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Thermodynamics in
Material Engineering
Research Group of the Dept. MTM
K.U.Leuven

Slag Solidification with Water-

Cooled Probe Technique
Mieke Campforts
Dept. Metallurgy and Materials Science
KULeuven (Belgium)
1
 Overview
z Introduction
z Slag solidification
z Water-Cooled Probe Technique

z Experimental
z Results
z Conclusions
z Future work

2
 Introduction Slag Solidification
z Freeze lining

= crust of solidified process material

on a cooled reactor wall
Water
cooling

Freeze
lining
3
 Introduction Slag Solidification
z Freeze lining
z Steady state: Heat input = Heat removal

z Transient state: Heat input Heat removal =

Latent heat (melting/solidification)

4
 Introduction Slag Solidification
z Advantages
z Increased process intensities

z Longer campaign times

z Increased freedom in slag chemistry

z Drawbacks
z Safety? Break through of reactor wall
z Stability? Total solidification of the bath
z Heat losses? Cooling reactor wall
5
Introduction Water-Cooled Probe
Technique

6
 Overview
z Introduction
z Experimental
z Industrial slag
z Synthetic slag

z Results
z Conclusions
z Future work

7
 Experimental Industrial Slag

z Industrial non-ferrous slag:

Lead blast furnace
z Composition:
main components
SiO2 CaO Fe Al2O3 ZnO MgO
25.60 18.15 26.00 6.35 5.41 1.35
minor components
S, Pb, Cu, As, Ni (matte, lead, speiss)
Cr2O3 (refractory)
8
 Experimental Industrial Slag
z Thermodynamic calculations Solidification path
z Data bases not optimized for all components
z Simplify system to main components

Equilibrium Scheil-Gulliver

9
 Experimental Synthetic Slag
z Synthetic Isasmelt slag
z Lead and Cupper production
z Only main components of industrial slag
z Composition

SiO2 PbO Fe2O3 CaO ZnO

20.9 40.9 21.8 8.5 7.9

No minor components!

10
 Experimental Synthetic Slag
z Thermodynamic calculations
z Data bases optimized for components in a large
composition range
Equilibrium solidification path

11
 Overview
z Introduction
z Experimental
z Results
z Industrial slag
z Synthetic slag

z Conclusions
z Future work

12
 Results Industrial Slag
z Microstructure

PROBE

BATH
200 m
13
Results Industrial Slag

1. Wustite
precipitate in
melilite matrix
2. Melilite
3. Spinel
4. Olivine
5. Amorphous
matrix
6. Matte/Speis/
Lead 14
 Results Industrial Slag
z 4 zones

PROBE

BATH
200 m
15
 Results Industrial Slag
z Amorphous matrix with precipitates

PROBE

200 m
BATH
200 m
16
 Results Industrial Slag
z Equiaxial crystals

PROBE

200 m
BATH
200 m
17
 Results Industrial Slag
z Cellular crystals

PROBE

200 m

BATH
200 m
18
 Results Industrial Slag
z Remaining slag bath

PROBE

200 m

BATH
200 m
19
 z Compared with the
equilibrium solidification
path

PROBE

BATH 20
200 m
 z Compared with the
Scheil-Gulliver
solidification path

PROBE

BATH 21
200 m
 Results Industrial Slag
z Concentration gradient (?)

22
 Results Industrial Slag
z Concentration gradient (?)

Melilite Bath

No enrichment in FeO (wustite)

23

Concentration gradient is limited

 Results Industrial Slag
z Composition phases: CaO

24
 Results Industrial Slag
z Composition phases: CaO

Melilite Bath

Matrix
Matrix

Spinel
25
 Results Industrial Slag
z Composition phases: SiO2

26
 Results Industrial Slag
z Composition phases: SiO2
Bath
Melilite

Matrix Matrix

Spinel
27
 Results Industrial Slag
z Composition phases: FeO

28
 Results Industrial Slag
z Composition phases: FeO
Bath

Spinel

Matrix

Matrix

Melilite
29
 Results Synthetic Slag
z Microstructure
PROBE

BATH
200 m
30
 z Compared with the
equilibrium solidification
path

PROBE

31
BATH
200 m
 Results Synthetic Slag
z Concentration gradient (?)

32
 Results Synthetic Slag
z Concentration gradient (?)
Bath

33
 Overview
z Introduction
z Experimental
z Results
z Conclusions
z Freeze lining
z Industrial slag
z Synthetic slag

z Modelling microstructure

z Future work
34
Conclusions Freeze Lining Industrial Slag
z Complex solidification behaviour
z Glass formation
z Cellular crystals/dendrites
z Eutectic growth

z primary phase
z Intermediate cooling rates = a mushy zone

35
Conclusions Freeze Lining Synthetic Slag
z Similar to industrial slag:
z 4 zones
z Amorphous
z Equiaxial crystals
z Dendrites
z Remaining slag bath

z Mushy zone at intermediate cooling rates

z Less complex
z Less phases that form
z Less components
36
 Conclusions Modeling Microstructure
z Microstructure = strongly dependent on thermal
history
z Model system:
z Sufficiently known thermodynamic databases!
z Implementing
z Heat transport
z Mass transport
z Glass phase metastable phases
z Nucleation criteria for preferred phase(s) to form
z Growth criteria for preferred phase(s) to grow
z Anisotropy 37
 Overview
z Introduction
z Experimental
z Results
z Conclusions
z Future work

38
 Future work
z Freeze lining:
z Experimental work:
Steady state
z Influence slag bath temperature
z Influence slag properties
Transient
z Modeling work:
z Microstructure

z Slag:
z SiO2-PbO-Fe2O3-CaO-ZnO (?)
z SiO2-CaO-Al2O3 39