4AF and
to 1)
: small alite
rate of
%MgO)
and belite size)
temperature
rise)
Note: To establish this table, we have taken all the results of the statistical study into account, plus some other results taken from Influence du Profil
thermique Comparison de 4 tudes de laboratoire P. Barriac, June 6, 1995.
Presentation: italics: explaining comments normal letters: comments on application (method, limits).
Clinker Reactivity supplement to the 10 Basic Facts.
R.1 or 2-d









 





6.27