Page 1
Oxides and Pyrometallurgy
- Copper Extraction from Sulfide Concentrates
- Using Equilib Program
• Selection of databases
• Phase selection
• ?Slag and ?Monoxide
• Transition calculation
2010MontrealOxides and Pyrometallurgy 1
• Transition calculation
• Export of results to Excel and plotting
- Phase Diagrams of Oxide Systems
• In equilibrium with metals
• At fixed or variable oxygen pressure
• Being on a join
Page 2
Copper Extraction from Sulfide Concentrates
Copper SulfideConcentrate SMELTING
Blast FurnaceReverberatory Flash
MitsubishiNoranda
Matte
Slag Discardor Treatment
25-30% Cu28-34% Fe28-34% S2-6% SiO2
Small amount of Pb, Zn, Ni, Ca, etc.
~1250oCP(O2) = 10-9-10-11
atmP(S2) = 10-2 atm
Slag
0.2-2% Cu0.2-1.3% S
40-73% Cu
ROASTING
2010MontrealOxides and Pyrometallurgy 2
CONVERTING
Blister Copper
Matte
Slag
or Treatment
~1250oCP(O2) = 10-6-10-9 atmP(S2) = 10-6 -10-7 atm
40-73% Cu30-6% Fe30-20% S2-8% Cu
25% SiO2
SlagCleaning
Page 3
Direct Smelting: Matte/Slag/Cu equilibrium- Can all three phases Matte/Slag/Cu be in equilibriu m?
- Operating variables:
• Temperature
• Oxygen pressure
• Fe/SiO2 ratio in the Slag
• Amount of CaO in the Slag
- Subjects to examine:
2010MontrealOxides and Pyrometallurgy 3
• Losses of Cu into Slag
• Distribution of minor elements, Pb and Zn, among Matte, Slag and Cu
- Chemical system: Cu-Fe-Si-O-S + Ca-Pb-Zn
- Does this task make sense?
- At T=const there are 4-2=2 degrees of freedom => fix P(O2), vary Fe/SiO2
- Study the effect of CaO at constant amount of CaO in the Slag
- Pb(Slag)/Pb(Cu) will approach a constant as the amount of Pb approaches zero
Page 4
Fe-Cu-O-S System
2010MontrealOxides and Pyrometallurgy 4
Page 5
Cu-S System
[79Mou]
[76Bal]2 Liquids [79Jud]
[51Sch]
[54Sud]
[90Mas]
[92Gla]
[84Nie]
[72Coo]
[66Ros]
[77Pot]
[60Weh]
[60Joh]
[47Jen]
T ( °° °°
C)
1000
1200
1400
1600
1800
2000
2200
2010MontrealOxides and Pyrometallurgy 5
[79Mou]
fcc + Digenite
[47Jen]
fcc + Chalcocite I
fcc + Chalcocite II
Digenite + Liquid
Covellite + Liquid
Mole fraction S0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
0
200
400
600
800
Page 6
Selection of DatabasesFactSage 6.1 - Summary of Databases
Compound Databases :
Coupled Compound & Solution Databases :
Package:
Other databases :
Overview of databases
FACT53 - FACT 5.3 compound database: Gaseous speciesSGPS - SGTE pure substances database
FToxid - oxide database for slags, glasses, ceramics, refractories Slag, OxidesFTsalt - salt database FThall - Hall alumium database FThelg - aqueous (Helgeson) database
FTmisc - miscealleneous database for sulfides, alloys, etc. Matte, Sulfides, Liquid metalsFTpulp - pulp and paper database (and corrosion and combustion)
2010MontrealOxides and Pyrometallurgy 6
Other databases :
Databases:
Databases :
Other Databases:
FTlite - light metal database (formerly FSlite) Metal phases
FScopp - copper alloy databaseFSlead - lead alloy database
FSstel - steel database Metal phasesFSupsi - ultrapure silicon database
SGnobl - noble metal database (formerly FSnobl) SGnucl - nuclear database
SGTE(2007) - alloy database (formerly SGTE (2004)) Metal phasesSGsold - solders database BINARY - (2004) free alloy database
TDNucl - Thermodata nuclear database
VV
V
V
Page 7
FTmisc - FACT miscellaneous databases
- the system S-Fe-Ni-Co-Cr :
Liquid sulfide [FTmisc-MAT2] – from pure metal to pure sulfur
Solid sulfide phases
- the matte smelting system S-Cu-Fe-Ni-Co-Pb-Zn-As :
Liquid matte [FTmisc-MATT] – liquid sulfide, does not extend to pure metal.
It is designed for calculation of matte / slag / metal equilibria
Consistent with FToxid-SLAG, FTmisc-CuLQ and FTmisc-PbLQ
2010MontrealOxides and Pyrometallurgy 7
It is not consistent with solid sulfide phases
- Liquid copper or speiss [FTmisc-CuLQ] – Cu-Pb-Zn-As-Fe-Ni-Au-S-O
- Liquid Fe [FTmisc-FeLQ] with dilute solutes Al, B, Bi, C, Ca, Ce, Co, Cr, Mg, Mn, Mo, N, Nb, Ni, O, P, Pb, S, Sb, Si, Te, Ti, V, W, Zn, Zr
- Liquid Pb [FTmisc-PbLQ] with dilute solues Ag, As, Au, Bi, Cu, Fe, Na, O, S, Sb, Sn, Zn
Page 8
Selection of Databases
2010MontrealOxides and Pyrometallurgy 8
Page 9
Input for Having Matte + Slag + Cu in Equilibrium
2010MontrealOxides and Pyrometallurgy 9
Page 10
Fixing Oxygen Pressure
2010MontrealOxides and Pyrometallurgy 10
Page 11
Selection of Stoichiometric Solids from FToxid
2010MontrealOxides and Pyrometallurgy 11
Page 12
Selection of Solutions
ASlag or ?Slag
2010MontrealOxides and Pyrometallurgy 12
ASlag or ?Slag?MonoxideDormant phases
Calculatetransitions
Page 13
Transitions
Check that the Matte and Cu phases contain the righ t amount of sulphur
2010MontrealOxides and Pyrometallurgy 13
Page 14
A Series of Calculations
2010MontrealOxides and Pyrometallurgy 14
Page 15
Output Results in Excel
2010MontrealOxides and Pyrometallurgy 15
Page 16
Select Species for Output
2010MontrealOxides and Pyrometallurgy 16
Page 17
Fe-Zn-Si-O System
2010MontrealOxides and Pyrometallurgy 17
Page 18
Cu losses to Slag
Wt%-Cu_FToxid-SLAGA#1
3.6
3.65
3.7
3.75W
t% C
u in
SLA
G
lgP(O 2)=-8
2010MontrealOxides and Pyrometallurgy 18
3.45
3.5
3.55
3.6
1 1.5 2 2.5 3 3.5 4
Fe/SiO2
Wt%
Cu
in S
LAG
Page 19
Distribution of Pb between Slag and Cu
Pb(Sl/Cu)
0.8
1
1.2
1.4W
t% P
b(S
lag)
/Wt%
Pb(
Cu)
lgP(O 2)=-8
2010MontrealOxides and Pyrometallurgy 19
0
0.2
0.4
0.6
1 1.5 2 2.5 3 3.5 4
Fe/SiO2
Wt%
Pb(
Sla
g)/W
t% P
b(C
u)
Page 20
Distribution of Pb between Slag and Matte
Pb(Sl/Mt)
3
4
5
6W
t% P
b(S
lag)
/Wt%
Pb(
Mat
te)
lgP(O 2)=-8
2010MontrealOxides and Pyrometallurgy 20
0
1
2
3
1 1.5 2 2.5 3 3.5 4
Fe/SiO2
Wt%
Pb(
Sla
g)/W
t% P
b(M
atte
)
Page 21
Wt%-Cu_FToxid-SLAGA#1
6.65
6.7
6.75
6.8
6.85
6.9W
t% C
u in
SLA
G
Cu losses to Slag
lgP(O 2)=-7
2010MontrealOxides and Pyrometallurgy 21
6.35
6.4
6.45
6.5
6.55
6.6
1 1.2 1.4 1.6 1.8 2 2.2
Fe/SiO2
Wt%
Cu
in S
LAG
Page 22
Pb(Sl/Cu)
2.5
3
3.5
4
4.5
5
Wt%
Pb(
Sla
g)/W
t% P
b(C
u)
Distribution of Pb between Slag and Cu
lgP(O 2)=-7
2010MontrealOxides and Pyrometallurgy 22
0
0.5
1
1.5
2
2.5
1 1.2 1.4 1.6 1.8 2 2.2
Fe/SiO2
Wt%
Pb(
Sla
g)/W
t% P
b(C
u)
Page 23
Pb(Sl/Mt)
10
12
14
16
18
Wt%
Pb(
Sla
g)/W
t% P
b(M
atte
)
Distribution of Pb between Slag and Matte
lgP(O 2)=-7
2010MontrealOxides and Pyrometallurgy 23
0
2
4
6
8
1 1.2 1.4 1.6 1.8 2 2.2
Fe/SiO2
Wt%
Pb(
Sla
g)/W
t% P
b(M
atte
)
Page 24
Fe-Zn-Si-O System
2010MontrealOxides and Pyrometallurgy 24
Page 25
Fe-O System
2010MontrealOxides and Pyrometallurgy 25
Page 26
Fe-O System
2010MontrealOxides and Pyrometallurgy 26
Page 27
Fe-O System
2010MontrealOxides and Pyrometallurgy 27
Page 28
Fe-O System
2010MontrealOxides and Pyrometallurgy 28
Page 29
Fe-O System
Fe-LIQUID + ASlag-liq
Fe(s) + ASlag-liq
Fe(s2) + AMonoxide
ASlag-liqASlag-liq + gas_ideal
ASpinel + gas_ideal
AM
ono
xid
e
AS
pin
el +
Fe 2
O3(
s)
AS
pin
el +
AM
ono
xid
e
1 atmT
(C)
1200
1400
1600
1800
2010MontrealOxides and Pyrometallurgy 29
Fe(s) + AMonoxide
Fe(s) + ASpinel
Fe2O3(s) + gas_ideal
AS
pin
el +
Fe
AS
pin
el +
AM
ono
xid
e
mole O/(Fe+O)
T(C
)
0 0.2 0.4 0.6 0.8 1
400
600
800
1000
Page 30
Fe-O System
2010MontrealOxides and Pyrometallurgy 30
Page 31
Fe-O System
ASlag-liq + gas_ideal
Fe(s2) + AMonoxide
Fe(s) + ASlag-liq
Fe-LIQUID + ASlag-liq ASlag-liq
AM
onox
ide
AS
pine
l
Fe 2
O3(s
)
P=10000 atm
T(C
)
1200
1400
1600
1800
2010MontrealOxides and Pyrometallurgy 31
Fe2O3(s) + gas_ideal
Fe(s) + ASpinel
Fe(s) + AMonoxide
AS
pine
l
Fe
mole O/(Fe+O)
T(C
)
0 0.2 0.4 0.6 0.8 1
400
600
800
1000
Page 32
Fe-O System
T, K
1200
1300
1400
1500
1600
1700
1800
1900
2000
Magnetite
Hem
atite
Wustite
SlagFe-liq+Slag
Fe-bcc+Slag
Fe-fcc+Slag
Fe-fcc+Wustite
1702
1801
1667
1644
1818
1863
[31Pfe][35Gre]
10-2
10-4
10-6
10-8
1
10-4
10-6
1
10-2
10-10
10-12
10-6
10-8
2010MontrealOxides and Pyrometallurgy 32
FeO-Fe2O3 phase diagram: experimental points and calculated lines. Dashed lines are oxygen isobars (atm).
Weight % Fe2O3
0 10 20 30 40 50 60 70 80 90 100
800
900
1000
1100
1200
FeO Fe2O3
827
[45Dar]
[57Egn]
[66Ack][65Val]
[69Lyk][70Cam][74Tou][80Tak]
[46Dar]
10-12
10-8
10-10
10-16
10-28
10-24
10-16
10-20
Page 33
Fe-Zn-O System
2010MontrealOxides and Pyrometallurgy 33
Page 34
Fe-Zn-O System
2010MontrealOxides and Pyrometallurgy 34
Page 35
Fe-Zn-O System
2010MontrealOxides and Pyrometallurgy 35
Page 36
Fe-Zn-O System
0.6
0.7
0.8
0.9 0.1
0.2
0.3
0.4
O
Zincite
ASlag-liq
ASpinel
Zincite+O2
ASpinel+O2
1500oC
2010MontrealOxides and Pyrometallurgy 36
0.1
0.2
0.3
0.4
0.5
0.10.20.30.40.50.60.70.80.9
0.5
0.6
0.7
0.8
0.9
Fe Znmole fraction
Fe-LIQUID + Zincite
ASlag-liq
ASlag-liq + BCC_A2
Page 37
FeO-ZnO System (oxide phases only)
2010MontrealOxides and Pyrometallurgy 37
Page 38
FeO-ZnO System (oxide phases only)
2010MontrealOxides and Pyrometallurgy 38
Page 39
FeO-ZnO System (oxide phases only)
2010MontrealOxides and Pyrometallurgy 39
Page 40
FeO-ZnO System (oxide phases only)
ASlag-liq
T(C
)
1400
1600
1800
2000
2010MontrealOxides and Pyrometallurgy 40
AMonoxide Zincite
mole ZnO/(FeO+ZnO)
0 0.2 0.4 0.6 0.8 1
800
1000
1200
Page 41
FeO-ZnO System (oxide phases only)
Phases do not have any Fe 2O3
2010MontrealOxides and Pyrometallurgy 41
Page 42
FeO-ZnO System (oxide phases and pure Fe)
2010MontrealOxides and Pyrometallurgy 42
Page 43
FeO-ZnO System (oxide phases and pure Fe)
2010MontrealOxides and Pyrometallurgy 43
Page 44
FeO-ZnO System (oxide phases and pure Fe)
ASlag-liq + Fe(liq)
ASlag-liq + Fe(s)
Zincite + Fe(s)
Zincite + Fe(liq)
T(C
)
1400
1600
1800
2000
Convergency problems, missing lines
2010MontrealOxides and Pyrometallurgy 44
AMonoxide ZinciteAMonoxide + Zincite + Fe(s2)
mole ZnO/(FeO+ZnO)
0 0.2 0.4 0.6 0.8 1
800
1000
1200
Page 45
FeO-ZnO System in Equilibrium with Metals
2010MontrealOxides and Pyrometallurgy 45
Oxide phases
Metal phases from FSstel
Page 46
FeO-ZnO System in Equilibrium with Metals
2010MontrealOxides and Pyrometallurgy 46
Oxide phases
Metal phases from FSstel
Page 47
FeO-ZnO System in Equilibrium with Metals
2010MontrealOxides and Pyrometallurgy 47
Page 48
FeO-ZnO System in Equilibrium with Metals
ASlag-liq + Fe-LIQUID
Zincite + Fe-LIQUID
ASlag-liq + BCC_A2
FeO - ZnO - Femole Fe/(FeO+ZnO+Fe) = 0.001
T(C
)
1600
1800
2000
2010MontrealOxides and Pyrometallurgy 48
Zincite + FCC(c,n)
AMonoxide + FCC(c,n)
AMonoxide+BCC_A2
AMonoxide+BCC_A2
Zincite + BCC_A2
mole ZnO/(FeO+ZnO+Fe)
T(C
)
0 0.2 0.4 0.6 0.8 1
800
1000
1200
1400
Page 49
FeO-ZnO in Equilibrium with Metals vs FeO-ZnO
ASlag-liq + Fe-LIQUID
Zincite + Fe-LIQUID
ASlag-liq + BCC_A2
ASlag-liq
FeO - ZnO - Femole Fe/(FeO+ZnO+Fe) = 0.001
T(C
)
1400
1600
1800
2000
2010MontrealOxides and Pyrometallurgy 49
Zincite + FCC(c,n)
AMonoxide + FCC(c,n)
AMonoxide+BCC_A2
AMonoxide+BCC_A2
Zincite + BCC_A2
AMonoxide Zincite
mole ZnO/(FeO+ZnO+Fe)
T(C
)
0 0.2 0.4 0.6 0.8 1
800
1000
1200
1400
Page 50
FeO-ZnO System in Equilibrium with Metals
2010MontrealOxides and Pyrometallurgy 50
Oxide phases
Metal phases from SGTE
Page 51
FeO-ZnO System in Equilibrium with Metals
2010MontrealOxides and Pyrometallurgy 51
Oxide phases
Metal phases from SGTE
Page 52
FeO-ZnO System in Equilibrium with Metals
ASlag-liq + BCC_A2
ASlag-liq + LIQUID
LIQUID + Zincite
FeO - ZnO - Femole Fe/(FeO+ZnO+Fe) = 0.001
T(C
)
1600
1800
2000
2010MontrealOxides and Pyrometallurgy 52
AMonoxide + FCC_A1
AMonoxide + BCC_A2BCC_A2 + Zincite
FCC_A1 + Zincite
AMonoxide + BCC_A2
mole ZnO/(FeO+ZnO+Fe)
T(C
)
0 0.2 0.4 0.6 0.8 1
800
1000
1200
1400
Page 53
FeO-ZnO in Equilibrium with Metals (FSstel vs SGTE)
ASlag-liq + BCC_A2
ASlag-liq + LIQUID
LIQUID + Zincite
ASlag-liq + Fe-LIQUID
Zincite + Fe-LIQUID
ASlag-liq + BCC_A2
FeO - ZnO - Femole Fe/(FeO+ZnO+Fe) = 0.001
T(C
)
1400
1600
1800
2000
2010MontrealOxides and Pyrometallurgy 53
AMonoxide + FCC_A1
AMonoxide + BCC_A2BCC_A2 + Zincite
FCC_A1 + Zincite
AMonoxide + BCC_A2
Zincite + FCC(c,n)
AMonoxide + FCC(c,n)
AMonoxide+BCC_A2
AMonoxide+BCC_A2
Zincite + BCC_A2
mole ZnO/(FeO+ZnO+Fe)
T(C
)
0 0.2 0.4 0.6 0.8 1
800
1000
1200
1400
Page 54
FeO-ZnO System in Equilibrium with Metals
2010MontrealOxides and Pyrometallurgy 54
Oxide phases
Stoichiometric metal phases from Fact53
Page 55
FeO-ZnO System in Equilibrium with Metals
2010MontrealOxides and Pyrometallurgy 55
Oxide phases
Stoichiometric metal phases from Fact53
Page 56
FeO-ZnO System in Equilibrium with Metals
Zincite + Fe(liq)
Zincite + Fe(s)ASlag-liq + Fe(s)
ASlag-liq + Fe(liq)
FeO - ZnO - Femole Fe/(FeO+ZnO+Fe) = 0.001
T(C
)
1400
1600
1800
2000
2010MontrealOxides and Pyrometallurgy 56
Zincite + Fe(s2)
Zincite + Fe(s)AMonoxide + Fe(s)
AMonoxide + Fe(s2)
mole ZnO/(FeO+ZnO+Fe)
T(C
)
0 0.2 0.4 0.6 0.8 1
800
1000
1200
1400
Page 57
FeO-ZnO in Equilibrium with Metals: FSstel vs pure Fe
Zincite + Fe(liq)
Zincite + Fe(s)ASlag-liq + Fe(s)
ASlag-liq + Fe(liq)ASlag-liq + Fe-LIQUID
Zincite + Fe-LIQUID
ASlag-liq + BCC_A2
FeO - ZnO - Femole Fe/(FeO+ZnO+Fe) = 0.001
T(C
)
1600
1800
2000
2010MontrealOxides and Pyrometallurgy 57
Zincite + Fe(s2)
Zincite + Fe(s)AMonoxide + Fe(s)
AMonoxide + Fe(s2)
Zincite + FCC(c,n)
AMonoxide + FCC(c,n)
AMonoxide+BCC_A2
AMonoxide+BCC_A2
Zincite + BCC_A2
mole ZnO/(FeO+ZnO+Fe)
T(C
)
0 0.2 0.4 0.6 0.8 1
800
1000
1200
1400
Page 58
FeO-ZnO System in Equilibrium with Metals
2010MontrealOxides and Pyrometallurgy 58
Oxide phases
Only one metal phase, Fe(s), from Fact53
Page 59
FeO-ZnO System in Equilibrium with Metals
ASlag-liq + Fe(s)
Zincite + Fe(s)
FeO - ZnO - Femole Fe/(FeO+ZnO+Fe) = 0.001
T(C
)
1600
1800
2000
2010MontrealOxides and Pyrometallurgy 59
AMonoxide + Fe(s)
Zincite + Fe(s)
mole ZnO/(FeO+ZnO+Fe)
T(C
)
0 0.2 0.4 0.6 0.8 1
800
1000
1200
1400
Page 60
FeO-ZnO in Equilibrium with Metals: FSstel vs Fe(s)
ASlag-liq + Fe(s)
Zincite + Fe(s)
ASlag-liq + Fe-LIQUID
Zincite + Fe-LIQUID
ASlag-liq + BCC_A2
FeO - ZnO - Femole Fe/(FeO+ZnO+Fe) = 0.001
T(C
)
1400
1600
1800
2000
2010MontrealOxides and Pyrometallurgy 60
AMonoxide + Fe(s)
Zincite + Fe(s)
Zincite + FCC(c,n)
AMonoxide + FCC(c,n)
AMonoxide+BCC_A2
AMonoxide+BCC_A2
Zincite + BCC_A2
mole ZnO/(FeO+ZnO+Fe)
T(C
)
0 0.2 0.4 0.6 0.8 1
800
1000
1200
1400
Page 61
FeO-ZnO in Equilibrium with Fe(s) vs FeO-ZnO
ASlag-liq + Fe(s)
Zincite + Fe(s)
ASlag-liq
FeO - ZnO - Femole Fe/(FeO+ZnO+Fe) = 0.001
T(C
)
1400
1600
1800
2000
2010MontrealOxides and Pyrometallurgy 61
AMonoxide + Fe(s)
Zincite + Fe(s)
AMonoxide Zincite
mole ZnO/(FeO+ZnO+Fe)
T(C
)
0 0.2 0.4 0.6 0.8 1
800
1000
1200
1400
Page 62
FeO-ZnO System in Equilibrium with Metals
2010MontrealOxides and Pyrometallurgy 62
Oxide phases
Pure Fe and Zn (sol. and liq.) from Fact53
Page 63
FeO-ZnO System in Equilibrium with Metals
ASlag-liq + Zn(liq)
ASlag-liq + Fe(liq)
Zincite + Zn(liq)
ASlag-liq + Fe(s)Zincite + Fe(s)
ASlag-liq + Zincite + Fe(liq)
FeO - ZnO - Femole Fe/(FeO+ZnO+Fe) = 0.001
T(C
)
1400
1600
1800
2000
2010MontrealOxides and Pyrometallurgy 63
AMonoxide + Fe(s2)
AMonoxide + Fe(s)
Zincite + Fe(s2)
Zincite + Fe(s)
mole ZnO/(FeO+ZnO+Fe)
T(C
)
0 0.2 0.4 0.6 0.8 1
800
1000
1200
1400
Page 64
FeO-ZnO in Equilibrium with Fe & Zn (s,l) vs FSstel
Zincite + Fe(s)
Zincite + Zn(liq)
ASlag-liq + Fe(s)
ASlag-liq + Fe(liq)
ASlag-liq + Zn(liq)
ASlag-liq + Fe-LIQUID
Zincite + Fe-LIQUID
ASlag-liq + BCC_A2
FeO - ZnO - Femole Fe/(FeO+ZnO+Fe) = 0.001
T(C
)
1400
1600
1800
2000
2010MontrealOxides and Pyrometallurgy 64
AMonoxide + Fe(s2)
AMonoxide + Fe(s) Zincite + Fe(s)
Zincite + Fe(s2)
Zincite + FCC(c,n)
AMonoxide + FCC(c,n)
AMonoxide+BCC_A2
AMonoxide+BCC_A2
Zincite + BCC_A2
mole ZnO/(FeO+ZnO+Fe)
T(C
)
0 0.2 0.4 0.6 0.8 1
800
1000
1200
1400
Page 65
FeO-ZnO System in Equilibrium with Metals and Gas
2010MontrealOxides and Pyrometallurgy 65
Oxide phases
Metal phases from FSstel
Gaseous species from Fact53
Page 66
FeO-ZnO System in Equilibrium with Metals and Gas
2010MontrealOxides and Pyrometallurgy 66
Oxide phases, all Metal phases from FSstel
Gaseous species only from Fact53
Page 67
FeO-ZnO System in Equilibrium with Metals and Gas
2010MontrealOxides and Pyrometallurgy 67
Page 68
FeO-ZnO System in Equilibrium with Metals and Gas
ASlag-liq + gas_ideal
ASlag-liq + BCC_A2
ASlag-liq + Fe-LIQUID
FeO - ZnO - Femole Fe/(FeO+ZnO+Fe) = 0.001
T(C
)
1600
1800
2000
2010MontrealOxides and Pyrometallurgy 68
AMonoxide + FCC(c,n)
AMonoxide + BCC_A2 BCC_A2 + Zincite
Zincite + FCC(c,n)
gas_ideal + ZinciteAMonoxide + gas_ideal
ASlag-liq + FCC(c,n)
mole ZnO/(FeO+ZnO+Fe)
T(C
)
0 0.2 0.4 0.6 0.8 1
800
1000
1200
1400
Page 69
FeO-ZnO System in Equilibrium with Metals and Gas
ASlag-liq + gas_ideal
ASlag-liq + BCC_A2
ASlag-liq + Fe-LIQUID
ASlag-liq + Fe-LIQUID
Zincite + Fe-LIQUID
ASlag-liq + BCC_A2
FeO - ZnO - Femole Fe/(FeO+ZnO+Fe) = 0.001
T(C
)
1400
1600
1800
2000
Red and blue curves are calculated without gas
2010MontrealOxides and Pyrometallurgy 69
AMonoxide + FCC(c,n)
AMonoxide + BCC_A2 BCC_A2 + Zincite
Zincite + FCC(c,n)
gas_ideal + Zincite
AMonoxide + gas_ideal
ASlag-liq + FCC(c,n)
Zincite + FCC(c,n)
AMonoxide + FCC(c,n)
AMonoxide+BCC_A2
AMonoxide+BCC_A2
Zincite + BCC_A2
mole ZnO/(FeO+ZnO+Fe)
T(C
)
0 0.2 0.4 0.6 0.8 1
800
1000
1200
1400
Page 70
FeO-ZnO in Equilibrium with Metals at P=100 atm
2010MontrealOxides and Pyrometallurgy 70
Page 71
FeO-ZnO in Equilibrium with Metals at P=100 atm
ASlag-liq + BCC_A2
ASlag-liq + Fe-LIQUID
ASlag-liq + gas_ideal
gas_ideal + Zincite
Fe-LIQUID + Zincite
FeO - ZnO - FeP=100 atm, mole Fe/(FeO+ZnO+Fe) = 0.001
T(C
)
1600
1800
2000
2010MontrealOxides and Pyrometallurgy 71
AMonoxide + BCC_A2
AMonoxide + FCC(c,n)
BCC_A2 + Zincite
Zincite + FCC(c,n)
AMonoxide + BCC_A2
mole ZnO/(FeO+ZnO+Fe)
T(C
)
0 0.2 0.4 0.6 0.8 1
800
1000
1200
1400
Page 72
Fe-Zn-O System
0.6
0.7
0.8
0.9 0.1
0.2
0.3
0.4
O
Zincite
ASlag-liq
ASpinel
Zincite+O2
ASpinel+O2
1500oC
2010MontrealOxides and Pyrometallurgy 72
0.1
0.2
0.3
0.4
0.5
0.10.20.30.40.50.60.70.80.9
0.5
0.6
0.7
0.8
0.9
Fe Znmole fraction
Fe-LIQUID + Zincite
ASlag-liq
ASlag-liq + BCC_A2
Page 73
Oxide Phase Diagrams under Reducing Conditions
- Metal phases must be selected
- Step a bit off an oxide section towards metals
- FSstel is needed to see the right metal phases in equilibrium
2010MontrealOxides and Pyrometallurgy 73
- Metal phases often have only a minor effect on oxide phase boundaries
- If you do not have FSstel or SGTE database for meta l phases, select metals from Fact53
- Do not forget the gas phase
Page 74
FeO-CoO System in Equilibrium with Metals
2010MontrealOxides and Pyrometallurgy 74
Oxide phases, Gaseous species
Metal phases from FSstel
Page 75
FeO-CoO System in Equilibrium with Metals
2010MontrealOxides and Pyrometallurgy 75
Page 76
FeO-CoO System in Equilibrium with Metals
2010MontrealOxides and Pyrometallurgy 76
Page 77
FeO-CoO System in Equilibrium with Metals
BCC_A2 + AMonoxide
FCC(c,n) + AMonoxide
FeO - CoO - Femole Fe/(FeO+CoO) = 0.001
T(C
)
700
900
1100
1300
2010MontrealOxides and Pyrometallurgy 77
BCC_A2 + ASpinel
FCC(c,n) + ASpinel
HCP(c,n) + ASpinel
HCP(c,n) + ASpinel + AMonoxide
FCC(c,n) + ASpinel + AMonoxide
mole CoO/(FeO+CoO)
T(C
)
0 0.2 0.4 0.6 0.8 1100
300
500
700
Page 78
FeO-CoO System in Equilibrium with Pure Fe and Co
2010MontrealOxides and Pyrometallurgy 78
Oxide phases, Gaseous species
Metal phases from Fact53
Page 79
FeO-CoO System in Equilibrium with Pure Fe and Co
2010MontrealOxides and Pyrometallurgy 79
Oxide phases
Fe and Co from Fact53
Page 80
FeO-CoO System in Equilibrium with Pure Fe and Co
AMonoxide + Co(s2)
AMonoxide + Fe(s2) + Co(s2)
AMonoxide + Fe(s2)
AMonoxide + Fe(s) + Co(s2)
FeO - CoO - Femole Fe/(FeO+CoO) = 0.001
T(C
)
700
900
1100
1300
2010MontrealOxides and Pyrometallurgy 80
ASpinel + AMonoxide + Co(s)
ASpinel + AMonoxide + Co(s2)
ASpinel + Fe(s) + Co(s)
ASpinel + Fe(s) + Co(s2)
ASpinel + Co(s)
ASpinel + Co(s2)
mole CoO/(FeO+CoO)
T(C
)
0 0.2 0.4 0.6 0.8 1100
300
500
700
Page 81
FeO-CoO in Equilibrium with Fe and Co vs FSstel
AMonoxide + Fe(s2)
AMonoxide + Co(s2)
BCC_A2 + AMonoxide
FCC(c,n) + AMonoxide
FeO - CoO - Comole Co/(FeO+CoO) = 0.001
900
1100
1300
2010MontrealOxides and Pyrometallurgy 81
ASpinel + Fe(s) + Co(s)
ASpinel + Fe(s) + Co(s2)
ASpinel + Fe(s)
AMonoxide + Fe(s)
ASpinel + Co(s2)
ASpinel + Co(s)
AMonoxide + Co(s)
BCC_A2 + ASpinel
FCC(c,n) + ASpinel
HCP(c,n) + ASpinel
BCC_A2 + AMonoxide
HCP(c,n) + ASpinel + AMonoxide
FCC(c,n) + ASpinel + AMonoxide
mole CoO/(FeO+CoO)
T(C
)
0 0.2 0.4 0.6 0.8 1100
300
500
700
Page 82
FeO-CoO System in Equilibrium with Pure Co
AMonoxide + Co(s2)
FeO - CoO - Femole Fe/(FeO+CoO) = 0.001
T(C
)
700
900
1100
1300
2010MontrealOxides and Pyrometallurgy 82
ASpinel + Co(s)
ASpinel + Co(s2)
mole CoO/(FeO+CoO)
T(C
)
0 0.2 0.4 0.6 0.8 1100
300
500
700
Page 83
FeO-CoO System in Equilibrium with Pure Fe
AMonoxide + Fe(s)
AMonoxide + Fe(s2)
FeO - CoO - Femole Fe/(FeO+CoO) = 0.001
T(C
)
700
900
1100
1300
2010MontrealOxides and Pyrometallurgy 83
ASpinel + Fe(s)
AMonoxide + Fe(s)
mole CoO/(FeO+CoO)
T(C
)
0 0.2 0.4 0.6 0.8 1100
300
500
700
Page 84
Fe-Co-O System in Equilibrium with Metals
2010MontrealOxides and Pyrometallurgy 84
Page 85
Fe-Co-O System in Equilibrium with Metals
2010MontrealOxides and Pyrometallurgy 85
Page 86
Fe-Co-O System in Equilibrium with Metals
0.6
0.7
0.8
0.9 0.1
0.2
0.3
0.4
0.5
O
AS
pinel + AM
onoxide + BC
C_A
2
Fe2O3(s)AMonoxide
AMonoxide
ASpinel
700oC
2010MontrealOxides and Pyrometallurgy 86
0.1
0.2
0.3
0.4
0.5
0.10.20.30.40.50.60.70.80.9
0.5
0.6
0.7
0.8
0.9
Fe Comole fraction
BCC_A2 FCC(c,n)
AS
pinel + AM
onoxide + BC
C_A
2
ASpinel + AMonoxide + FCC(c,n)ASpinel + FCC(c,n) + BCC_A2
Page 87
Fe-Co-O System in Equilibrium with Pure Metals
2010MontrealOxides and Pyrometallurgy 87
Oxide phases
Fe and Co from Fact53
Page 88
Fe-Co-O System in Equilibrium with Pure Metals
0.6
0.7
0.8
0.9 0.1
0.2
0.3
0.4
O
ASpinel + gas_ideal
AMonoxideAMonoxide
ASpinel
Fe2O3
700oC
2010MontrealOxides and Pyrometallurgy 88
0.1
0.2
0.3
0.4
0.5
0.10.20.30.40.50.60.70.80.9
0.5
0.6
0.7
0.8
0.9
Fe Comole fraction
Co(s2) + AMonoxide + Fe(s)
Page 89
Fe2O3-Cr2O3 System in Equilibrium with Air
2010MontrealOxides and Pyrometallurgy 89
Gas phase must be selected even though it does not form
Page 90
Fe2O3-Cr2O3 System in Equilibrium with Air
2010MontrealOxides and Pyrometallurgy 90
Page 91
Fe2O3-Cr2O3 System in Equilibrium with Air
ASlag-liq
Fe2O3 - Cr2O3 - O2p(O2) = 0.21 atm
T(C
)
2100
2300
2500
2010MontrealOxides and Pyrometallurgy 91
ASpinel
M2O3(corundum)
mole Cr2O3/(Fe2O3+Cr2O3)
T(C
)
0 0.2 0.4 0.6 0.8 11300
1500
1700
1900
Page 92
MgO-Cr2O3 System at P(O2)=10-5.5 atm
2010MontrealOxides and Pyrometallurgy 92
Page 93
MgO-Cr2O3 System at P(O2)=10-5.5 atm
2010MontrealOxides and Pyrometallurgy 93
Page 94
MgO-Cr2O3 System at P(O2)=10-5.5 atm
ASpinel
AM
onox
ide
ASlag-liq
gas_ideal
ASlag-liq
MgO - Cr 2O3 - O2p(O2) = 10
-5.5 atm
T(C
)
2200
2600
3000
2010MontrealOxides and Pyrometallurgy 94
ASpinel
AM
onox
ide
ASpinel + Cr2O3(s)
mole Cr2O3/(MgO+Cr2O3)
T(C
)
0 0.2 0.4 0.6 0.8 11000
1400
1800
Page 95
MgO-Cr 2O3 System at P(O2)=10-5.5 atm
2010MontrealOxides and Pyrometallurgy 95
Gas phase must be selected, but it can be made dormant
Page 96
MgO-Cr2O3 System at P(O2)=10-5.5 atm, Dormant Gas
AM
onox
ide
ASpinel
ASlag-liq
MgO - Cr 2O3 - O2p(O2) = 10
-5.5 atm
T(C
)
2200
2600
3000
2010MontrealOxides and Pyrometallurgy 96
AM
onox
ide
ASpinel
ASpinel + Cr2O3(s)
mole Cr2O3/(MgO+Cr2O3)
T(C
)
0 0.2 0.4 0.6 0.8 11000
1400
1800
Page 97
Fe-Cr-O System at 1300 °C
2010MontrealOxides and Pyrometallurgy 97
Oxide phases
Metal phases from FSstel
Page 98
Fe-Cr-O System at 1300 °C
2010MontrealOxides and Pyrometallurgy 98
Oxide phases
Nothing from Fact53 and from FSstel
Page 99
Fe-Cr-O System at 1300 °C
2010MontrealOxides and Pyrometallurgy 99
Page 100
Fe-Cr-O System at 1300 °C
ASpinel
M2O3(corundum)
AMonoxide
Fe - Cr - O21300
oC
2)) (
atm
)
-10
-8
-6
-4
-2
0
2010MontrealOxides and Pyrometallurgy 100
BCC_A2
FC
C(c
,n)
FCC(c,n) + ASpinel
FCC(c,n) + M2O3(corundum)
BCC_A2 + M2O3(corundum)
mole Cr/(Fe+Cr)
log 1
0(p(
O2
0 0.2 0.4 0.6 0.8 1-20
-18
-16
-14
-12
-10