02-01-podfa-basic Know How Of Clinker Production.ppt

Clinker Production – Basic know how of clinker production Training PODFA New Kiln 7 Dry Line Project - JSC Podilsky Cement / Ukraine November 2010

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Clinker Production – chemistry basics - Content

What is cement? Clinker minerals Raw material Clinker production Phase diagram Burnability index BI Grinding fineness Separation factor SF Phase composition Calculation with Bogue formula Basic know how of clinker production Training PODFA November 2010 2

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What is cement ? Answer (EN 197-1)

Cement is a hydraulic binder, i.e. a finely ground inorganic matter which mixed with water to cement paste solidifies by hydration and hardens to cement stone of a defined strength. The solidified cement remains dimensionally stable and maintains it strength also under water. Basic know how of clinker production Training PODFA November 2010 3

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Clinker minerals - Topics

Alite

3CaO  SiO 2

C3S

Belite

2CaO  SiO 2

C2S

Calciumaluminate

3CaO  Al2O 3

C3A

Brownmillerit

4CaO  Al2O 3  Fe 2O 3

C4AF

Dicalciumferrit

2CaO  Fe 2O 3

C2F

Free lime

CaO

CaOfr.

Basic know how of clinker production Training PODFA November 2010 4

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Clinker minerals Tricalciumsilicate, Alite C3S

C2S

Formation: Above 1250°C by a reaction of C2S and C Can be metastably by rapid cooling

Phases / Structure: Melts at 2070°C Decomposition at temperatures lower than 1250°C

Basic know how of clinker production Training PODFA November 2010 5

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C 3A

C4AF

Clinker minerals Tricalciumsilicate, Alite C3S

C2S

Properties: Highly hydraulic, high initial strength, good afterhardening, moderate setting heat, average tendency towards shrinkage

Smaller alite crystals are: More reactive, easier to grind

Size depends on: Amount and viscosity of melt Fine quartz and calcite favour small crystals Steep temperature profile, short retention time Amount of foreign atoms

C3S can incorporate up to 3% SO3( but lower hydraulicity) Basic know how of clinker production Training PODFA November 2010 6

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C 3A

C4AF

Clinker minerals Electron microscopy record of alite C3S

C2S

Basic know how of clinker production Training PODFA November 2010 7

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C 3A

C4AF

Clinker minerals Dicalciumsilicate, Belite C3S

C2S

Properties: Slower hardening than alite, reduced setting heat. Same strength as alite in the long term. Takes up larger amounts of SO3 than alite - modification stabilized by alkali Normally only ß-modification found Very difficult to quantify by X-ray diffraction Hard to grind (harder than alite) Spherical crystal shape Basic know how of clinker production Training PODFA November 2010 8

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C 3A

C4AF

Clinker minerals Electron microscopy record of belite C3S

C2S

Basic know how of clinker production Training PODFA November 2010 9

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C 3A

C4AF

Clinker minerals Tricalciumaluminate C3S

C2S

Properties: Responsible for early setting times ("rapid setting") Fast hardening, high initial strength, high setting heat, high tendancy towards shrinkage, susceptible to sulphate attack Alkalies lead to a change in modification cubic

orthorhombic

monoclinic

changed reactivity

absolute amount of C3A rises with Na2O-content

Absolute content and reactivity important for gypsum optimization Basic know how of clinker production Training PODFA November 2010 10

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C 3A

C4AF

Clinker minerals Brownmillerite C3S

C2S

Properties: Low hydraulic properties, low setting heat, Reduced tendency towards shrinkage Can incorporate 3-4% MgO Contains most of the alkalies 3-5 times higher conc. of K2O and 4-10 times more Na2O than silicates alite and belite Larger amounts of C4AF

difficult to grind

Quick crystallization Basic know how of clinker production Training PODFA November 2010 11

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C 3A

C4AF

Clinker minerals

3CaO  SiO 2

Alit Belit

2CaO  SiO 2

Aluminat

3CaO  Al 2 O 3

Brownmillerit

4CaO  Al2 O 3  Fe 2 O 3

Dicalciumferrit

2CaO  Fe 2 O3

Free lime

CaO

CaO

SiO2

Al2O3

C3S

high

medium

low

C2S

80 %

63 %

45 %

C3A

32 %

16 %

0%

C4AF

14 %

8%

4%

C 2F

15 %

11 %

7%

CaOfr. Fe2O3

MgO

TiO2

Mn2O3

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K2O

Na2O

Raw material CaO

SiO2

Al2O3

Fe2O3

MgO

TiO2

Enters raw mix as: Massive limestone, marl, chalk, fossiliferous limestone argillaceous limestone, blue lias, dolomite, feldspars, clay etc.

Burnability: Large amounts of crystal defects in calcite favourable Grain size influence less important than SiO2 Impurities of Si, Al, Fe lower decomposition temperature

Reactivity sequence: easy: calcite > dolimite > ankerite > marble :difficult Basic know how of clinker production Training PODFA November 2010 13

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Mn2O3

K2O

Na2O

Raw material CaO

SiO2

Al2O3

Fe2O3

MgO

TiO2

Enters raw mix: as quartz (coarse grained quartz) as diatomite (fossile origin),Silex (very finly dispersed) from clay minerals, feldspars, mica, slags (fine) from fuel ash (fine)

Sequence of raw material reactivity: quartz < chalcedony < opal < cristobalite < silica from feldspars (albite, orthoclas) < silica from mica / amphiboles < silica from clay minerals < silica of glassy slags

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Mn2O3

K2O

Na2O

Raw material CaO

SiO2

Al2O3

Fe2O3

MgO

TiO2

Enters raw mix as: Pyrite cinder Fe2O3 (industrial waste) Hematite Fe2O3 (natural material) Laterite Fe2O3 + FeOOH (natural material) Hammer slag Fe3O4 ( industrial waste) Clayous Fe2O3 carriers eg. ferric illite

Reactivity: Important influence on burnability

Basic know how of clinker production Training PODFA November 2010 15

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Mn2O3

K2O

Na2O

Raw material CaO

SiO2

Al2O3

Fe2O3

MgO

TiO2

Manganese oxide: Leads to more dense clinker (lower viscosity) Acts as mineralizer Normally less than 2 % Normally found in C4AF phase

Basic know how of clinker production Training PODFA November 2010 16

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Mn2O3

K2O

Na2O

Raw material CaO

SiO2

Al2O3

Fe2O3

MgO

TiO2

Enters raw mix as: Impurity in iron ores, from residual minerals like ilmenite, rutile

Effect: Substitutes for Si, Al, Fe in clinker phases Reduces surface tension of the liquid phase, drop in viscosity Favourable for alite formation Gives darker colour to clinker Retards early hydration, slows down setting times 1% TiO2 can increase 3-90 day strength

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Mn2O3

K2O

Na2O

Raw material CaO SiO2 Enters raw mix:

Al2O3

Fe2O3

MgO

TiO2

From nearly all main components used especially dolomite (Ca, Mg)CO3, rarely magnesite silcates like diopsite, chlorites etc.

Role in burning process: MgO lowers viscosity of melt Favours mineral formation (increase for alite and C4AF, lowers C2S, C3A)

Effects: Some authors: up to 3% MgO can increase cement strength ? Creates defect lattices of alite and belite Gives darker cement color Approx. 2% can be incorporated in clinker phases Basic know how of clinker production Training PODFA November 2010 18

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Mn2O3

K2O

Na2O

Raw material CaO

SiO2

Al2O3

Fe2O3

MgO

TiO2

Enters raw mix: From orthoclas, albite, plagioclas, micas, illite, montmorillonite

Effects: Stabilisation of the -modification of belite Preferably incorporated in belite and C3A (Na > K) Negative effects in concrete (with active SiO2 ) Responsible for inner recycles

Increasing alkali volatization in the order feldspars < micas < illit and montmorillonite

Increased volatility by adding chloride (e.g. 0.5% CaCl2) increase in H2O -partial pressure Basic know how of clinker production Training PODFA November 2010 19

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Mn2O3

K2O

Na2O

Clinker production Preheater Precalciner

Transition-Zone

Cooling-Zone

Calciner-Zone

Sinter-Zone

M.-%

T / °C 1400 1200

CaCO3

CaOfrei

1000 C3 S

800

C2 S

600

SiO2 Al2O3 Fe2O3

400 C12A7 5

C2A,F 10

C4AF 15

C3A

Melt

20

25

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200 30

t / min

Clinker production Temp. / °C

Process

20 … 200

Drying

200 … 450

Elimination of adsorbed water

450 … 600

Decomposition of clay, formation of metakaolinit

Al (OH) Si O  2(Al O  2SiO )  4H O

600 … 950

Decomposition of metakaolinit

Al O  2SiO  Al O  2SiO CaCO  CaO  CO

800 … 1000

Decomposition of limestone, formation of CS and CA

1000 … 1300

Formation of clinker minerals

1300 … 1450

Chemical reactions

4

2

8

3

4

10

2

2

2

3

3

2

2

2

2

3CaO  2SiO  Al O  2(CaO  SiO )  CaO  Al O CaO  SiO 2  CaO  2CaO  SiO 2 2

2

3

2

2

CaO  Al2 O 3  2CaO  3CaO  Al2 O 3 CaO  Al2 O 3  3CaO  Fe2 O3  4CaO  Al2O 3  Fe 2 O 3

2CaO  SiO 2  CaO  3CaO  SiO 2

Formation of C3S

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3

Phase diagram CaO

SiO2

Al2O3

Fe2O3

MgO

TiO2

0 100

80

40 60

SiO 2

Ca Oi n%

20

in %

60

40

PZ-Klinker 80

20

100 0

40

20

60

80

100

Al2O3 + Fe2O3 in % Basic know how of clinker production Training PODFA November 2010 22

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Mn2O3

K2O

Na2O

Phase diagram Hydraulic Modulus CaO

SiO2

Al2O3

Fe2O3

MgO

TiO2

K2O

Mn2O3

Na2O

0

100 20

1.7 … 2.3

Typical:

~ 2.0

60

in %

Limit value:

40

SiO 2

CaO SiO 2  Al 2 O 3  Fe 2 O 3

Ca Oi n%

HM 

80

60

40

OPC-Clinker 80

20

100 0

20

40

60

Al2O3 + Fe2O3 in % Basic know how of clinker production Training PODFA November 2010 23

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80

100

Phase diagram Lime standard I (Kühl) CaO

SiO2

Al2O3

Fe2O3

MgO

TiO2

K2O

Mn2O3

Na2O

0

100 20 80

90 … 100

Typical:

92 … 98

60

in %

Limit value:

in %

40

SiO 2

100  CaO 2,8  SiO 2  1,1  Al 2 O 3  0,7  Fe 2 O 3

Ca O

LS I 

60

40

OPC-Clinker 80

20

100 0

20

40

60

Al2O3 + Fe2O3 in % Basic know how of clinker production Training PODFA November 2010 24

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80

100

Phase diagram Lime standard II (Lea, Parker) CaO

SiO2

Al2O3

Fe2O3

MgO

TiO2

K2O

Mn2O3

Na2O

0

100 20

60

in %

Limit value: Typical:

40

60

90 … 100 92 … 98

SiO 2

100  CaO 2,8  SiO 2  1,18  Al 2 O 3  0,65  Fe 2 O 3

Ca O

LS II 

in %

80

40

OPC-Clinker 80

20

100 0

20

40

60

Al2O3 + Fe2O3 in % Basic know how of clinker production Training PODFA November 2010 25

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80

100

Phase diagram Lime standard III (Spohn, Woermann, Knöfel) CaO

SiO2

Al2O3

Fe2O3

MgO

TiO2

K2O

Mn2O3

Na2O

0

100 20

60

in %

Limit value: Typical:

40

60

90 … 100 92 … 98

SiO 2

100  CaO  0,75  MgO 2,8  SiO 2  1,18  Al 2 O 3  0,65  Fe 2 O 3

Ca O

LS III 

in %

80

40

OPC-Clinker 80

20

100 0

20

40

60

Al2O3 + Fe2O3 in % Basic know how of clinker production Training PODFA November 2010 26

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80

100

Phase diagram Lime saturation factor CaO

SiO2

Al2O3

Fe2O3

MgO

TiO2

K2O

Mn2O3

Na2O

0

100 20

40 60

SiO 2

100  CaO 2,8  SiO 2  1,65  Al2 O 3  0,35  Fe 2 O 3

Ca O

LSF 

in %

80

in %

60

40

OPC-Clinker 80

20

100 0

20

40

60

Al2O3 + Fe2O3 in % Basic know how of clinker production Training PODFA November 2010 27

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80

100

Phase diagram Silica ratio CaO

SiO2

Al2O3

Fe2O3

MgO

TiO2

K2O

Mn2O3

Na2O

0

100 20

1.8 … 3.9

Typical:

2.2 … 2.6

60

in %

Limit value:

40

SiO 2

SiO 2 Al 2 O 3  Fe 2 O 3

Ca Oi n%

SR 

80

60

40

OPC-Clinker 80

20

100 0

20

40

60

Al2O3 + Fe2O3 in % Basic know how of clinker production Training PODFA November 2010 28

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80

100

Phase diagram Silicic acid ratio CaO

SiO2

Al2O3

Fe2O3

MgO

TiO2

K2O

Mn2O3

Na2O

0

100 20

2.0 … 4.5

Typical:

2.5 … 3.5

60

in %

Limit value:

40

SiO 2

SiO 2 Al2 O 3

Ca O

SAR 

in %

80

60

40

OPC-Clinker 80

20

100 0

20

40

60

Al2O3 + Fe2O3 in % Basic know how of clinker production Training PODFA November 2010 29

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80

100

Phase diagram Alumina ratio CaO

SiO2

Al2O3

Fe2O3

MgO

TiO2

K2O

Mn2O3

Na2O

0

100 20

1.5 … 2.9

Typical:

1.6 … 2.0

60

in %

Limit value:

40

SiO 2

Al 2 O 3 Fe 2 O 3

Ca O

AR 

in %

80

60

40

OPC-Clinker 80

20

100 0

20

40

60

Al2O3 + Fe2O3 in % Basic know how of clinker production Training PODFA November 2010 30

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80

100

Phase diagram Sodium equivalent CaO

SiO2

Al2O3

Fe2O3

MgO

TiO2

Na 2 O (equ.)  Na 2 O  0,658  K 2 O

Basic know how of clinker production Training PODFA November 2010 31

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Mn2O3

K2O

Na2O

Phase diagram Liquid phase CaO

SiO2

Al2O3

Fe2O3

MgO

TiO2

Mn2O3

LEA1400 C  2,95  Al2 O 3  2,2  Fe 2 O 3  MgO  Na 2 O  K 2 O

typical: 24 … 28

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K2O

Na2O

Burnability Index BI CaO BI 

SiO2

Al2O3

Fe2O3

MgO

TiO2

F1  CaO1350C  F2  CaO1400C  F3  CaO1450 C  F4  CaO1500 C  F8 F5  x F6  CaO1350C  F7  CaO1500 C

very easy:

< 60

easy:

60 – 80

normal:

80 – 100

slightly difficult:

100 – 120

difficult:

120 – 140

very difficult:

140 – 160

extremly difficult:

>160

Basic know how of clinker production Training PODFA November 2010 33

Mn2O3

Polysius

K2O

Na2O

Grinding fineness CaO

SiO2

Al2O3

180

Fe2O3

MgO

TiO2

K2O

Mn2O3

Na2O

extremly difficult

R 90µm ~ 12 - 18%

KST 100 160

Burnability Index BI

R 200µm ~ 1 - 3%

very difficult

140

difficult KST 95

120

slightly difficult KST 92

100

normal KST 90

80

easy

60

very easy

40 4

6

8

10

12

Fineness %R90µm

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14

16

18

Separation Faktor SF CaO

SFLSF 

SiO2

Al2O3

Fe2O3

MgO

TiO2

KST I ( 32µm) KST I (RM)

Difficulter burnability: > 1,2 Typical:

0,8 … 1,2

Easier burnability:

< 0,8%

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Mn2O3

K2O

Na2O

Phase composition Mixture No. 1 Raw mix compounds: Limestone hard Kolub Marl Clay Mix ( Yellow : Diverse = 1 : 2 ) Iron Ore Fuel: Coal Mixture No. 2 Raw mix compounds: Limestone soft Kolub Marl Clay Mix ( Yellow : Diverse = 1 : 2 ) Iron Ore Fuel: Coal

content [%] 77.15 9.65 11.87

heat consumption: 740 kcal/kg

1.33 content [%] 7.29 content [%] 75.80 9.65 12.84

heat consumption: 740 kcal/kg

1.71 content [%] 7.32

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Phase composition % LOI % SiO2 % Al2O3 % TiO2 % Fe2O3 % Mn2O3 % CaO % MgO % SO3 (total sulfur) % P 2 O5 % Na2O % K2O % Cl Total

based on 36.30 13.57 2.78 0.14 2.18 0.20 42.93 1.02 0.57 0.08 0.14 0.57 0.003 100.47

LOI

free of LOI

free of LOI + ash

--21.15 4.33 0.22 3.40 0.31 66.89 1.59 0.88 0.12 0.22 0.88 0.005 100.00

--22.25 4.76 0.24 3.59 0.31 67.02 1.64 1.16 0.12 0.23 0.96 0.010 102.30

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free of LOI + ash

(based on 100%)

--21.75 4.66 0.23 3.51 0.30 65.51 1.60 1.14 0.12 0.23 0.94 0.009 100.00

Phase composition % LOI % SiO2 % Al2O3 % TiO2 % Fe2O3 % Mn2O3 % CaO % MgO % SO3 (total sulfur) % P 2 O5 % Na2O % K2O % Cl Silica ratio Alumina ratio Lime standard (KUEHL)

based on

LOI

36.30 13.57 2.78 0.14 2.18 0.20 42.93 1.02 0.57 0.08 0.14 0.57 0.003

free of LOI

free of LOI + ash

--21.15 4.33 0.22 3.40 0.31 66.89 1.59 0.88 0.12 0.22 0.88 0.005

--22.25 4.76 0.24 3.59 0.31 67.02 1.64 1.16 0.12 0.23 0.96 0.010

2.56 1.23 100.1

(based on 100%)

--21.75 4.66 0.23 3.51 0.30 65.51 1.60 1.14 0.12 0.23 0.94 0.009 2.50 1.28 95.0

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free of LOI + ash

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Phase composition % LOI % SiO2 % Al2O3 % TiO2 % Fe2O3 % Mn2O3 % CaO % MgO % SO3 (total sulfur) % P 2 O5 % Na2O % K2O % Cl % Liquid phase (acc. to LEA 1400 °C)

based on 36.30 13.57 2.78 0.14 2.18 0.20 42.93 1.02 0.57 0.08 0.14 0.57 0.003

LOI

free of LOI

free of LOI + ash

--21.15 4.33 0.22 3.40 0.31 66.89 1.59 0.88 0.12 0.22 0.88 0.005

--22.25 4.76 0.24 3.59 0.31 67.02 1.64 1.16 0.12 0.23 0.96 0.010

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free of LOI + ash

(based on 100%)

--21.75 4.66 0.23 3.51 0.30 65.51 1.60 1.14 0.12 0.23 0.94 0.009 25.6

Phase composition % LOI % SiO2 % Al2O3 % TiO2 % Fe2O3 % Mn2O3 % CaO % MgO % SO3 (total sulfur) % P 2 O5 % Na2O % K2O % Cl % C3 S % C2 S % C3 A Basic know how of clinker production Training PODFA % C4AF November 2010 40

based on 36.30 13.57 2.78 0.14 2.18 0.20 42.93 1.02 0.57 0.08 0.14 0.57 0.003

LOI

free of LOI

free of LOI + ash

--21.15 4.33 0.22 3.40 0.31 66.89 1.59 0.88 0.12 0.22 0.88 0.005

--22.25 4.76 0.24 3.59 0.31 67.02 1.64 1.16 0.12 0.23 0.96 0.010

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free of LOI + ash

(based on 100%)

--21.75 4.66 0.23 3.51 0.30 65.51 1.60 1.14 0.12 0.23 0.94 0.009 ? ? ? ?

Calculation with Bogue formula C3S C2S CaOfr.

LS  CaO -  2,8  SiO 2  1,65  Al2 O3  0,35  Fe 2 O3 

C3A C4AF

AR 

Al2 O 3* Fe 2 O 3*

C2F AR > 0,638; LS = negativ AR < 0,638; LS = negativ AR > 0,638; LS = positiv AR < 0,638; LS = positiv

   

Calculation Group 1 A Calculation Group 1 B Calculation Group 2 A Calculation Group 2 B

* - molecular weights Basic know how of clinker production Training PODFA November 2010 45

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Calculation with Bogue formula AR > 0,638; LS = negativ  Calculation Group 1 A

C2S

 4.071  CaO  0.46   3.043  Fe2 O3   0.62   2.65  Al2 O3 - 1.692  Fe2 O3   1.87  SiO 2   4.071 CaO - 7.6  SiO 2  6.718  Al2O3  1.430  Fe 2O3  8.6 2.87 SiO   SiO  0.26 Al  C23S O3  1.079  Fe2O3  3.071 CaO 2 2 5.068

C3A

 2.65  Al2 O3 - 1.692  Fe 2 O3

C3S

C4AF

 3.043 Fe 2 O 3

C 4 AF  3.043 Fe 2 O 3 C3 A  2.65 Al 2 O 3

C3A  1.692 Fe 2 O 3

3  CaO  0.62 C3A

C3S  4.071 CaO

4  CaO  0.46 C 4 AF

2  CaO  1.87 SiO 2

SiO 2  0.26 C3S

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C 2S  2.87 SiO 2

Calculation with Bogue formula AR < 0,638; LS = negativ  Calculation Group 1 B

C3S

 4.071 CaO - 7.6  SiO 2  4.479  Al2 O3  2.860  Fe 2O3

C2S

 8.6  SiO 2  3.379  Al2 O 3  2.157  Fe2O 3  3.071 CaO

C2F

 1.702  Fe 2O 3 - 2.666  Al 2O 3

C4AF

 4.766  Al 2 O 3

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Calculation with Bogue formula AR > 0,638; LS = positiv  Calculation Group 2 A

C3S CaOfr. C3A C4AF

 3.8  SiO 2

 CaO - 2.8  SiO 2  1.65  Al2 O3  0.351 Fe2O3  2.65  Al2O 3 - 1.692  Fe 2 O3  3.043  Al 2 O 3

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Calculation with Bogue formula AR < 0,638; LS = positiv  Calculation Group 2 B

C3S CaOfr. C2F C4AF

 3.8 SiO 2  CaO  2.8  SiO 2  1.1 Al2O3  0.702  Fe2 O3  1.702  Fe 2O3 - 2.666  Al2O3  4.766  Al 2 O 3

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Phase composition based on % LOI % SiO2 % Al2O3 % TiO2 % Fe2O3 % Mn2O3 % CaO % MgO % SO3 (total sulfur) % P2O5 % Na2O % K2O % Cl % C3S % C2S % C3A % C4AF Basic know how of clinker production

36.30 13.57 2.78 0.14 2.18 0.20 42.93 1.02 0.57 0.08 0.14 0.57 0.003

LOI

free of LOI

free of LOI + ash

--21.15 4.33 0.22 3.40 0.31 66.89 1.59 0.88 0.12 0.22 0.88 0.005

--22.25 4.76 0.24 3.59 0.31 67.02 1.64 1.16 0.12 0.23 0.96 0.010

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free of LOI + ash

(based on 100%)

--21.75 4.66 0.23 3.51 0.30 65.51 1.60 1.14 0.12 0.23 0.94 0.009 63.0 14.9 6.5 11.6

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