PYROPROCESSING

Friday, February 5, 2021

 INTRODUCTION

 Basis: Introduction to Process:

 kiln system description
 kiln pyro-processing zones
 Objective - increase understanding of
 kiln system benefits & constraints
 interaction between equipment selection,
clinker chemistry, & process control

You can become a rotary cement kiln

pyro-processing expert

Friday, February 5, 2021

 TYPES OF ROTARY KILNS

 Wet-Process Kilns
 WSK, PLD, SEA, (RMD K1, K2)
 Semidry Kilns
 Lafarge France
 Dry Kilns
 STC, BFD, KAM, ALP, SCK, EXS K4,
 JPA K1, BTH
 Preheater Kilns
 WHL, (Demopolis), BTH, JPA K2
 Precalciner Kilns
 EXS K5, RMD, SCK II, (Balcones)

Friday, February 5, 2021

 KILN HEAT CONSUMPTION

5.5

4.5
Million BTU/ton

3.5

2.5

1.5
Long Wet Long Dry Preheater Precalciner

Friday, February 5, 2021

 ROTARY KILN LENGTH
Drying Preheating Calcination Clinkerization Cooling Kiln Types

Long
Wet

Long
Dry

55 to 60%

Preheater

85 to 90%
Precalciner

Kiln Inlet Kiln Processes Kiln Discharge

Friday, February 5, 2021
 EVOLUTION OF ROTARY KILN

 Decreasing capital costs per tonne of clinker

 Primary driver
 Reduction in specific heat consumption
 Secondary benefit
 Greatest benefit is wet to dry
 Environmental issues
 Driver in new kiln design

Operations: lever advantages while understanding

process constraints

Friday, February 5, 2021

 WET PROCESS

 Feed enters the kiln in the form of slurry

 Moisture content up to 40%
 Additional dehydration zone requires the kiln be
longer than dry kilns
 Requires more fuel

ADVANTAGES

Uniformly blended feed

Lower dust losses
More suitable for moist climate regions
Friday, February 5, 2021
 WET PROCESS
OPERATIONAL COMMENTS
 Small kilns
 no economy of scale
 small “divisor” for fixed costs
 High specific heat consumption
 waste fuels
 Robust process
 waste fuels
 high moisture alternative raw materials
 Brick life limitations
 high heat loading in BZ

Friday, February 5, 2021

 SEMIDRY PROCESS
 Grate Process or Lepol Kiln
 Kiln exit gases pass through the granular feed bed
 Partly calcined feed enters the kiln
 Kiln controls are much more difficult.
from cyclones Auxilary Stack
Material

350°C 900°C
Cold chamber = Drying Hot chamber = Decarbonation

120°C 400°C to the Kiln

Grate

Material : to cyclones
Nodule feed= SEMI-WET PROCES
Granular feed = SEMI-DRY PROCESS
Friday, February 5, 2021
 DRY PROCESS

 Operate with a high back-end temperature

 Typically have chain sections at the feed end
 Suitable for cogeneration of electrical power
 Issues
 combustion emissions
 operator control practices

Friday, February 5, 2021

 CHAINS

 Chains provide large surface area in small length of

the kiln

Example: 12’ x 450’ kiln; 750 t/d

18,750 ft2 (1742 m2) chains
equivalent kiln length = 500’
i.e. kiln length for the same heat exchange = 950’

 Without chains, heat consumption is much higher

but can be recuperated (Alpena)

Friday, February 5, 2021

 CHAIN DESIGN

Optimum: Decreasing SHC vs Dust Generation

 SHC improves with increased chains

 Dust is important heat exchange mechanism
 Entrained dust S.A.  2x chain S.A.
 Dust generation is often limiting factor
 Chains increase gas velocity
 Dust pick-up = kV 2
 Wet kilns - possibility to trap dust
 slurry flow problems in plastic zone
 Dry kilns - limit dust generation
 poor trapping  uniform chain density

Friday, February 5, 2021

 LONG DRY PROCESS
OPERATIONAL COMMENTS
 Highly competitive
 if entire process (plant) optimised
 St. Constant - extremely low cost
 Reasonable specific heat consumption
 not a precal but not wet process
 not “forced” to use waste fuels
 Volatile cycles must be recognized & managed
 BTH, JPA
 Tendency to overburn
 long burning zone, lower quality

Friday, February 5, 2021

 PREHEATER KILNS

 Feed is preheated and partly calcined

 by the kiln exit gases in cyclone tower
 Heat exchange mechanism
 cold material in suspension with hot gases in
cyclones
 Tower plug-ups
 High concentration of alkalis, sulfur and
chlorine in the kiln exit gases
 often requires bypass

Friday, February 5, 2021

CYCLONES

Friday, February 5, 2021

 PRECALCINING SYSTEMS

through rotary kiln (AT)

either
Combustion Air
or
through separate duct
(AS)

either in the preheater

Precalcining Performed
or
in a separate vessel

Friday, February 5, 2021

 44 STAGE
STAGE PREHEATER
PREHEATER
WITH
WITH PRECALCINER
PRECALCINER
Gas out
360°C

Feed in 1st stage

50°C

540°C 350°C
2nd stage
690°C

530°C
3rd stage

880°C 630°C
4th stage

(Precalciner)
850°C 750°C

1200°C

Drying Burning
Cooling
Calcination Zone

Friday, February 5, 2021

 ADVANTAGES OF PRECALCINING
(In a Preheater System)
 Smaller dimensions of rotary kiln
 Lower specific thermal load of kiln tube
 Increased refractory life
 Possibility of large capacities (8000 t/d per kiln)
 Independent calcining fuel control
 More stable kiln operation
 Fire low grade fuel in precal
 Lower downtime (stability, refractory life)
 Increase capacity of existing pre-heater kilns
 Volatile problems
 more easily controlled

Friday, February 5, 2021

 PRECALCINER COMBUSTION
PERFORMANCE CONCERNS

1) Fuel Distribution

2) Retention Time

3) Air-Gas supply favorable

4) Raw Mix / Fuel / Air Mix Uniform

Friday, February 5, 2021

 THERMAL PROFILES

Dry Process Wet Process

Feed preheating Calcining Clinkering Cooling 4450 Slurry Evaporation Feed preheat Calcination Clinkering Cooling 4450
preheat
2400 4200 2400 4200
2200 2200 3850
3850
2000 3500 2000 3500
1800 1800 3150
3150

deg. F
deg. F
1600

deg. C
deg. C

1600 2800 2800

1400 1400 2450
2450
1200 1200 2100
Gas 2100
1000 1000 Gas 1750
1750
800 800 1400
1400
Material 600
600 1050 1050
400 700
400 700 Material
200 350
200 350

20 80 100 140 180 220 260 300 340 380 420 460 500 540 ft
20 80 100 140 180 220 260 300 340 380 420 460 500 540 ft
m
m 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160
10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160

Feed
Feed
End
End

Friday, February 5, 2021

 THERMAL PROFILES

Pre-heater Pre-calciner

Preheating Calcining Clinkering Cooling 4450 Feed Calcining Clinkering Cooling 4450
preheating
2400 4200 2400 4200
2200 2200 3850
3850
2000 3500 2000 3500

1800 1800 3150

3150

deg. F
deg. F
1600

deg. C
1600 2800
deg. C

2800
1400 2450
1400 2450
1200 Gas 2100
1200 2100
Gas
1000 1750
1000 1750
800 1400
800 1400
600 Material
600 1050
Material 1050
400 700
400 700
200 350
200 350

20 40 60 80 100 120 140 ft

20 40 60 80 100 120 140 ft
m
10 20 30 40
m
10 20 30 40
1 2 3

Flash
Calciner

Friday, February 5, 2021

 ZONES OF THE KILN

1) Evaporation of free water

2) Dehydration of water combined in clay
3) Calcining
4) Sintering
5) Cooling

Friday, February 5, 2021

 EVAPORATION ZONE
(100 - 400 °C)
 100-400 °C:
H2O (l) + heat  H2O (g) H = + 44.2 kJ/mol

Wet Process

Slurry Evaporation Feed preheat Calcination Clinkering Cooling 4450

preheat
2400 4200
2200 3850
2000 3500
1800 3150

deg. F
1600
deg. C

2800
1400 2450
1200 2100
1000 Gas 1750
800 1400
600 1050
400 700
Material
200 350

20 80 100 140 180 220 260 300 340 380 420 460 500 540 ft

m
10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160

Feed
End

Friday, February 5, 2021

 DEHYDRATION ZONE
(350 - 650 °C)
 350-650 °C:
 Clay loses water of crystallization
2SiO2•Al2O3•2H2O + heat  2SiO2•Al2O3 + 2H2O
H = +274 kJ/mol
 400 °C:
 Decarbonization of magnesium carbonate
MgCO3 + heat  MgO + CO2 H = +120 kJ/mol
 Vapourization, oxidation of organics & suphides
FeS2 + O2  Fe2O3 + SO3
 550 °C:
 Decomposition of calcium carbonate
 900 °C in pure state
 occurs sooner due to impurities and acidic environment

Friday, February 5, 2021

 CALCINING ZONE
(600 - 1200 °C)
 600-900C
 break down of clays minerals into oxides
Al2O3•SiO2  Al2O3 + SiO2
 solid solution reactions with clay oxides
CaO, SiO2, Al2O3  CA, C12A7, CS, C2S.CC, C2S
 850-900°C
 rapid decomposition of calcium carbonate
CaCO3  CaO + CO2 H = +474 kJ/mol
 free-lime reacts first with silica
2CaO + SiO2  2CaO.SiO2 H = -143 kJ/mol
 free-lime then reacts with alumina & iron
2CaO + Al2O3, Fe2O3  2CaO.Al2O3, 2CaO.Fe2O3

Friday, February 5, 2021

 CALCINATION ZONE
SPEED OF DECARBONATION
 Temperature of the material,
 determines the partial pressure of
decomposition of CaCO3 to CO2.
 Gas temperature
 controls the transfer of heat from decarbonated
material to the crystals of SiO2, Fe2O3, Al2O3
 The partial pressure of CO2,
 sum of the decomposition pressure of CaCO3
and the pressure of the combustion gases

Friday, February 5, 2021

 CALCINING ZONE
(600 - 1200 °C)
 Also at 850-900°C
 Free CaO combines with SO3 to give anhydrite
CaO + SO3  CaSO4
 SO3 affects the compounds formed
CaO + Na2O, K2O  Na2SO4, K2SO4, 3K2SO4.Na2SO4
 If alkalis in excess
Na2O + C3A  NaC8A3
K2O + C2S  KC23S12

Friday, February 5, 2021

 ALKALI SULPHATE REACTIONS
(850-900 °C)
 Changes in alkali balance may change quality
 cycling which is often not noticed in clinker sampling
 erratic setting times, strengths, flow problems
 Build-ups, rings

 3(K2SO4.Na2SO4)
 double salts: calcium langbenite, syngenite
 flow problems
 NaC8A3
 quicker setting time, higher water demand
 lower strength development
 KC23S12
 behaves like C2S; but stable compound, will not form C3S
 lower C3S (strength), higher f-CaO (setting time)

Friday, February 5, 2021

 BEGNINING OF BURNING ZONE
KILN OPERATORS VIEW
 Upper transition (5-15 min)
 Exothermic clinkerization reaction starts
 analoguous to a combustion
 beginning of reaction termed “Ignition Point”
 Ignition Point
 temperature of the material rises very quickly
 visually look up the BZ and under the flame
 material changes from black to white within 5-6 ft
 As the clinkerization progresses
 presence of the flux
 the material starts to stick on walls and coating
 then starts tumbling at an angle of ~45 degre

Friday, February 5, 2021

 CLINKERING ZONE
(1200-1450 °C)
 1200°C
 Belite (C2S) is completely formed
2CaO + SiO2  2CaO.SiO2 H = -125 kJ/mol
 C12A7, CaO becomes C3A
 Solid solution of C4AF
4CaO + Al2O3 + Fe2O3  C4AF H = -50.4 kJ/mol
 1250- 1300°C
 C3A and C4AF liquefy and constitute the flux.
 Alkalis, SO3 volatilized
R2SO4, CaSO4 + heat  R2O, CaO + SO2 + 1/2 O2
 if reducing condition: Fe2O3  2FeO + 1/2O2
 1310-1450 °C
CaO + C2S  C3S H = -125 kJ/mol
 facilitated by presence of liquid; also solid-solid reaction
Friday, February 5, 2021
 END OF BURNING ZONE
KILN OPERATORS VIEW
 Lower limit :
 Difficult to precisely define end of BZ
 Could be at 2-3 or 15 feet from the nosering
 Depends on the temperature of the material in
the burning zone
 Position of the burner pipe important
 One arbitrary rule is that the front end of the coating
is where the burning zone ends

Friday, February 5, 2021

 COOLING ZONE
(1400-1250 °C)
 1400°C to 1250°C
 -C2S crystallizes to the more hydrolizable ß-C2S
 If slowly cooled C3S will decompose to C2S, CaO
(Birefringence)
 Alkali sulfates precipitate from the melt
 C3A and C4AF crystallize
 Molten sulfates crystallize

Friday, February 5, 2021

PHASE DIAGRAM

Friday, February 5, 2021

 HEAT OF REACTION IN THE KILN

HEAT ABSORBED (kJ/kg Clinker)

1) Heating of raw materials from 20 to 450°C 714
2) Dehydration of clay 168
3) Heating of material from 450° to 900°C 820
4) Decarbonation at 900°C 1995
5) Heating the decarbonated material from 900° to 1400°C 525
6) Heat for melting 105

4327

HEAT LIBERATED
1) Crystallization of dehydrated clay 42
2) Formation of clinker phases 420
3) Cooling of clinker from 1400°C to 20°C 1512
4) Cooling of gases from 900°C to 20°C 588

2562

Heat necessary for producing 1 kg clinker 1765

Friday, February 5, 2021
 CONCLUSION

 Kiln system design

 driven by capital cost reduction
 each system has advantages & disadvantages
 Thermal loading is important concept
 Heat input
 calcination - quanitity
 clinkerization - quality
 Complex, obscure thermo-reactions
 explain operational reactions
 important impact on quality

Friday, February 5, 2021

 GLOSSARY
Terminologies
Primary air: Combustion air introduced through a burner pipe.
Secondary air: Combustion air from an adjacent part of the process.
Tertiary air: Typically, hot gasses from the clinker cooler. Combustion air
introduced from a point in the process not adjacent to the
burner. Typically, hot clinker cooler gases used in the
precalciner.
Kiln back end: Feed end of the kiln, kiln inlet.
Kiln front end: Kiln clinker discharge.
Burning zone: Hottest area of the kiln. C3S is formed here.
Calcining zone: Area of kiln/preheat tower where the material is heated, driving
off all gases short of fusing it.
Clinker cooling zone: Front end at the kiln where clinker is somewhat cooled prior to
discharge.
Clinker quenching: Quick, air cooling of clinker in the clinker cooler.
ID fan: Induced Draft fan used to draw air through the kiln
Kiln coating: Natural build-up on the kiln refractory that protects the
refractory and insulates the kiln.
Volatilization: Evaporation of elements at high temperatures.

Friday, February 5, 2021