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Processes
Winny Wulandari
Declaration
The author declares that this thesis:
contains no material which has been accepted for the award to the
candidate of any other degree or diploma, except where due reference is
made in the text of the thesis;
Winny Wulandari
February 2013
ii
Abstract
The current dominant route for producing magnesium is via the Pidgeon
process, a batch pyrometallurgical route that uses silicothermic reduction for
extracting magnesium in the form of metal vapour. While this process is
versatile and offers simple operation, the productivity of this process is very
low. Other silicothermic processes such as the Magnetherm and the Mintek
process attempt to increase the productivity of the silicothermic reduction
process by carrying out the reduction at higher temperatures in a liquid oxide
phase. The higher temperature and correspondingly increased productivity is
likely to lead to greater impurities in the magnesium metal. While the
silicothermic processes has been operative over seventy years, there is limited
information on the thermodynamics and kinetics of the process. In particular,
there is limited information on the behaviour of magnesium vapour and its
impurities in these processes. The purpose of this study is to investigate the
fundamental chemistry associated with the silicothermic processes, with
emphasis on the behaviour of impurities in the process, by using
thermodynamic modelling and kinetics analysis, and test the predictions from
thermodynamic modelling by performing an experimental study.
The first stage of the study focused on the thermodynamic modelling of
silicothermic processes using the Gibbs energy minimisation method.
Thermodynamic modelling predicted the limit of magnesium recovery from the
process at specific operating condition. The results showed the model overpredict experimental and industrial data from literature: For example between
1100 and 1200 C, the model predicted 99 wt% of conversion while data
showed that conversion varied between 87 and 89 wt%. A solution model for
the metallic phases was developed using data from critically analysed literature
to describe the interaction between binary metals involved in the magnesiumimpurities system. A multistage equilibrium model of vapour condensation
predicted impurities to segregate in the process at temperature ranges between
iii
the reaction and condenser zone; that is between 482 and 1100 C, with
impurities comprising of the species Fe, FeSi, CaO, and Mg2Ca.
In the next stage of research, a kinetics study was carried out to analyse the
kinetics of the process under a flowing inert gas atmosphere. The experimental
data used for this study was from a previous work on the silicothermic reaction
under argon atmosphere. The kinetics analysis considered a number of kinetic
models with different controlling factors and the mass transfer kinetics of
magnesium vapour from the briquettes to the bulk gas phase. Based on the
analysis, it was concluded that the silicothermic process under inert
atmosphere was controlled by solid state diffusion of reactants, with the Jander
and Ginstling-Brounshtein models being the best models to describe the kinetics
of the process. The analysis also predicted that gas-film mass transfer of
magnesium to the bulk gas phase was not limiting the overall kinetics of the
process.
In order to test prediction of the thermodynamic modelling study, an
experimental apparatus was developed and experimental work was performed
using the Pidgeon processs chemistry to investigate the behaviour of impurities
in the process. Some condensates were found in the cooler part of the furnace,
with MgO as the major phase. The magnesium metal condensate had been
purposedly oxidised after formation. The variation of concentration of the
condensates as predicted from the thermodynamic modelling study was not
observed in the experimental study. The Classical Nucleation Theory predicts
that homogeneous nucleation for the species occurs at different temperature,
which corresponds to different position in the horizontal tube. However, due to
very low vapour pressure of Ca, SiO, and Fe in this temperature range, these
species would not to be expected to be observed in the experimental study,
which was consistent with the experimental results.
In conclusion, there is no evidence that impurities present in magnesium vapour
can be practically separated by selective condensation, eventhough it is
thermodynamically feasible. Experimental work at higher concentrations and
temperature range are required to fully explore this option.
iv
Acknowledgments
I would like to express my gratitude to Allah, the Almighty, who guides me
throughout my PhD study and beyond.
I also would like to thanks Dr. James Wang for assisting me conducting
SEM/EDS analysis, and Dr. Francois Malherbe from Faculty of Life and Social
Sciences for assisting me conducting XRD analysis and also introducing me to
his research group.
Bernard Xu, Reiza Mukhlis, Abdul Khaliq, Saiful Islam, and Shabnam Sabah. In
particular, I would like to thank Neslihan, Nazmul, and Morshed for all
wonderful discussions and sharing of knowledge and experiences during the
duration of my PhD journey.
vi
vii
viii
Table of Contents
Declaration ......................................................................................................................................... i
Abstract .............................................................................................................................................iii
Acknowledgments .......................................................................................................................... v
Table of Contents ........................................................................................................................... ix
List of Figures.............................................................................................................................. xvii
List of Tables ................................................................................................................................xxv
Nomenclatures .......................................................................................................................... xxix
1
Introduction ............................................................................................................................ 1
2.1.1
2.1.2
2.1.2.1
2.2
2.3
2.3.1
2.3.2
2.3.3
2.4
2.4.1
2.4.2
2.4.3
2.5
3
3.1.1
3.1.2
3.1.3
Solution Models.................................................................................................. 48
3.1.3.1
3.1.3.2
3.1.3.3
3.1.3.4
3.1.3.5
3.1.3.6
3.1.3.7
3.1.4
3.2
3.1.4.1
Chemix-Thermodata ................................................................................ 55
3.1.4.2
HSC ................................................................................................................. 56
3.1.4.3
FactSage........................................................................................................ 56
3.1.4.4
MTDATA ....................................................................................................... 57
3.2.1
3.2.2
3.2.3
3.2.3.1
3.2.3.2
3.2.4
3.2.4.1
3.3
3.2.4.2
Heterogeneous Nucleation.................................................................... 76
3.2.4.3
Growth of Particles................................................................................... 77
Research Issues................................................................................................................... 87
5.2
5.2.1
5.2.1.1
5.2.1.2
Results........................................................................................................... 97
5.2.2
5.2.2.1
5.2.2.2
Results.........................................................................................................100
5.2.3
5.2.3.1
5.2.3.2
Results.........................................................................................................102
5.2.4
5.2.4.1
5.2.4.2
Modelling of Impurities Behaviour of Vapour produced from
the Pidgeon Process ....................................................................................................105
5.2.4.3
Modelling of Impurities Behaviour of Vapour produced from
the Magnetherm Process ...........................................................................................107
5.2.4.4
Modelling of Impurities Behaviour of Vapour produced from
the Mintek Process.......................................................................................................107
5.2.5
5.3
5.3.1
5.3.1.1
5.3.1.2
5.3.1.3
5.3.1.4
Fe-Si System..............................................................................................116
5.3.1.5
5.3.1.6
5.3.1.7
5.3.2
Modelling Formulation..................................................................................121
5.3.3
Results .................................................................................................................123
5.3.3.1
5.3.3.3
5.4.1
5.4.2
5.5
6
Discussion ...................................................................................................................137
Introduction ...............................................................................................................143
6.2
6.2.1
6.2.2
Results .................................................................................................................151
6.3
6.3.1
6.3.1.1
6.3.1.2
Pore Diffusion...........................................................................................160
6.3.2
6.4
Results .................................................................................................................161
6.3.2.1
6.3.2.2
Discussion ...................................................................................................................165
6.4.1
6.4.2
6.5
Conclusion...................................................................................................................168
xii
7.1.1
7.1.1.1
7.1.1.2
7.1.1.3
7.1.2
7.1.2.1
Reactants....................................................................................................176
7.1.2.2
7.1.2.3
7.1.3
7.1.4
7.1.4.1
7.1.4.2
7.1.4.3
7.1.4.4
Inductively Couple Plasma Atomic Emission Spectroscopy
(ICP-AES) 186
7.1.4.5
7.2
Experimental Results..............................................................................................187
7.2.1
7.2.2
7.2.3
Condensates Characterisation....................................................................193
7.2.4
8.1.1
8.1.2
Supersaturation ...............................................................................................208
8.2
Results ..........................................................................................................................211
8.2.1
8.2.2
8.2.3
8.2.4
Condensation of Iron......................................................................................219
8.3
Discussion ...................................................................................................................220
8.4
Conclusion...................................................................................................................223
9
10
Discussion ...........................................................................................................................225
Conclusions and Recommendations .....................................................................233
References ....................................................................................................................................237
Appendixes
Appendix A: Species and Phases in the Silicothermic System................................... A-1
A.1 Calcined Dolomite........................................................................................................... A-1
A.2 Ferrosilicon....................................................................................................................... A-2
A.3 Flux........................................................................................................................................A-3
A.4 Dicalcium Silicate.......................................................................................................... ..A-3
Appendix B: FactSage Program............................................................................................... B-1
B.1 Description of Program................................................................................................ B-1
B.2 Customised Solution Models...................................................................................... B-4
B.3 Examples of Computational Thermodynamics.................................................. B-7
B.3.1 Pidgeon Process Equilibrium at 1100 C and 7 Pa.................................. B-7
B.3.2 Condensation of Magnesium Vapour at 1050 C...................................... B-7
Appendix C: Temperature Profile Measurement............................................................. C-1
C.1 Temperature Profile with and without Condenser.......................................... C-1
C.2 Temperature Profile with Different Argon Gas Flow...................................... C-2
C.3 Temperature Profile at 1140 1145 C ................................................................ C-2
C.4 Temperature Profile at Different Set Point Temperature.............................. C-3
C.5 Isothermal Position inside Horizontal Tube Furnace......................................C-3
Appendix D: Error Analysis...................................................................................................... D-1
D.1 Errors in Experimental Procedures....................................................................... D-1
D.1.1 Weighing Error....................................................................................................... D-1
D.1.2 Temperature Measurement Error.................................................................. D-1
D.1.3 Error in Sample Position inside Furnace.................................................... D-2
D.1.4 Flow Rate Errors.................................................................................................... D-2
D.2 Errors in Analytical Technique..................................................................................D-2
D.2.1 Error in EDS Analysis............................................................................................D-2
xiv
xv
xvi
List of Figures
Figure 2.1 The Pidgeon Process Flow Diagram15 ............................................................... 7
Figure 2.2 Schematic of Horizontal Retort and Condenser18 ........................................ 8
Figure 2. 3 Silicon Activities (aSi) for the Fe-Si System: a. aSi at 1200 C,
Reference State to Solid Silicon23, b. aSi at 1500 C, Reference State to Molten
Silicon24, and c. aSi at 1600 C, Reference State to Molten Silicon25 ............................ 9
Figure 2. 4 Gibbs Energy of Reaction26 Calculated using FactSage 6.2 ................... 11
Figure 2. 5 Kinetics of Silicothermic Reaction at Vacuum Condition of 0.5 mmHg
(After Toguri and Pidgeon16, 35) ............................................................................................. 13
Figure 2.6 Magnesium Recovery from the Pidgeon Process. Dolomite type A:
white, hard and macrocrystalline; Dolomite B: brown, friable to hard,
microcrystalline ........................................................................................................................... 15
Figure 2.7 Arrhenius Plot for the Jander Constants (Wynnyckyj et al36) .............. 16
Figure 2.8 Effect of Pressure on Conversion of Magnesium (after Pidgeon12 and
Toguri and Pidgeon35) ............................................................................................................... 17
Figure 2.9 Effect of Ferrosilicon Grade on Magnesium Conversion ........................ 18
Figure 2.10 Effect of Silicon (75%FeSi) Stoichiometry on Magnesium Conversion
............................................................................................................................................................ 19
Figure 2. 11 Effect of Time and Temperature on Conversion of Magnesium in
Argon Atmosphere at 2.510-4 m3/min (After Morsi et al34) ..................................... 21
Figure 2.12 Effect of Hydrogen Flow Rate on Magnesium Conversion.
Temperature: 1150 C; pellet radius: 9 mm; Compaction pressure: 68 MPa.
(after Barua and Wynnyckyj37) .............................................................................................. 22
Figure 2.13 The presence of CaSi2 in MgO-CaO-Si system. C: CaSi2, : -Ca2SiO4
(after Wynncykyj and Pidgeon28).......................................................................................... 24
Figure 2.14 Predicted Conversion Profile for Typical Experimental Condition.
Radius: 1.0 cm, Temperature: 1177 C, ke = 418 J/msK36............................................ 25
Figure 2.15 Effect of Pellet Radius on the Conversion Profile and Temperature
Distribution within the Briquette, Predicted by the Model. Temperature: 1177
C, ke= 418 J/msK, Time: 60 min36 ........................................................................................ 26
xvii
Figure 2.16 Calculated Magnesium Pressure on the Briquette Surface and Bulk
Gas37 .................................................................................................................................................. 27
Figure 2. 17 Bolzano Reactor48............................................................................................... 28
Figure 2.18 The Schematic of Magnetherm Process53 .................................................. 29
Figure 2.19 The Phase Diagram of CaO-MgO-SiO2-Al2O3 System at 10%
Al2O3(Temperature is in K)61. The Grey Area is the Magnetherm Operation
Condition......................................................................................................................................... 31
Figure 2.20 Phase Diagram of CaO-MgO-Al2O3-SiO2 System at 10 wt%
Al2O3(Temperature in K)61. The black area is the Mintek Operating Condition . 35
Figure 2.21 Layout of the MTMP Pilot Plant70.................................................................. 37
Figure 3.1 Different Modes of Diffusion133 ........................................................................ 59
Figure 3.2 Representation of a Reacting Particle when Diffusion through Gas
Film is the Controlling Resistance136. .................................................................................. 60
Figure 3.3 Diffusion of Species A from a Solid Surface into a Moving Gas
Stream134......................................................................................................................................... 69
Figure 3.4 Basic Steps of Crystal Growth from Condensation of Vapours. A.
Generation. B. Bulk Transport. C. Boundary Layer Transport. D.
Adsorption/Desorption. E. Migration. F. Nucleation165 ................................................ 71
Figure 3.5 The Schematic of Graphite Retort (After Toguri and Pidgeon)38 ........ 79
Figure 3.6 Experimental Configuration in Horizontal Tube Furnace (After
Hughes et al29) .............................................................................................................................. 80
Figure 3.7 Effect of Hydrogen Flow Rate on the Apparent Reaction Pressure at
1159 C (after Pidgeon and King27) ...................................................................................... 80
Figure 3.8 The Schematic of Vapour Pressure Measurement (after Pidgeon and
King27) .............................................................................................................................................. 82
Figure 3.9 Magnesium Reduction Apparatus (after Morsi et al40) ........................... 83
Figure 3.10 Schematic of Experimental Study (after Misra et al32) ......................... 83
Figure 3.11 Schematic of Experimental Study of Mg Vapour Condensation183 ... 84
Figure 5.1 Thermodynamic Modelling Methodology .................................................... 91
Figure 5.2 Schematic of Equilibrium Calculations .......................................................... 96
Figure 5.3 Equilibrium Calculation of the Pidgeon Process at 1100 C and 7 Pa 97
xviii
Figure 5.4 Equilibrium calculations for the Magnetherm Process at 1550 C and
5 kPa. ..............................................................................................................................................101
Figure 5.5 Equilibrium Calculation for the Mintek Process at 1750 C and 85
kPa. ..................................................................................................................................................103
Figure 5.6 Schematic of Multistage Equilibrium modelling ......................................105
Figure 5.7 Predicted Impurities Distribution from Multistage Equilibrium
Calculations using Vapour Predicted from the Pidgeon Process ............................105
Figure 5.8 Predicted Impurities Distribution from Multistage Equilibrium
Calculations using Vapour Predicted from the Magnetherm Process ..................106
Figure 5.9 Impurity distribution of the Mintek Process .............................................108
Figure 5. 10 Phase Diagram of Mg Rich Region in Mg-Ca System211 .....................112
Figure 5. 11 Activity of Mg and Ca106 at 550 C..............................................................113
Figure 5.12 (a) Phase Diagram of Mg-Si system, (b) Phase Diagram of Mg-rich
Region on Mg-Si System217 ....................................................................................................114
Figure 5. 13 Activity of Mg and Si217 at 550 C ..............................................................115
Figure 5. 14 Phase Diagram of Mg-Si System (after Grobner et al220) ..................115
Figure 5.15 Phase Diagram of Fe-Si (after Lacaze and Sundman221) ....................116
Figure 5.16 Schematic of Model Representations ........................................................121
Figure 5.17 Schematic of Thermodynamic Modelling of the Pidgeon Process..121
Figure 5.18 Effect of Temperature to Magnesium Recovery via the Pidgeon
Process ...........................................................................................................................................124
Figure 5.19 Effect of Pressure to Magnesium Recovery via the Pidgeon process
..........................................................................................................................................................125
Figure 5.20 Effects of Pressure and Temperature to Magnesium Recovery
Predicted by Thermodynamic Modelling .........................................................................125
Figure 5.21 The Predicted Fugacity of Magnesium Vapour in the Pidgeon
Process System at Various Temperature and Presssure ...........................................126
Figure 5.22 Magnesium Impurities by Single Stage Equilibrium ...........................127
Figure 5.23 Comparison between (a) Ideal Solution Model and (b) Random
Mixing Solution Model from the Modelling of the Pidgeon Process Impurities at
1160 C Temperature. .............................................................................................................130
xix
xxi
xxii
Figure A.1 The CaO-MgO Phase Diagram after Doman et al253. The dashed lines
is the assestment results of Hillert and Wang 254 ...........A-1
Figure A.2 Fe-Si Phase Diagram (after Masallski and Okamoto258)..............A-3
Figure A.3 CaO-SiO2 Phase Diagram14..............A-4
Figure A.4 Phase Diagram of Ca2SiO4-Mg2SiO4 System119 .............................A-5
xxiii
xxiv
List of Tables
Table 1.1 Operating Conditions and Impurities in Magnesium Extracted from the
Silicothermic Processes ............................................................................................................... 2
Table 2.1 Comparison of Some Reductions of Magnesium Oxide 11 ........................... 6
Table 2.2 Dolomite and Calcined Dolomite Composition, at wt% ............................... 7
Table 2.3 Summaries of Briquette Properties and Experimental Conditions Used
by Previous Investigators ......................................................................................................... 14
Table 2.4 Impurities in the Magnesium Produced from the Magnetherm Process
Before and After Refining (using MgCl2 and KCl fluxs) process, in wt%59 ............ 32
Table 2.5 Composition of Magnesium Process in Heggie-Iolaire Process64 ......... 34
Table 2.6 Composition of Calcined Dolomite (Cal.dol) and Reducing Agent
(%wt)67 ............................................................................................................................................ 34
Table 2. 7 Composition of Condensed Magnesium (wt%)66 ....................................... 38
Table 2.8 Slag Composition in Mintek Process (wt%)66............................................... 38
Table 2.9 Chemical Analyses of Various Fluxes, Mass per Cent8............................... 39
Table 2. 10 Chemical Analyses of Crude and Clean Magnesium, wt%8 .................. 40
Table 2.11 Physical Properties of Magnesium48.............................................................. 42
Table 2. 12 Pure Magnesium Specification and Mean Impurity Content9 ......... 42
Table 2. 13 Composition of Magnesium Alloys ................................................................ 43
Table 5.1 Operating Condition of Silicothermic Processes ......................................... 92
Table 5.2 FactSage204 Built-in Compound Database Used in This Study ............... 93
Table 5.3 FactSage204 Built-in Solution Database Used in This Study..................... 94
Table 5.4 Possible Species for The Pidgeon Process System in Gas and
Condensed Phases ....................................................................................................................... 96
Table 5.5 Possible Species for The Magnetherm and Mintek process Systems 100
Table 5.6 Predicted Vapour Compositions of Silicothermic Process from
Thermodynamic Modelling ...................................................................................................104
Table 5.7 Comparison of Element Composition Calculated from the Present
Study, Previous Modelling Work73 and Actual Chemical Analysis8, 35, 59..............109
xxv
xxvi
Table 6.10 Magnesium Vapour Pressure at 1150 C at Surface and Bulk Gas
(Argon Gas Flow Rate: 0.2510-3 m3/min) ......................................................................163
Table 6.11 Magnesium Vapour Pressure at 1300 C at Surface and Bulk Gas
(Argon Gas Flow Rate: 0.2510-3 m3/min) ......................................................................164
Table 7.1 Purity and Composition of Raw Materials ...................................................176
Table 7. 2 Silicothermic Experiments in Vacuum Conditions ..................................191
Table 7.3 Semi-quantitative Analysis of Condensates using EDS analysis..........198
Table 8.1 Properties Data of Species183, 243, 245, 246 ........................................................207
Table 8.2 Surface energy of Condensing Species ..........................................................207
Table 8.3 Equilibrium Vapour Pressure Constants (as per Equation 8.7) ..........209
Table 8.4 Molar Partial Fraction of Vapours Predicted from Thermodynamic
Modelling at 1140 C using FACT53 database ...............................................................211
Table 8.5 Summary of T* ........................................................................................................221
Table 8.6 Summary of Condensation of Vapour ............................................................221
xxvii
xxviii
Nomenclatures
Concentration of reactant
Cp
Heat capacity
Self-diffusion coefficient
Interdiffusivity of species A and B
Knudsen Diffusion
Inter-atomic spacing
EA
Activation energy
Enthalpy of reaction
AB
AB
Nucleation rate
Rate constant
kc
kB/k
,
,
Molecular mass
NA
ai
Activity of species i
Pi
pi: 3.14159
Radius
Re
Density of species i
Supersaturation/supercooling
Sc
Sh
Surface tension
Temperature
Time
Velocity
Kinematic viscosity
wt%
Weight percent
Conversion
xi
Composition of species i
yi
xxx
1 Introduction
Magnesium is a light metal that has a density of 1783 kg/m3, which is two thirds
of aluminium and one sixth of steel. It also has a number of other desirable
properties including good ductility, excellent castability and high specific
strength1. The strength-to-weight ratio of magnesium, 158 kNm/kg, is 17%
higher than the strength-to-weight ratio of aluminium. These attractive
properties have ensured a steady increase in the consumption of magnesium in
the recent years with a growth rate of 7% per annum2. It is used as an alloying
element in aluminium alloys, die casting, for steel desulphurisation, and as an
industrial chemicals3. The aluminium industry utilises magnesium to increase
the strength, ductility and corrosion resistance of aluminium alloys.
Magnesiums use in both aluminium and steel production strongly links its
demand to these two other metal commodities.
While the Pidgeon Process is slow and energy intensive, this process has
become the dominant process for producing magnesium in the world, with
China over 70% of all magnesium4. This process suits the local economy of
China, where the labour costs are cheap and raw materials are available. The
growing demand for magnesium has stimulated research into new methods of
producing magnesium. The Magnetherm process had been operated in the past
1
Table 1.1 Operating Conditions and Impurities in Magnesium Extracted from the
Silicothermic Processes
Operating
Condition
Pidgeon5, 6
Magnetherm7
Mintek8
13-67 Pa
~1 atm
1100 - 1200
1550 - 1600
1700 1750
50 kg
20 tonne
100 tonne
Pidgeon9
Magnetherm7
Al
0.004
Si
Pressure
Temperature (C)
Productivity per
retort per day
Impurities
(wt%)
Mintek8
Crude
Clean
0.01
0.066
0.04
0.01
0.05
0.281
0.095
Ca
0.005
N.A.
0.385
0.023
Fe
0.007
0.005
0.25
0.047
Mn
0.01
0.05
N.A.
N.A.
The productivity of the process has strong correlation with the impurities found
in the magnesium. Table 1.1 shows the typical impurities of magnesium resulted
from various silicothermic processes. The Pidgeon process typically produces
50 kg of magnesium per retort per day, while the Magnetherm process and the
Mintek process produce approximately 20 and 100 tonnes per retort per day,
respectively. While a higher temperature process offer higher productivity, the
increase in operating temperature results in higher impurities. The Pidgeon
process, which operates between a temperature of 1100 and 1200 C, produces
the highest purity of magnesium (>99.96 wt%). Conversely, the Mintek process
which operates at a temperature between 1700 and 1750 C produces a low
purity of magnesium (less than 99 wt% for the crude magnesium). The purity
required for 9980 A-grade commercial magnesium is a minimum of 99.80 wt%
Mg, with the impurities such as Ca, Al, Si, and Fe are below 0.05 wt% each10.
2
Based on the literature review, the research issues are identified in Chapter 4.
The thermodynamic modelling results are described in Chapter 5, while the
kinetic modelling results are described in Chapter 6. The results of experiments
are described in Chapter 7. Chapter 8 provides analysis based on the Classical
Nucleation theory on the condensation behaviour. The general discussion is
provided in Chapter 9, while Chapter 10 will provide conclusions and
recommendation for further studies.
2.
3.
4.
5.
(2. 1)
Reductant
T (C)
Carbon
1900
Calcium
Carbide
1700
Aluminium
1700
H = 285.79 kJ/g Mg
Si = 57.5 g/g Mg (80% Si)
H = 229.21 kJ /g Mg
Si = 113 g/g Mg (80% Si)
1200
Silicon
1200
Reaction
H = 604.76 kJ/mol Mg
H = 153.23 kJ/mol Mg
CaC2 = 120 g/g Mg (80% CaC2)
H = 166.67 kJ/g Mg
RAW DOLOMITE
FERROSILICON 75%
Crushing
Jaw crusher
Sizing
Ball mill
CALCINATED DOLOMITE
(via calcining kilns)
Storage
Retort
Residue to waste
Dolomite from
Haley,Ontario17
MgO
CaO
CO2
SiO2
FeO
H2O
21.12
31.27
47.22
0.12
0.22
0.02
Calcined Dolomite16
Theoretical
CaMg(CO3)2
21.86
30.41
47.73
-
Compounds
Compositions
CaO
MgO
L.O.I
Insoluble
R2O3
Minor
57.5
38.8
1.38
0.48
0.4
1.44
' ,+
+
-.1 ,)*1 ,/0
(2. 2)
+
()*
,/0
(2. 3)
Figure 2. 3 Silicon Activities (aSi) for the Fe-Si System: a. aSi at 1200 C,
Reference State to Solid Silicon23, b. aSi at 1500 C, Reference State to Molten
Silicon24, and c. aSi at 1600 C, Reference State to Molten Silicon25
Ellingsaeter and Rosenqvist23 measured the activities of solid silicon of the Fe-Si
alloy in the silicothermic reaction system. This silicon activity was compared
with the activity of molten silicon in the Fe-Si system at 1500 C24-25 and
described in Figure 2.3. These curves show a similar trend as the curve of solid
9
The equilibrium constant correlates with the Gibbs energy at the corresponding
temperature with this relationship:
3 ' 45678
(2.4)
(2. 5)
(2. 6)
(2. 7),
the Gibbs free energy of reaction in Equation (2.1) can be calculated to be:
$.: ' $.; $.< $.=
10
(2. 8)
23
suspected this
11
The use of vacuum has been found more effective to remove magnesium from
the briquettes compared with utilising a streaming inert gas16. An experimental
study on the silicothermic reaction in argon atmosphere34 found that the overall
yield of magnesium is lower than those in vacuum. This is supported by the
determination of a lower apparent activation energy of silicothermic in
vacuum35 compared to in a stream of inert gas34. The morphologies of
magnesium collected from those two methods are also different. Silicothermic
in vacuum produces a dense condensate while silicothermic in streaming gas
produces a loose powdered condensate16.
29, 32-37.
The experimental
Several investigations29,
32, 35
and pressure between 0.13 Pa and 35 kPa. The results of magnesium conversion
over time at different reaction temperature are shown in Figure 2.5. They
reported that the magnesium recovery increased by a factor of 1.55 for a 50 C
increase in temperature over the range 1050 to 1560 C.
13
14
Table 2.3 Summaries of Briquette Properties and Experimental Conditions Used by Previous Investigators
Reactant size
Investigators
Pidgeon12
Toguri and
Pidgeon35
Misra et al32
Hughes et al29
Peirce et al18
Yucel et al33
FeSi grade/
excess
Briquette
Pressure
Reactor
Pressure
(Pa)
Catalyst
Time
(h)
Silicon
Dolime
44-853 m: 28%
<44m: 38.5%
178-221m: 43%
44-221m:15%
75.7%Si/ 0
N.A.
0.13
N.A.
N.A.
N.A.
75%Si/15%
20 MPa
0.13
None
<74m
-147m
>147m: 19%
<74m: 65%
N.A.
N.A.
81%Si/18%
20 MPa
13
0.8% CaF2
78.6%Si/17%
200 MPa
0.13
CaF2
75%Si/0
FeSi 75%
13.7 MPa
N.A.
13
100
CaF2 2.5%
CaF2
8
3
<74m: 90%
N.A.
N.A.
Figure 2.6 Magnesium Recovery from the Pidgeon Process. Dolomite type A:
white, hard and macrocrystalline; Dolomite B: brown, friable to hard,
microcrystalline
Based on Figure 2.6, there is some appreciable magnesium recovery at 1000 C,
i.e. 13 to 40 wt%12,
29, 32.
The rate of the silicothermic reaction was found to follow first order kinetics16.
The general equation integrates to:
A0
>? ' 78 @
A0 BA
(2. 9)
D1 4 1 4 F:/$ H '
$IJ
KL+
' >?
(2. 10)
(2. 11)
Figure 2.7 Arrhenius Plot for the Jander Constants (Wynnyckyj et al36)
16
The Arrhenius plot for experimental data based on Jander model is described in
Figure 2.7. The activation energy was calculated from the following Arrhenius
equation:
> ' W exp @
B[\
]3
(2. 12)
d100%
(2. 13)
18
%V&0 l0 B%V&m lm
%V&0 l0
d100%
(2. 14)
20
21
22
In the reaction between MgO and Si, Mg2SiO4 is formed instead of SiO230, 38. This
reaction can be represented by:
4
(2. 15)
The vapour pressure of magnesium associated with reaction (2.15) was 253 Pa
at 1200 C30. When CaO is added to the system (in the form of calcined
dolomite), the solid product becomes Ca2SiO4. Ca2SiO4 formation is favoured
since it has a lower Gibbs energy formation. The Gibbs energy formation of
Ca2SiO4 and Mg2SiO4 are 1513 and 1666 kJ/mol, respectively. The addition of
CaO has several advantages. First is the optimisation of MgO utilisation to
produce Mg. In a CaO-MgO-Si system, 1 mole MgO will produce 1 mole of Mg
instead of 1 mole MgO to 0.5 Mole Mg on the MgO-Si as in reaction of Equation
(2.15). Secondly, since the Gibbs energy of reaction in the CaO-MgO-Si system is
lower than the MgO-Si system (48 kJ/mol for CaO-MgO-Si system and 174
kJ/mol for MgO-Si system at 1100 C), the vapour pressure of magnesium in
CaO-MgO-Si system is significantly higher than the vapour pressure in the MgOSi system.
' 2
$M
$ %
(2. 16)
Thus, silicon as reducing agent may present in liquid alloy phase as in Equation
(2.17) rather than as a solid phase:
4 2
M
(2. 17)
Therefore, when a system contains CaO, MgO and Si species, it is likely that
different competing reactions such as reaction in Equations (2.17) and (2.1)
take place.
This phenomenon was then confirmed with the presence of CaSi2 when a
mixture of MgO, CaO and Si was heated to 1150 C and no magnesium vapour
removed either by vacuum or entrainment gas28. Figure 2.13 shows the
presence of CaSi2 from XRD analysis of the reacted briquettes28. This was in
contrast with when magnesium was removed by entrainment method, where Ca2SiO4 was the dominant phase in the briquettes that detected by XRD.
occurs between the liquid alloy and MgO and CaO. The growth of Ca2SiO4 takes
place between MgO and CaO. Magnesium gas evolves from the solid phase and
diffuses out through the pores of the briquette to the bulk gas phase. The finding
from Wynncykyj42 was supported by Morsi et al34 which also found a solidified
liquid alloy inside a partly reacted briquette.
In general, the investigators agreed that the reaction mechanism of the Pidgeon
process reaction in vacuum condition is controlled by the solid diffusion in the
reactants. In addition, heat transfer also contributes as the limiting factors for
the Pidgeon process reaction. Wynnyckyj et al36 modelled the silicothermic
reaction of a single briquette by coupling heat transfer equation and reaction
rate as described in Figure 2.14. It was shown that there are large radial
temperature gradients in the briquette reacting freely in a vacuum furnace.
25
Figure 2.15 Effect of Pellet Radius on the Conversion Profile and Temperature
Distribution within the Briquette, Predicted by the Model. Temperature: 1177
C, ke= 418 J/msK, Time: 60 min36
Figure 2.15 also shows that there are gradual conversion and temperature
profiles within the briquette at different radial positions. Since there is a
gradient in the temperature and conversion profile, Wynnyckyj et al36
concluded that the conduction through briquette and the intrinsic reaction are
slow and limit the reaction.
(2. 18)
where kc is mass transfer coefficient, which was predicted from Ranz and
Marshall correlation43, PB and PS are the vapour pressures of gas in bulk stream
and surface, respectively.
26
Figure 2.16 Calculated Magnesium Pressure on the Briquette Surface and Bulk
Gas37
Figure 2.16 shows the calculated magnesium vapour pressure on the surface of
briquette and the bulk hydrogen gas. These calculations show that there is
significant resistance on the gas-film mass transfer of magnesium vapour,
especially at the beginning of the reaction.
The global warming potential (GWP) for this process was calculated to be 13.80
kg CO2/kg Mg ingot, which is approximately about a third of the Pidgeon
processs GWP49. The main reason for such diverging result lies in the fact that
the Bolzano process utilises an electric-heated reactor, where more than 80% of
the total used electricity comes from hydropower while the Pidgeon process
relies on a low-efficient coal-fired reactor49.
28
29
(2. 19)
The calcined dolomite, ferrosilicon and alumina dissolve in the slag phase
before the silicothermic reaction occurs. The process is operated at a
temperature of 1550 C and pressure of 5 kPa in an electric arc furnace. The slag
composition is maintained at 55 wt% of CaO, 25 wt% of SiO2, 14 wt% of Al2O3
and 6 wt% of MgO. A phase diagram for the CaO-SiO2-Al2O3-MgO system is given
in Figure 2.19. The slag composition lies on the dicalcium silicate area close to
the periclase border.
A simplified silicothermic reduction in the Magnetherm process can be written
as follows:
M,&
M
(2. 20)
There are few kinetic studies on the fundamental aspects of reduction of MgO in
the molten slag. Most of the studies only give a description7,
52, 56-59
of the
30
aluminium alloy in the MgO-Al2O3-CaO slag60 also found that the mass
transport in the slag/metal interfacial area controlled the overall reaction.
(2. 21)
31
(2. 22)
In addition to remove Ca, the flux also captures oxide inclusion and forms a
sludge of heavy oxy-chloride8. The refining practice can produce a magnesium
ingot with a standard composition as required by ASTM B92. However, the
refining stage means a higher production cost and less magnesium metal yield.
There is about 5-8% magnesium lost in the refining stage59.
Table 2.4 Impurities in the Magnesium Produced from the Magnetherm Process
Before and After Refining (using MgCl2 and KCl fluxs) process, in wt%59
Impurities
Before refining
After refining
Calcium
0.77 1.05
0.005
Silicon
0.11 0.16
0.063 0.11
0.037 0.088
< 0.05
Aluminium
32
Table 2.5 shows the typical composition of magnesium vapour produced via the
Heggie-Iolaire process. Whilst the best individual run may produce 99.06 wt%
of pure magnesium, the average purity of the product is similar to those from
the Magnetherm process.
Table 2.5 Composition of Magnesium Process in Heggie-Iolaire Process64
Element
Mg
Ca
Al
Si
97.4
1.28
0.68
< 0.07
99.06
0.46
<0.06
0.05
MgO
CaO
SiO2
Al2O3
FeO
MnO
LOI*
Cal.dol 1
Cal.dol 2
Alumina
Material
Aluminium
FeSi
38
35
Si
0.06
75.5
57.8
55.5
0.1
Fe
0.15
18.1
1.1
2.6
0.1
Al
99.8
2.4
0.4
1
99.3
C
N.A.
0.1
0.4
1.4
0.1
Ca
N.A
0.7
0.2
1.5
Mg
0.0025
0.03
0.3
0.5
Mn
0.13
0.1
*Loss of Ignition
34
(2. 23)
(2. 24)
35
Besides the operating conditions, the differences between the Mintek and the
Magnetherm processes lie in the slag chemistry. The Mintek process has a
higher liquidus temperature compared to the Magnetherm process. As
illustrated in Figure 2.20, the slag composition of the Mintek process (black
area) has a liquidus temperature of 1700 C. When MgO is reduced using
ferrosilicon and carried out at atmospheric pressure, the reaction is predicted
by thermodynamics to occur at temperatures above 1950 C. Barcza et al66
suggested that by adding bauxite, the liquidus temperature of the slag can be
lowered to between 1700 and 1750 C, so the furnace operating temperature
can be reduced as well. In a pilot scale plant, Abdellatif70 reported that the
temperature range of the system can adjusted to be in the range of 1600 to 1700
C with bauxite addition70.
While there are a number of papers from Mintek that explains the process
description, whether it is in a small scale67 or in a pilot plant scale69, 70, there is
no fundamental thermodynamics or kinetics study of this process in the
literature. A study based on a thermodynamic simulation of the Mintek process
using PyroSim (in-house thermochemical software owned by Mintek) was
carried out to determine the theoretical operating condition and slag
composition in the Mintek process69. However, there is no published article
explaining the detail of the work on the thermodynamics of the Mintek Process.
Cameron et al55,
72
physical and chemical details to the silicothermic reaction in molten slag such as
the Mintek process.
36
37
Barcza et al66 explained the work of small scale test of magnesium production at
nearly atmospheric pressure. They claimed that the produced magnesium has a
purity of 99.80 wt%. The typical composition of metallic element in the
magnesium metal based on this work is shown in Table 2.7, while the resulted
slag composition is presented in Table 2.8. In the test 1, the magnesium
produced contains 0.1 wt % of Ca, 0.03 wt % of Si, 0.01 wt% of Al, 0.01 wt% of
Fe and 0.02 wt% of Mn. The slag composition contains 6.3 to 8.5 wt% of MgO,
47.7 to 56.2 wt% of CaO, 22.3 to 31.9 wt% of SiO2 and 10.8 to 12.7 wt% of Al2O3.
This composition is comparable with the Magnetherms slag composition.
Abdellatif69 argued that the Mintek process has several advantages compared to
the Pidgeon and the Magnethem process. The potential risk of air-ingress into
the system is largely eliminated because the operation is carried out at
atmospheric pressure. Condensation to a liquid phase reduces the energy
requirements in the cleaning and refining operation, as the remelting of the
crude magnesium is not be been required69. However, condensing to a liquid
phase also implies that the condensing surface needs to be maintained at
relatively high temperatures (greater than 650 C)69 and requires a large
condensing area.
Table 2. 7 Composition of Condensed Magnesium (wt%)66
Test
Mg
Ca
Si
Al
Fe
Mn
99.81
0.10
0.03
0.01
0.01
0.02
99.84
0.08
0.02
0.01
0.01
0.03
99.80
0.09
0.02
0.02
0.02
0.04
99.80
0.10
0.02
0.02
0.02
0.02
MgO
CaO
SiO2
Al2O3
1
2
3
4
7.9
8.5
4.7
6.3
53.3
52.5
56.2
47.7
23.3
24.6
22.3
31.9
12.7
10.9
12.9
10.8
38
M130 Flux
Fluorspar
KCl
Mg
Al
Si
Ca
Fe
Cl
Na
K
F
9.69
0.08
0.37
2.13
0.20
56.15
NA
27.10
1.95
NA
0.44
0.215
48.45
0.236
0.0144
0.01
0.011
51.29
NA
0.12
0.94
0.019
0.03
47.55
0.01
50.90
NA
The crude magnesium produced by MTMP is refined in two stages8. In the first
step, crude metal is melted and M130 flux is added to the melt. M130 flux is an
MgCl2-KCl flux which has compositions listed in Table 2.9. M130 flux captures
the oxide and nitride inclusions of Mg, Al, Ca, and Si, and forms a thick chloride
sludge which settles out at the bottom of the refining crucible8. Calcium is
removed by following reaction:
7$M
PJ,M '
PJ,M 7$
(2. 25)
The subsequent refining uses mixtures of M130 flux and FeCl3. This stage is
carried out between temperature 715 and 760 C. Ferric chloride is used to
capture silicon impurity in the molten magnesium metal and convert it into a
39
PJ,M
PJ,M !"7rM ' !"
$
7$M
$
(2. 26)
This refining is not only reducing the silicon content of the metal, but also
lowering metallic impurities such as Fe, Mn, Cr, Ni, and Al. Table 2.10 shows the
chemical analysis of the crude and the refined magnesium. The refining
operation was claimed to reduce the impurities content in the magnesium, such
as Al, Si, Ca and Fe to be less that 0.01 wt%8.
Table 2. 10 Chemical Analyses of Crude and Clean Magnesium, wt%8
Element
ASTM B92
Grade 9980A
Crude Mg
Clean Mg
Avg.
Max.
Min.
Al
0.05 max
0.066
0.040
0.253
0.003
Si
0.05 max
0.281
0.095
0.500
0.014
Ca
0.05 max
0.385
0.023
0.102
0.005
Fe
0.05 max
0.250
0.047
0.100
0.002
The Mintek Process has potential future for magnesium production. In 2004,
Gossan Resources Ltd. which holds a high-purity dolomite property at Inwood,
Manitoba, Canada conducted a preliminary study to produce magnesium using
Mintek Process77. The development of this process leads to the Gossan-Zuliani
process, which operates at temperature higher than 1550 C at atmosphere
pressure. The utilisation of hydro power gives a great advantage over the
Chinese Pidgeon process in terms of greenhouse emissions78.
41
Value
Melting point
Boiling point
Latent heat of fusion
Latent heat of evaporation
Heat of combustion
Specific heat at 20 C
Specific heat at 600 C
Electrical resistivity at 20 C
Thermal conductivity at 25 C
Thermal expansion at 20 C
Thermal expansion at 20 300 C
Density (solid) at 600 C
Standard redox potential
650 + 2 C
1107 + 10 C
0.37 MJ/kg
5.25 MJ/kg
25.1 MJ/kg
1030 J.kg-1K-1
1178 J.kg-1K-1
4.45 .cm
155 Wm-1K-1
25.2 10-6 K-1
27-28 10-6 K-1
1622 gcm-3
-2.372 V
Commercial
99.80
Grade
% max
High-purity
99.80 Grade
% max
Aluminum
(1)
(1)
Zinc
(1)
(1)
Manganese
0.10
0.01
Iron
(1)
0.0070
Nickel
0.001
0.001
Copper
0.02
0.005
Silicon
(1)
0.010
Lead
0.01
0.005
Calcium
0.010
0.005
Tin
0.01
0.001
Cadmium
Others, each
0.05
0.012
0.20
0.100
Others, total
Controlled by limits for other, each
Super Purity
99.95 Grade
Spec %
Mean %
max
(1)
0.0040
(1)
0.0045
0.01
0.0030
0.03
0.0015
0.001
<0.0005
0.002
<0.0005
0.010
0.0045
0.003
0.0010
0.003
0.0012
0.001
<0.001
0.01
0.03
-
Ultra Purity
99.98 Grade
Spec %
Mean %
max
0.004
0.0030
0.007
0.0045
0.002
0.0015
0.002
0.0015
0.0005
<0.0005
0.0005
<0.0005
0.003
0.0025
0.001
<0.0010
0.003
0.0012
0.001
<0.0010
<0.0001
0.005
0.02
-
Magnesium ingot is the main material to produce magnesium alloy AZ91 D. The
composition of magnesium alloys AZ91D and AM60A is listed in Table 2.13.
Elements such as Fe, Ni, and Cu are harmful to corrosion properties, and strict
specification limits apply for these elements
80.
materials to precipitate Fe. For AZ91D (8.3-9.7% Al, 0.15% Mn, 0.35 1.0% Zn),
after Mn, Al, and Zn is added to molten Mg, the temperature of molten alloy is
lowered to the casting temperature. During alloying and equilibrating process,
Fe precipitated as intermetallic compounds that settle in the bottom of furnace.
42
AZ91D (wt%)
AM60A (wt%)
Al
8.3 to 9.7
5.5 to 6.5
Mn
0.15 min.
0.13 min
Zn
0.35 to 1.0
0.22
Si
0.10 max.
0.50 Si max.
Fe
0.005 max.
N.A.
Cu
0.030 max.
0.35 max.
Ni
0.002 max.
0.03
Zn
N.A.
0.22
others
N.A.
Mg
balance Mg.
balance Mg
43
44
(3. 1)
(3. 2)
The function which decides whether a process will occur is called the free
energy change, G, which is defined by:
' 4 6
where
(3. 3)
y {
,,z
. }
,\
,|
45
(3. 4)
(3. 5)
When there is more than one compounds in a solution, a partial Gibbs energy,
, is introduced. The partial Gibbs energy is related to the activity of
component i in the solution, ai, which is defined as follows:
' 5678
(3. 6)
(3. 7)
In the Gibbs minimisation method81-83, the total Gibbs energy of all phases in the
system is kept at a minimum. The total Gibbs energy can be calculated either
from knowledge of chemical potential of component i, , by:
' 8
(3. 8)
(3. 9)
' d ' d 5678
(3. 10)
The ni-values must be non-negative, while the mass balance constraints must be
satisfied as in Equation (3.11)82.
S 8 ' t p ' 1,2,
:
(3. 11)
where aji is the number of atom of element j and bj is the total atom of element j.
= d @]30 C dJ J,M @
]3
L.
C 78 @
L.
(3. 12)
(3. 13)
The Gibbs energy of each phase, Gfor real system can be divided into three
contributions91, 92:
' ,
47
(3. 14)
term, which relates to real behaviour of the solution91, 92. The detail of different
solution models will be described in Section 3.1.3.
(3. 15)
' 4 _6 4 8 4 16
(3. 16)
(3. 17)
These databases were collected and critically assessed before included in the
thermochemical software as data sources for thermodynamic calculations. Some
established database are JANAF thermochemical tables26, SGTE (Scientific
Group Thermodata Europe)93, NPL, and FACT database94.
(3. 18)
(3. 19)
The ideal solution model is often used for a mixture of vapour in atmospheric
pressure, as the behaviour of vapour in this condition follows Raoults law96.
While it is common for many researchers to use the ideal solution model as a
starting point for their calculation, the complex condensed phase such as slag
and metallic phase necessitate more sophisticated models.
49
(3. 20)
(3. 21)
where
has a constant value based on the Henrian concentration range and
may be obtained directly from . Interaction coefficients98 are introduced to
allow this model to be applied to higher order systems. The partial Gibbs energy
is then defined as follows:
'
5678d 56 d
(3. 22)
(3. 23)
(3. 24)
(3. 25)
| ,J JP
SPK,JRKP 3+
50
' 3
+
(3. 26)
Some examples of the application of the regular solution model are in the MgOFeO solid solution102, Thallium-Tin system103, and Iron-Nickel system104.
A sub-regular model is used for a more complex systems, where the interaction
coefficients at certain temperature are considered to change linearly with
composition101:
' d d
d
d
(3. 27)
, d 4 d
(3. 28)
,
, ' t 6
with
(3. 29)
where Li,j is a binary interaction parameter, while an and bn are the model
parameters. When n = 0, the excess Gibbs energy become regular and is similar
to the regular solution model. When n = 1, the excess Gibbs energy become
subregular.
(3. 30)
` ' 0
(3.31)
The relationship between mole fraction (xi) and fractional site (yi) is described
by the following equation:
d '
(3. 32)
:B
.
where yVa indicates the vacancy site fraction. The interaction parameter of the
excess Gibbs energy is also described using the Redlich-Kister polynomial. The
Gibbs energy of solution is defined by the following equation:
' 8 56 ` 78` ` ` I ` 4 `
(3. 33)
The application of the sublattice model includes interstitial phases and complex
intermetallic compounds92, for example in the Fe-Cr-C steel and Ni-Al solid
solution109. Fe and Cr in f.c.c crystal form with C as intersititial, the phase can be
modelled as (Fe,Cr)1(C,Va)2110. There are also several models which developed
based on the sublattice models, such as Compound Energy Formalism108 and
ionic liquid models111.
52
The Gibbs energy expression in the CEF per formula unit of solution is written
as follows:
' `V$ `V: 4 6A P
(3. 34)
(3. 35)
at
around
specific conditions
and compositions.
Modified
(3. 36)
The Gibbs energy for the liquid using this model can be written as follows:
Ma ' 8 Ma 8 Ma 4 6A
0
$
P ,Ma
(3. 37)
where ni and nj are the number of moles of the component i and j, nij is the
number of (i-j) pairs, and SC is the configurational entropy of mixing given for
randomly distributing the (i-i), (i-j), and (i-j) pairs. The configurational entropy
is defined as:
0
T U& ' 45D8 lnd 8 lnd H 4 5 8 78 00+ 8 78 + 8 78
0
(3. 38)
The molar and entropy change gAB is noted as (-T). Coordination-equivalent
fractions, yi, and Z, coordination number is introduced in the model, which is
describes as follows:
0 0
` '
0 0
(3. 39)
00
(3. 40)
00 0
'
:,
d :,
d
:
(3. 41)
The parameters such as
,
and is optimised using experimental data.
There are also some other approaches which have been adapted to described an
ordered system, such as Cluster Varian Method (CVM)121, Monte Carlo (MC) and
Bragg-William-Gosrsky (BWG)122,
123
The free energy of the system is then described in terms of these order
parameters, and the equilibrium of the system is determined by minimising the
free energy of the system with respect to the order parameter.
3.1.4.1 Chemix-Thermodata
Chemix was a part of the CSIRO-SGTE Thermodata System, which was
developed by CSIRO minerals in the 1980s. The databases used in Chemix are
SGTE 1977, JANAF, NPL, and CSIRO. This module uses Solgasmix minimisation
subroutine to calculate equilibrium of multi-component and multiphase system.
A number of applications in extractive metallurgy has been reported, such as
direct smelting of zinc concentrate124, bauxite purification system125, solid
solution formation between arsenic and antimony oxides126, and carbothermic
of magnesium production127.
The activity coefficient models which are available in Chemix include fixed
activity coefficient, polynomial, Redlich-Kister, Margules, Virial, Redlich-Kwong,
and Pitzer dilute solution. The activity coefficient for each phase must be
entered by user, which can be obtained from a private database or available
literature. Whilst widely used in Australia during the 1990s, CSIRO has stopped
providing technical support for the software.
55
3.1.4.2 HSC
HSC Chemistry was developed by Outokumpu Technology in 1974. The
database used in HSC are taken from Barin128 and JANAF26 thermochemical
database. The Solgasmix routine83 based on Gibbs energy minimisation is also
used in the equilibrium module. In HSC, definition of system is crucial step and
carried out by the user. The users must specify the species that may be present
at equilibrium, though the software can readily identify the possible
combinations. The activity coefficients for individual species may be entered as
a constant number, or as a polynomial function of composition and
temperature. HSC has wide applications and is widely used in industry because
of its user-friendliness and calculating power. It is also used extensively for
calculating heat and mass balances for process flowsheets.
3.1.4.3 FactSage
FactSage is an integrated database computing system for chemical
thermodynamic. This package has optimized database for solutions, such as
alloys, liquid and solid oxides, and slags. For pure components, the data are
taken from JANAF Thermochemical Tables26, FACT data, and SGTE data128. The
details of this thermochemical package, which includes the databases and
various calculation modules, can be found elsewhere94. The solution models and
database for common systems have been optimised by the developer, such as
for oxide systems, slag, matte, salt, and light metals.
The user can use his/her own private database in FactSage software using the
Compound module for the species properties (G, H, S, Cp) and the Solution
module for solution interaction parameters. Thermochemical solution models
for various systems are available, for example random solution model, CEF, and
modified quasichemical models.
compounds are react to reach the state of equilibrium. Phases from the
compound and solution databases are retrieved and listed as possible products
in the equilibrium result. React module calculates the enthalpy and Gibbs
energy of reaction, and a Phase Diagram module for generating phase
diagram.
3.1.4.4 MTDATA
MTDATA (Metallurgical and Thermochemical Databank) was developed by
National Physical Laboratory, England. The principle of MTDATA is similar with
other thermochemical packages, which is a software/data package for the
calculation of phase equilibria in multi-component and multiphase systems
using critically assessed thermodynamic data129. Computational interface for
thermodynamic calculations with MATLAB also has been reported130. It uses
Gibbs energy minimisation routine to predict equilibrium and has a number of
different modules allowing presentation and analysis of its predictions in
different formats such as Pourbaix, Kellogg or phase diagrams. It primary
calculation module for complex equilibria in metallurgical systems is called
Multiphase. The specifics of the minimisation routine used are dependent on the
level of accuracy required in the calculation. The highest accuracy minimisation
routine is essentially consistent with Solgasmix131.
57
The kinetics of reaction is highly dependent on the condition of the system. The
reaction is called homogeneous when it includes one phase and heterogeneous
when involves two or more phases. Metallurgical reactions are largely
heterogeneous reactions, for example gas-solid reactions and slag-metal
reactions. A number of parameters may influence the kinetics of reaction,
including temperature, pressure and interfacial area. The analysis of overall
reaction kinetics of a system has been based on the expressions that either
involve a number of assumptions or are empirical133. This section will describe
the fundamental kinetics of heterogeneous reaction, with an emphasis to the
solid-solid reaction and gas-solid reaction.
is in the interface between the product (AB2O4) and AO. Conversely, when
counter-diffusion is involved, the product growth will occur on both side of the
interface.
(3. 42)
When the resistance of the gas film controls the overall reaction, as described in
Figure 3.2, the concentration of gaseous reactant is zero at the surface of
particle. Hence, the concentration driving force is constant during the reaction.
(3. 43)
rxI* A\*
60
| ]
(3. 44)
144,
146,
Other gas-solid reaction models include the Volume Reaction model149, the
Particle-Pellet/Grain model150, 151, the Modified Volume reaction models142, 149
and the Modified Grain model152,
153.
149.
The
Modified Grain model also takes account the structural changes, where the
radius of the grain is assumed to change due to the differences in the molal
volume of the products and reactants152,
provided elsewhere138.
61
153.
There are several reaction models for mixed powder reaction based on three
different rate-limiting controls:
'
(3. 45)
` ' i1 4 1 4 d
62
(3. 46)
1 4 1 4 F $ '
$IJ
K+
' >?
(3. 47)
1 4 F ' @+ C + exp @4
+ + J
+
(3. 48)
1 4 F ' @+ C + exp @4
where K = 2D/L2.
+ + J
+
(3. 49)
c. Ginstling-Brounshtein model
Ginstling-Brounshtein model156 is based on the radial steady-state
diffusion in a sphere using a constant reactant concentration on the
phase boundaries. In this model, product thickness is assumed as a
spherical shell. Ficks equation in the case of spherical symmetry and in
spherical coordinates has the following form:
A
J
+ A
$ A
' @K + K K C
63
(3. 50)
'
A ]]B
(3. 51)
K +
(3. 52)
I J
KL+
' ?
(3. 53)
d. Valensi-Carter model
Valensi-Carter157 pointed that Jander model154 has two simplifications.
First, the thickness of the product layer in the Jander model is assumed
to be a planar surface. The second simplification was made from the
assumption that the specific volume of the product is similar to the
specific volume of reactant. Both simplifications will result in
inconsistency between Jander model and experimental data at a large
conversion157.
$:BI2 J
KL+
a. For a sphere reacting from surface inwards, the conversion versus time
can be written as follows:
>? ' 1 4 1 4 F:/r
(3. 55)
138,
(3. 56)
(3. 57)
4 1 ' >?
B: :B
(3. 58)
(3. 59)
p
' 4 @ \ C
(3. 60)
where jAx is the molar rate of flux A in the x-direction (mol.s-1.cm-2), DA is the
diffusion coefficient or diffusivity of A (cm2s-1) and CA is the concentration of A
(mol.cm-3).
'4
\
+ A
(3. 61)
Ficks second law can be solved using appropriate boundary conditions that
determined by experiment.
66
' $ h
(3. 62)
<
where is the inter-atomic spacing and v is jump frequency of the atom. Selfdiffusion may also apply to a homogeneous alloy.
is used to
When a concentration gradient present, inter-diffusion coefficient (
determine the rate of flux A or B atom in the A-B system. The diffusion of atom
in non-metals similar with the diffusion in metals, but there is additional effects
applied due to the varying degrees of polarisation between cations and
anions163. The diffusion coefficient in solids is a function of temperature based
on the Arrhenius law161:
' " B[\/]3
(3. 63)
:/$ 3 /+
' r @
(+
(3. 64)
Gas diffusion studies have been concerned with measuring and predicting
diffusion coefficients in gaseous mixtures161. In a multi-component gas,
diffusivity of species A in A-B gas mixture is similar to the diffusivity of species B
67
.:::;r3
(\|
+
z,\|
V V
\
(3. 65)
:
$
.
Diffusion of gaseous species in porous solid is more complicated and much less
well understood. The actual diffusion path will not follow the straight line but
will quite tortuous. In addition, the pores that may be small enough to the
species and the pressure gradient may affect the actual diffusion134. Hence, the
rate of pore diffusion is smaller than that of the molecular diffusion for
comparable driving force. The effective diffusivity is introduced to describe
diffusion in porous medium, which is a function of porosity, , and tortuosity, :
(3. 66)
If gas diffusion occurs in a very fine pore, particularly at low pressure, the mean
free path of the molecules may be larger than the diameter of the passage. Thus,
collision with the wall becomes much frequent compared to the collision with
other molecules. This diffusion is called Knudsen diffusion134. Knudsen
diffusivity, DK, is defined as the following equation:
$
' @rC iS h3
(3. 67)
where rp is the radius of the pore and vT is the average velocity of molecules.
Mason et al164 proposed the diffusion flux of species A in an isothermal porous
solid to be represented by the following equation:
68
(3. 68)
The first term represents effective diffusion, the second term represents bulk
flow due to diffusion, and the third term represents transport due to gradient in
pressure. ' PUU /PUU , ' PUU /I , and :
,PUU
B:
(3. 69)
Figure 3.3 Diffusion of Species A from a Solid Surface into a Moving Gas
Stream134
Figure 3.3 shows the schematic representation of diffusion from a solid surface
into the gas stream. The rate of mass transfer of species A from the solid into the
gas stream is given by:
' >T 4
(3. 70)
where NA is the mass transfer rate per unit solid surface area, kc, is the mass
transfer coefficient, CAs and CAo are the concentration of species A at the solid
surface and the gas stream, respectively.
'(
(3. 71)
70
the other hand, the formation of solid particle demands a quantity of energy to
form solid surface. Therefore, the quantity of work required to form a stable
nucleus can be written and expanded as follows:
%
' 4i $ 4 i r
r
$
K
' r i $
(3. 72)
78 '
(3. 73)
]3K
' r]3Mc+
(3. 74)
This expression indicates that when the system is completely saturated, with
supersaturation reaches one, the amount energy for nucleation is infinite. The
system need to be supersaturated in order to create a homogeneous nucleation.
The free energy associated with the homogeneous nucleation comprises the
surface excess free energy, , and the volume excess free energy, . In a
supersaturated condition, this becomes:
%
(3. 75)
TKJ ' r
+
'
%y
r
(3. 76)
where rc is the critical nucleus, which represent the minimum size of a stable
nucleus. Correspondingly, the critical radius of nucleus is defined as follows:
72
iT '
(3. 77)
I3Mc
The rate of nucleation, J, e.g. the number of nuclei formed per unit time per unit
volume, can be expressed as Arrhenius equation:
' W "d 4
y0
I3
:< b +
(3. 78)
$ :/$
:$ "d
B:< +
rI 3 Mc+
(3. 79)
where is the surface free energy of molecule, m is the mass of the condensing
molecule, V is the volume of condensing molecule, N1 is the number density of
the monomer, and k is Boltzmanns constant (1.38010-23 J/K). This equation
indicates that the rate of nucleation is affected by three variables: temperature,
degree of saturation, and interfacial tension.
While the Classical Nucleation Theory (CNT) has been widely used as a main
tool for calculations of nucleation rates in practically relevant systems, the
magnitude and temperature dependence of the Classical Nucleation Rate is
often contradicted with experiments172. The discussion of the failure of CNT has
been focused on two explanations: (1) CNT miscalculates the degrees of
freedom of cluster, (2) the use of macroscopic thermodynamic properties to
molecular-size system is inaccurate173, 174, and (3) assuming steady state at the
liquid/solid-gas interface175. There have been various corrections to this
theory176,
177,
180.
well for some substances and conditions, but fail in other cases just like the
original theory181.
surface tension, 0 6 4 6, excess surface entropy and critical point quantities
to describe the homogeneous nucleation rate into an approximate material
independent form.
where:
c3
SKP
' A @
c(. $
(-
I3
(3. 80)
(3. 81)
T ' @ Q- C y I3 y
%
(3. 82)
y y
' @r C
+/ I3
@3C
@C
(3. 83)
Tc, Pc, T , and T are the critical temperature, pressure, density, and inverse
thermal wavelength of material, respectively. By replacing the bulk surface
tension with scaled surface tension, 0 6 4 6, the exponential term is
expressed as a reduced form :
4 I3 ' 4 @
:<
r
C r @ 3y 4 1C @Mc+ C
(3. 84)
is 1.5 to 2.2 for most simple and associated liquid176 and 0.8 for most metallic
liquids182.
74
For a flux of 1 cm3/s, this model predicts the critical supersaturation ratio, Scr,
correlates to:
3
ln TK r/$ 3- 4 1
r/$
(3. 85)
'@
:< :/r
r
78
B:/$
( 3. 86)
r/$
' 78TK .
(3. 87)
where Q represents the bracketed terms. The Scaled Nucleation Theory has
been reported to be consistent with experimental study of nucleation of several
vapours to solid, such as magnesium, silicon monoxide, and cesium vapour141,
183-185.
According to the SNT, the surface energy can be estimated by the scaled
I/+/
' 6A 4 6
(3. 88)
186.
75
c
(3. 89)
where JCNT is the CNT expression for the homogeneous nucleation rate J, and
is:
'
r</
(3. 90)
+/ I3
33
4 1
r/$
(3. 91)
where
AA3
'@
:< :/$
r
78
36:/r @ 3y 4 1C
B:/$
(3. 92)
TKJ
' TKJ
(3. 93)
Where is less than unity. The factor that controlling heterogeneous nucleation
is interfacial energy, , that closely related to contact angle.
'
(3. 94)
$ :/$
:$ "d
76
B:< + U
rI 3 Mc+
(3. 95)
with the factor f() accounting for the decreased energy barrier to nucleation
due to a foreign solid phase.
(3. 96)
77
78
Figure 3.5 The Schematic of Graphite Retort (After Toguri and Pidgeon)38
Toguri and Pidgeon38 determined the reaction rate by measuring the weight
loss of briquette reactants in a high-temperature vacuum furnace incorporating
a thermo-balance, as illustrated in Figure 3.5. This arrangement enables the
monitoring of weight loss of the reactants over the time without opening the
furnace.
40
also
employed a horizontal tube furnace to heat the reactants and collected the
magnesium condensate at the cooler part of the apparatus.
79
Figure 3.7 Effect of Hydrogen Flow Rate on the Apparent Reaction Pressure at
1159 C (after Pidgeon and King27)
80
Kubaschewski and Alcock193 noted a few points regarding the technical details
of the transpiration method. A constriction should be made in the furnace tube
to minimise the counter-diffusion of vapour. A heavier gas, such as argon, is
preferred to minimise this occurrence. Whist the transporting gas must be quite
pure, the total gas flow should be measured by a volume rather than a flow
meter, since the fundamental quantity being measured is the total volume over
a known time193.
An example of interest is a study of magnesium vapour pressure measurement
by Pidgeon and King27, which is schematically described in Figure 3.8.
Magnesium vapours saturate the hydrogen in the reaction zone (25) and are
carried to an iron tube condenser (34) containing a steel wool mesh (34a). The
retort tube (20) made of 28 wt% chromium steel is 0.90 m long with 2.510-2 m
inside diameter and 310-3 m thick. The condenser, a 0.23 m length of malleable
iron pipe, was machined to give a close tight the retort to prevent magnesium
vapours from passing between it and retort tube. A strip of steel wool (34a),
weighing 1.00 g and 0.1 m in length, fills the cross-sectional area with the
condenser at the area where condensation takes place. This configuration
enables a pure magnesium vapour pressure measured from the calculation
derived from the weight loss of the reactant.
81
Figure 3.8 The Schematic of Vapour Pressure Measurement (after Pidgeon and
King27)
The horizontal configuration is usually applied for the study of the Pidgeon
process. Another essential factor in the experimental study, in particular to
examine the magnesium condensate, is the design of condenser. The condenser
material used to cool magnesium vapour varies from steel to copper, with
usually use water as a cooling fluid. Morsi et al34 used a U-shaped copper cooling
tube at the end of the furnace tube. This is described in Figure 3.9.
Misra et al32 employed a specially designed split type condenser with perforated
stainless steel discs. These were placed at regular intervals for collection of
deposits of magnesium at different temperature zones. In this way, the
condensation characteristic of magnesium can be studied. Iron wool was placed
at the cooler end of the condenser to collect traces of alkalies present in the
dolomite. The experimental design from Misra et al 32 is shown in Figure 3.10.
82
83
Absorption (ARAS) at the wavelength of 271.9 nm. These data has been
modelled and fit the nucleation model.
84
(3. 97)
$%;
3
85
4 1.206
(3. 98)
86
4 Research Issues
Review of literatures covering the fundamental of silicothermic processes
suggests that the fundamental thermodynamics of the Pidgeon process has been
established, while previous works have been focused to ascertain the kinetics of
this process, especially in vacuum. While a number of parameters affecting the
process have been examined, there is no general conclusion what really controls
the kinetics of the process. Previous studies of the Pidgeon processs
thermodynamics did not include a thorough treatment of solid solution
behaviour. The knowledge of thermodynamics and kinetics of other
silicothermic processes is also inadequate. It is known that the Pidgeon process
has a relatively low impurities compared to the silicothermic processes
conducted at higher temperatures, such as the Magnetherm and the Mintek
process. However, there is limited information on the behaviour of magnesium
vapour and its impurities in these processes.
The aim of this project is to investigate the fundamental physical chemistry
associated with the silicothermic processes. This study is also concerned with
the behaviour of impurities in the process.
87
The approach used in the study was to first develop thermodynamic modelling
of the silicothermic processes using the Gibbs energy minimisation. Defining the
species involved in the phases and system, identifying the appropriate solution
models for the system and applying a number of assumptions were required in
the development of the thermodynamic modelling. Thermodynamic modelling
was used to predict the variation of magnesium produced from the processes,
including the impurities at different operating conditions.
The second part of the study was to analyse the kinetics of silicothermic
reduction of calcined dolomite, in particular under a flowing gas atmosphere.
Fortunately, there is a set of experimental data for this condition34, which will
be used as the data for kinetics analysis. The kinetics analysis of the process
includes the kinetics of reaction and the mass transfer kinetics of magnesium
vapour from the briquettes to the bulk gas phase.
88
83,
(5. 1)
(5. 2)
where aij is the number of atoms of element j and bj is the total atom of element
j.
The methodology of thermodynamic modelling is schematically described in
Figure 5.1. The thermodynamic modelling was carried out based on these
orders:
1. Definition of species and phases in the system
In order to conduct appropriate thermodynamic modelling, it is essential
to evaluate the possible species and phases in a particular system. When
an important species or phase is not considered, the thermodynamic
calculation may result a deviation from the correct finding. The definition
of species and phases in silicothermic system was carried by evaluating
the available literature.
2. Database definition
Thermodynamic properties database which include H, S, Cp, and G is
important
elements
in
the
thermodynamic
calculation.
Most
90
5. Equilibrium Calculation
Equilibrium calculation based on Gibbs energy minimisation is carried
using Equilib Module in the FactSage software. The calculation details
are described in Appendix E.
91
5.2 Thermodynamic
Processes
Analysis
of
Silicothermic
This section describes a preliminary study carried out in the early research
work. The purpose of this preliminary study is to identify the compounds and
species
of
the
multiphase
system
resulted
from
the
equilibrium
The calculation for this thermodynamic analysis was based on 1000 kg calcined
dolomite. Each process had different compositions and raw materials. As listed
in Table 5.1, the input for the Pidgeon process was calcined dolomite and
ferrosilicon, while the alumina and aluminium were added as the additional
input for the Magnetherm and the Mintek process. Fluorspar (CaF2) as catalyst
was not used in this study35.
Table 5.1 Operating Condition of Silicothermic Processes
Process
Pidgeon
Magnetherm
Mintek
Raw
Materials
Calcined Dolomite
Ferrosilicon
Calcined Dolomite
Ferrosilicon
Alumina
Operating
conditions
T: 1100 to 1200 C
P: 7 20 Pa
T: 1550 C
P: 5 kPa
Calcined dolomite
Ferrosilicon
Aluminium
Alumina
T: 1700 to 1800 C
P: 85 kPa (atmospheric)
92
FTMisc
Description
The FToxid compound database contains all
stoichiometric solid and liquid oxide compounds
evaluated/optimized by the FACT group to be
thermodynamically consistent with the FToxid
solution database.
FACT Miscellaneous databases contain various
databases such as liquid Fe with dilute solutes, liquid
Sn, liquid Pb, light metal alloys etc.
This database contains data for over 4500
compounds. Most of the data for those compounds
which have been evaluated/optimized to be
thermodynamically consistent with the FToxid,
FTsalt, FThall, . . . etc. solution databases.
Table 5.2 shows the description of thermodynamic database which are used in
this study, while the solution models used in the thermodynamic modelling of
silicothermic processes are listed in Table 5.3. The FACT53 compound database
contains thermochemical properties of thousands of compounds from standard
compilations, while the FToxid compound database contain data for pure oxides
and oxide solutions of 20 elements (as well as for dilute solutions of S, SO4, PO4,
H2O/OH, CO3, F, Cl, I, C, N and CN in the molten slag phase). FTMisc contain
databases for various liquid alloys and mattes.
93
FToxid-bC2S51, 170
FToxid-aC2S119, 207
FToxidSLAGA51,167-169
FTmisc_FeLQ208
Description
Monoxide solution with rock salt
(NaCl) structure.
Compounds:
Fe(II)O,CaO,MgO,Mn(II)O,NiO,CoO at
all compositions +
(Al,Fe(III),Cr(III),Ti(IV),Zn,Zr in
dilute amounts)
4Ca2SiO4 solid solution.
Temperature range: 25 to 1437 C
Compounds:
Ca2SiO4 + (Mg2SiO4, Fe2SiO4, Mn2SiO4,
Pb2SiO4, Zn2SiO4, Ca3B2O6 in dilute
amounts). Ca2SiO4 must be present.
-Ca2SiO4 solid solution.
Temperature range: 1437 to 5000 C
Ca2SiO4 + (Mg2SiO4, Fe2SiO4, Mn2SiO4,
Ca3B2O6 in dilute amounts)
Ca2SiO4 must be present.
Liquid oxide solution.
Major oxide components: Oxides of
Al,Ca,Fe(II),Fe(III),Mg,Si
Liquid steel solution. Don't use with
any other liq metal phase. For
Iron/Steelmaking Processes, not
solidification. Fe-rich(not for
stainless)
Compounds: Fe, Mg, MgO, Ca, Al, Si,
O, SiO, AlO, Al2O
Type of Solution
Model
These models take
into account the
mixing of various
cations on
crystallographically
different
sublattices.
Substitutional
model
Substitutional
model
Modified
Quasichemical
model
Associate Model
94
Database used for equilibrium calculation of the Pidgeon process were FACT53
and FACT-Oxid database. The description of these databases is given in Table
5.2. In the event of duplication of compound database (FACT53 and FTOxid),
FTOxid database was preferentially selected with regards to FACT53 since
FTOxid compound database had been evaluated to be consistent with FTOxid
Solution database.
The solution models used for the Pidgeon process equilibrium calculation were
as follows:
1. Vapour phase : ideal gas
2. Oxides in calcined dolomite: Built-in Monoxide solution model with
rocksalt (NaCl) type crystal structure (FTOxid-MeO).
3. Dicalcium silicate: -Ca2SiO4 solution model (FT-Oxid-bC2S). Ca2SiO4 is
the dominant species, while the minor species includes Mg2SiO4 and
Fe2SiO4. The description of the FTOxid-MeO and FT-Oxid-bC2S solution
models are given in Table 5.3.
4. Metallic phase: ideal solution. Metallic phase contains magnesium and its
metallic impurities.
The description of these phases is provided in Appendix A.
In the FactSage software, defining the species resulted from equilibrium
calculation is not necessary since by default, FactSage will include all possible
combinations of species existing in its database for the equilibrium calculation.
Table 5.4 shows the possible species for the Pidgeon process system generated
by FactSage.
The equilibrium calculation was divided into two parts. First, equilibrium was
evaluated at reduction condition, i.e. at 1100 C and 7 Pa. The condition of
equilibrium replicated the practical operation5, 35. The equilibrium calculation at
the reaction temperature resulted a vapour phase and a number of solid phases.
95
Table 5.4 Possible Species for The Pidgeon Process System in Gas and
Condensed Phases
Species in theGas Phase
(FACT53 Database)
SiO, Si3, Si2, Si, O3, O2, O, MgO, Mg2,
Mg, FeO, Fe, CaO, Ca2, Ca, AlO2,
Al2O, Al2, Al, (AlO)2
Condensed Phases
(FTOxid and FACT53 Database)
SiO2,
MgSiO3, MgO, MgAl2O4, Mg4Al10Si2O3,
Mg2Al2Si3O2, Mg2SiO4, Mg2Si, Mg
FeSiO3, FeSi2, FeSi, FeO, FeAl3, FeAl2O4,
Fe3Si, Fe3O4, Fe3Al2Si3O12, Fe2SiO4,
Fe2O3, Fe2Al4Si5O18, Fe
CaSiO3, CaSi2, CaSi, CaOMgOSiO2, CaO2,
CaO, CaMgSi2O6, CaMg2Al16O27, Mg2Ca,
CaFeSi2O6, CaFe4O7, CaAl4O7, CaAl2Si2O8,
CaAl12O19, Ca3SiO5, Ca3Si2O7,
Ca3MgSi2O8, Ca3MgAl4O10, Ca3Fe2Si3o12,
Ca3Al2O6, Ca2SiO4, Ca2Si, Ca3MgSi2O7,
Ca2FeSi2O7, Ca2FeAl2O7, Ca, Al8Mg5,
Al4Ca, Al2SiO5, Al2Si2O7, Al2O3, Al2Fe2O6,
Al2Ca, Al
96
5.2.1.2 Results
The result of the equilibrium calculations were combined and shown in Figure
5.3. From the equilibrium calculation, the product of silicothermic reduction of
calcined dolomite predicted from thermodynamic calculation at a temperature
of 1100 C and 7 Pa are a vapour phase, solid phases, and a number of single
phases (pure compounds). The vapour phase consists of magnesium vapour
with 99.63% purity and consists of the following impurities: Ca(g), Fe(g), SiO(g)
and Al(g). Calcium vapour was found to be the dominant impurity in the vapour
phase with a concentration of 0.35 wt%. The solid phases include -Ca2SiO4
phase as a side product, oxide phase (which contains 99.62% CaO); while the
predicted pure solid compounds are FeSi, Fe, and calcium aluminate (Ca3Al2O6).
Dolime 1000 kg
SiO2
0.42%
FeO
1.34%
MgO 36.13%
CaO
61.74%
Al2O3
0.37%
FeSi
Fe
Si
194 kg
25%
75%
Silicothermic
reduction at
1100 C & 7 Pa
Vapour 218 kg
Mg(g) 99.63%
Ca (g) 0.35 %
Fe (g) 0.01%
SiO(g) 21.1 ppm
Al (g)
0.5 ppm
- Ca2SiO4 796 kg
Ca2SiO4
99.44%
Mg2SiO4
0.56 %
Oxide
MgO
CaO
Al2O3
FeSi
Fe
Ca3Al2O6
95 kg
0.13%
99.62%
0.25%
Condensation of
vapour at 482 C, 7 Pa
Total amount:
218 kg
% Mg to total:
Mg(s) 98.63%
Single Phases
Mg2Ca1.29%
Fe_b.c.c 0.02%
Fe3Si
0.02%
MgO
34.8ppm
FeAl3
0.6 ppm
52 kg
24 kg
9 kg
97
As illustrated in Figure 5.3, the vapour phase generated from the reduction
process is predicted to have 99.63 wt% purity of magnesium, while the metallic
magnesium resulting in equilibrium calculation at 482 C has a purity of
98.63wt%.
The purity of metallic magnesium is lower than its vapour. The thermodynamic
calculation predicts that calcium vapour interacts with magnesium to form
Mg2Ca inter-metallic compound, while aluminium vapour interact with iron
vapour to form FeAl3. This inter-metallic compounds may be formed by the
following reactions:
2& & ' $ ; %$ A ' 4251.822 >/g7
(5. 3)
(5. 4)
Silicon monoxide vapour dissociates to be silicon vapour and reacts with iron to
form Fe3Si with the following reactions:
& & '
&
&
98
(5. 6)
The possible species resulted from the multiphase equilibria of the Magnetherm
process is shown in Table 5.5. The solution models employed in the
thermodynamic analysis of the Magnetherm process were as follows:
1. Vapour phase: ideal gas
2. Oxides in calcined dolomite: Monoxide solution model with rocksalt
(NaCl) type crystal structure (FTOxid-MeO).
3. Slag phase: liquid oxide solution (FToxid-SLAGA).
4. Dicalcium silicate phase: Alpha dicalcium silicate (-Ca2SiO4) solution
model phase was included in the equilibrium calculation. Based on the
literature, -Ca2SiO4 is stable above 1420 C 209 (see Appendix A for the
phase description).
5. Liquid metal in the reduction process: FT-Misc FeLQ solution model208
was included in the model to describe liquid Fe-rich phase.
6. Liquid magnesium: pure liquid magnesium
99
Table 5.5 Possible Species for The Magnetherm and Mintek process Systems
Phase
Species
operating
condition;
and
secondly,
equilibrium
at
the
5.2.2.2 Results
The results of thermodynamic analysis of a typical Magnetherm operation are
shown in Figure 5.4. The predicted purity of magnesium vapour from the
Magnetherm process at 1550 C and 5 kPa is 99.59 wt%. The major impurities
predicted from the thermodynamic calculation are Ca(g), SiO(g) and Fe(g). This
results are similar to a previous investigation that found SiO(g) has an
appreciable vapour pressure above 1300 C38.
100
Dolime 1000 kg
SiO2
0.23%
FeO
0.42%
MgO 38.88%
CaO
60.40%
Bauxite 154 kg
Al2O3 100%
FeSi
194
kg
Fe
25%
Si
75%
Slag 338 kg
SiO2
25%
Al2O3
14%
MgO
6%
CaO
55%
Condensation of
Reduction at 1550 C
and 5 kPa
- Ca2SiO4
Ca2SiO4
Mg2SiO4
Slag
MgO
CaO
Al2O3
SiO2
448 kg
97.12%
2.88%
953 kg
6.52%
52.96 %
21.12%
19.40%
magnesium at
Vapour 206 kg
Mg(g) 99.59 %
650C, 5 kPa
Ca (g)
0.28%
SiO(g)
0.075%
Fe (g)
0.05%
Al (g)
14.5 ppm Mg(l) Metal 206 kg
Mg2(g) 8.07 ppm % Mg to total:
Al2O(g) 0.6 ppm 98.98%
Si(g)
0.2ppm
Single Phases
CaMgSi 1.18%
MgO 0.44%
CaO
0.15%
FeSi 706ppm
CaAl2 144 ppm
FeSi 79 kg
Figure 5.4 Equilibrium calculations for the Magnetherm Process at 1550 C and
5 kPa.
The liquid magnesium predicted from equilibrium calculation at 650 C has a
purity of 98.98 wt%. The 650 C condensation temperature was chosen from
typical condenser temperature in the Magnetherm process. The impurities
predicted from the calculations are in the form of inter-metallic compounds,
which includes CaMgSi (1.18 wt%), MgO(0.44 wt%), CaO (0.15 wt%), FeSi (706
ppm) and CaAl2 (144 ppm).
The compound database and solution model database were similar with those
employed in the Magnetherm process simulation. The compound databases
include FACT53, FTMisc and FTOxid database. The possible species included in
the equilibrium calculation of the Mintek process is given in Table 5.5. The
solution models used in the equilibrium calculation were as follows:
1. Vapour phase: ideal gas
2. Oxides in calcined dolomite: monoxide solution model
3. Slag phase: liquid oxide solution (FToxid-SLAG A).
4. Dicalcium silicate phase: alpha dicalcium silicate (-Ca2SiO4)
5. Liquid metal in the reduction process: FT-Misc FeLQ solution model208
was included in the model to describe liquid Fe-rich phase.
6. Liquid magnesium: pure liquid magnesium
5.2.3.2 Results
The results of thermodynamic analysis of the Mintek process are shown in
Figure 5.5. Thermodynamic calculation predicts magnesium vapour with the
purity of 98.15 % resulted from equilibrium of the Mintek process system at a
temperature of 1750 C and atmospheric pressure. The major impurities are
similar with those in the Magnetherm case, which includes Ca(g), SiO(g) and Fe(g).
The compositions of produced slag are predicted to be as follows: 60.41 wt%
CaO, 15.11 wt% Al2O3, 21.32 wt% SiO2 and 3.14% MgO.
102
Dolime 1000 kg
SiO2
1.07%
Fe2O3 0.32%
MgO 40.31%
CaO
57.94%
Al2O30.36%
FeSi 227 kg
Fe
25%
Si
75%
Aluminium 18.5kg
Fe
0.15%
Si
0.06%
Al
99.75%
Mn
0.002%
Silicothermic reduction at
1750 C and 85 kPa
Slag
194 kg
MgO 3.14%
CaO
60.41%
Al2O3
15.11%
SiO2
21.32%
FeSi 79 kg
- Ca2SiO4 702 kg
Ca2SiO4
98.76%
Mg2SiO4 1.23%
Vapour 239 kg
Mg(g) 98.15%
Ca (g) 1.64%
SiO(g) 0.18%
Al (g)
0.01 %
Mg2(g) 0.01%
Al2O(g)11 ppm
Si(g)6 ppm
Fe (g)1 ppm
Mn(g)
1 ppm
Condensation of
magnesium at
750C, 85 kPa
Metal 239 kg
Mg metal: 225
kg
%Mg to total
93.49%
metal:
Single Phases
Mg2Ca 5.21%
CaO
0.42%
Fe_b.c.c 0.02%
FeSi
0.6 %
FeAl3
0.03 %
Liquid Metal 32 kg
Fe
20.47 %
Si
46.16%
Al
14.95 %
Mg
14.53 %
Ca
3.54 %
Figure 5.5 Equilibrium Calculation for the Mintek Process at 1750 C and 85
kPa.
The produced vapour is further condensed into a liquid phase at 750 C, which
is a typical Mintek condenser temperature. The liquid magnesium is predicted
to have a purity of 93.49 wt%. This prediction is the lowest purity compared to
the Pidgeon process and the Magnetherm process prediction, which is
consistent with available data. Calcium is predicted to be the most dominant
impurity in the vapour phase with 1.64 wt% composition and is followed by SiO
vapour with 0.18 wt% composition.
Pidgeon
Magnetherm
Mintek
Temperature
Mg(g)
Ca(g)
SiO(g)
Fe(g)
Al(g)
Mg2(g)
Al2O(g)
Si(g)
Mn(g)
1100 C
99.63 wt%
0.35 wt%
21.1 ppm
0.01 wt%
0.5 ppm
-
1550 C
99.89 wt%
0.28 wt%
0.075 wt%
0.05 wt%
14.5 ppm
8 ppm
0.6 ppm
0.2 ppm
-
1750 C
98.15 wt%
1.64 wt%
0.18 wt%
1 ppm
0.01 wt%
0.01 wt%
11 ppm
6 ppm
1 ppm
104
Vapour
1100 C
Stage 1
1050 C
solid
impurities
vapour
1050 C
Stage 2
1000 C
vapour
1000 C
solid
impurities
vapour
500 C
Stage ..
482 C
metal
solid phase,
were
treated as
pure
At temperature range between 950 and 1100 C, there are significant amount of
FeSi and CaO compounds which condensed from the system, while the
condensation of Fe is predicted to occur between 850 and 1100 C.
Condensation of Fe vapour is favoured at this temperature range.
The Gibbs energy condensation of Fe is 207.3 kJ/mol at 1050 C. FeSi and CaO
are the results of Ca, Fe, and SiO vapour interaction:
& & !"& ' !"
(5. 7)
107
The order of condensed compound with the decreasing vapour temperature can
generally be written as follows:
FeSi > Fe > CaO/Ca2SiO4/CaAl3O6> CaSi > Al2Ca > Mg2Ca > Mg
108
Pidgeon
Magnetherm
Mintek
99.63
99.98
99.59
99.89
98.15
99.42
0.35
0.02
0.02 0.06
0.28
0.11
0.44 1.11
0.771.05
1.69
0.58
0.03 0.385
0.0002
N.A
0.03 0.07
0.075
N.A.
0.44 - 1.19
0.11 0.16
0.18
N.A
0.1 1.1
0.00005
N.A
-
0.0014
N.A
0.0012
0.0034
0.037 0.088
0.01
N.A.
-
Magnesium (wt %)
Single Stage Equilibrium
Multistage equilibrium
Calcium (wt %)
Single Stage Equilibrium
Multistage equilibrium
Previous Work 73
Actual Data
Silicon (wt %)
Single Stage Equilibrium
Multistage equilibrium
Previous Work73
Actual Data
Aluminium (wt %)
Single Stage Equilibrium
Multistage equilibrium
Previous Work 73
Actual Data
0.007 0.02
0.01 0.066
*previous modelling work and actual data were taken from the literatures
109
For the Pidgeon process, the impurities (such as Ca, Si, and Al) predicted by
current multistage model is in agreement or even lower compared with actual
data. The impurities predicted from the Magnetherm and the Mintek processes
are in the range impurities from actual plant data.
59.
It should be noted that this analysis has not included a detailed literature
evaluation of thermodynamic properties of elements in the system, instead has
only used available thermodynamic data and solution models included in the
FactSage software. The metallic system used in the study was assumed as ideal,
i.e. there is no solid solution behaviour in the metallic system. However, in the
reality, there may be a solid solution between elements in the condensed phase.
The scope of this study and the rest of this thesis will be limited to the Pidgeon
process. While the Pidgeon system is simpler compared to the Magnetherm and
Mintek process, the distribution of impurities predicted from thermodynamic
calculation for the Pidgeon process will have similar tendency with the other
silicothermic processes. This choice is consistent with the goals of this thesis.
111
112
random mixing model to Mg-h.c.p solid solution and liquid solution, while
others211 re-modelled these system using the Modified Quasichemical Model116
for the liquid phase and therandom mixing model for the solid phase. The
thermodynamic solution model of Mg-Ca solid solution was described as a
regular solution model; with the interaction parameter is a function of
temperature.
The excess Gibbs energy for solid solution in Mg-Ca system based on regular
solution model (random mixing solution model) was defined as follows106:
P
(5. 8)
113
215
(b)
(a)
Figure 5.12 (a) Phase Diagram of Mg-Si system, (b) Phase Diagram of Mg-rich
Region on Mg-Si System217
The solid solution and liquid solution of Kevorkov et als work
217were
described by a regular solution model. The excess Gibbs energy for solid
solution in Mg-Ca system based on regular solution model was defined as
follows217:
P
114
(5. 9)
The phase diagram of Ca-Si system, as shown in Figure 5.14, has the
following phases: liquid phase, Ca-b.c.c and Ca-f.c.c phases, and Si-diamond
phases. The compounds involved in the Ca-Si system include Ca2Si, CaSi and
CaSi2 inter-metallic compounds.
The Ca-Si f.c.c and b.c.c solid solution has been described by means of regular
solution model219. The excess Gibbs energy of this system is described by:
P
P
(5. 10)
(5. 11)
116
The excess Gibbs energy for Fe-Si solid solution based on random mixing model
are as follows221:
PBc,UTT '
dP dc @4125247.7 41.1166 4142707.6dP 4dc
P
89907.3dP 4dc C
P
(5. 12)
3890dP 4dc C
(5. 13)
Al-Mg system: random mixing solution model for Al (f.c.c and b.c.c) solid
solution112
Al-Ca system: random mixing solution model for Al (f.c.c and b.c.c) solid
solution219
, d 4 d
(5. 14)
,
, ' t 6
with
(5. 15)
Interaction Parameter
oL
118
1L
2L
1480 2.08T
3500
900 + 0.423T
950
-142707.6
12500
89907.3
-3975 - 5T
-11544
3890
The FTlite database is compiled from European COST 507 and FACT Consortium
Project 2000-2003-NSERC204. The binary systems have all been completely
assessed, modelled and optimised for all phases at all compositions. The model
used for the liquid phase is indicated for each system. All binary systems using
the Modified Quasichemical Model in the Pair Approximation (MQMP) for the
liquid are unique to FactSage.
The SGTE alloy database was based on SGTE database204. In the assessments,
the liquid phase has been described using a simple substitutional solution
approach based on the Redlich-Kister-Muggianu polynomial expression. Most of
the solid phases have been described using sub-lattice models which include
interstitials and vacancies where appropriate. The references used for FTLite
and SGTE alloy database are shown in Tables 5.9 and 5.10, respectively.
Model
Source Data
Ca-Mg
MQMP
Mg-Si
Ca-Si
MQMP
Al-Ca
MQMP
Ca-Fe
Bragg-Williams R-K
Polynomial
Mg-Fe
MQMP
119
Table 5.10 Database for Some Metal System in SGTE alloy 2007 database
Binary System
References
Ca-Mg
Mg-Si
Ca-Si
Al-Ca
Ca-Fe
Not available
Mg-Fe
Not available
Al-Si
While in the duration of this study, there have been some improvements on
FactSage database, especially on the light metal system that has important
element, it has been considered that this study uses an in-house solution
database which has been constructed from literature evaluation. Some of the
original references of the FTLite and SGTE Alloy databases were not available to
public, which made difficult to assess.
120
121
Amount (g)
5972 (57.5%)
4030 (38.8%)
42 (0.4%)
50 (0.48%)
Species
Amount (g)
Ferrosilicon
(75%Si)
Fe
Si
535
1605
150 (1.44%)
Calcined Dolomite : FeSi = 82.72% : 17.28%
The details of the input data used in this study are listed in Table 5.11. The ratio
of calcined dolomite and ferrosilicon is stoichiometric (i.e. 2 moles of calcined
dolomite to 1 mole of silicon). FACT53 and FTOxid compound database were
used for the thermodynamic properties of species involved in the modelling.
122
The solution models used for thermodynamic modelling of the Pidgeon process
comprise the following models:
1. Vapour phase : ideal solution
2. Oxides in calcined dolomite: Built-in Monoxide solution model (FTOxidMeO).
3. Dicalcium silicate: built-in -Ca2SiO4 solution model (FT-Oxid-bC2S).
4. Metallic phase:
a. Ideal solution
b. In-house metallic solution models, as explained in Section 5.3.1.6,
which includes h.c.p solution models, f.c.c solution models, b.c.c
solution models
5.3.3 Results
5.3.3.1 Effect of Some Variables on Magnesium Recovery
5.3.3.1.1 Effect of Temperature
Figure 5.18 shows the predicted magnesium recovery compared with data from
literatures. The predicted value is based on the amount of magnesium vapour
produced by reaction in Equation (2.1) at pressure of 7 Pa calculated using
thermodynamic modelling, while the data are obtained from several previous
works at different time, ranging between one and eight hours, where the details
of their process conditions have been given in Table 2.3.
The recovery of magnesium of the published data was calculated from the
following equation:
l0 %V&0 Blm0. %V&m0.
l0
d100%
(5. 16)
where Win and Wfinal is the weight of initial and final charge, while %Mgin is the
composition of magnesium in the initial charge and %Mgfinal is the composition
of magnesium in the reacted charge.
123
It can be seen that the predicted magnesium conversion increases sharply after
900 C. At a temperature between 1100 and 1200 C, Model I over-predict the
published data by 10 to 12%. At a higher temperature, i.e. 1300 C,
thermodynamic model agrees well with the data.
Figure 5.19 shows the effect of pressure and temperature to the magnesium
recovery. At 0.07 Pa, some discrepancies were observed between the
thermodynamic calculation and the experimental data. Thermodynamic
calculation predicts that significant magnesium is obtained at 800 C and above,
while experimental data12 shows 76 wt% of magnesium recovery is obtained at
1100 C.
124
Figure 5.19 Effect of Pressure to Magnesium Recovery via the Pidgeon process
100
80
60
0.07 Pa
40
0.7 Pa
7 Pa
20
67 Pa
667 Pa
0
600
800
1000
Temperature
1200
(oC)
Model II predicts a higher Ca content to the Toguri and Pidgeons data35, i.e.
0.001 to 1 wt% compared to 0.0008 to 0.0003 wt%. The predicted Si and Fe
content are also higher than the Si and Fe from the data35. Conversely, it
predicts a lower Al content in magnesium, i.e. 10-4 compared to 10-2 wt% in the
data.
126
Table 5.12 lists the detail of impurities composition resulted from the single
stage equilibrium model of vapour condensation. The random mixing solution
model for the metallic phase was used in the modelling. The phases that present
at condensation temperature of magnesium and pressure of 7 Pa based on the
single stage equilibrium model are Mg (h.c.p phase), Fe (b.c.c phase), Mg2Ca, Fe,
Fe3Si, MgO and CaSi inter-metallic compound. Mg h.c.p mainly consists of 99.90
wt% of Mg, 0.10 wt% of Ca with a trace amount of Al and Si. Fe b.c.c phase
consists of 94 wt% of Fe and 6 wt% of Al. In general, the amount of impurities,
both in the form of solid solution and intermetallic compound, increases with
the increasing temperature.
127
Table 5.12 Details of Composition and Phase Present predicted from Model II
Single stage Condensation (per 100 mol Mg) using random Mixing Solution
Model for the Metallic Phases
Condensed Species
Mg h.c.p phase, g
Mg, wt %
Ca, wt %
Al, wt%
Si, wt%
Fe b.c.c phase, g
Fe, wt %
Al, wt %
Single Phase, g
Mg2Ca
Fe
Fe3Si
MgO
Ca2Si
1100
2330
99.90
0.10
0.0042
0.0101
0.01
94.09
5.91
33
0.46
0.32
0.07
-
93
0.82
1.84
4.48
271
3.43
5.05
1.04
-
1250
2116
99.90
0.10
0.101
1.43
94.09
5.91
525
6.03
19.57
4.04
-
Table 5.13 Details of Phase Present predicted from Model II Single stage
Condensation (per 100 mol Mg) using Ideal Solution for the Metallic Phases
Condensed Species
Mg
Mg2Ca
Fe
Fe3Si
MgO
FeAl3
Ca2Si
1100
2324.80
38.17
0.46
0.34
0.07
2.6210-3
-
1250
2111.40
529.80
7.30
59.59
4.04
0.14
-
As for comparison, the single stage modelling of vapour condensation were also
carried out by using ideal solution for the metallic phase. The result is presented
in Table 5.13. The amounts of condensed single phase such as Fe3Si, MgO, FeAl3,
and Ca2Si are similar with the results from single stage condensation model
using random mixing solution model for the metallic phase. The different lies in
the Mg and Fe phase, where Mg h.c.p phase and Fe b.c.c phase have some
impurities dissolved in the phase. Mg h.c.p phase also has a maximum capacity
to dissolve Ca. This is consistent with the phase diagram of Mg-Ca system, which
is shown in Figure 5.10. At 97 to 99 wt% of Mg (the remaining is Ca), typical
purity of Mg produced the Pidgeon process simulation, and the stable phase at
equilibrium is Mg h.c.p and Mg2Ca.
128
The mass and mass fraction of impurities/condensed phase over the range of
temperatures calculated using ideal solution for the metallic phase are plotted
in Figure 5.23 (a). The mass of condensed phase is based on 100 moles of Mg;
while the mass fraction of the condensed phases is with reference to total mass
of condensed phase at correlating temperature. The details of mass of each
129
Figure 5.23 Comparison between (a) Ideal Solution Model and (b) Random
Mixing Solution Model from the Modelling of the Pidgeon Process Impurities at
1160 C Temperature.
Figure 5.23(b) shows the predicted condensed phase calculated using the
random mixing model for the metallic phase, which are represented by mass
and mass fraction of the condensed phase. Fe f.c.c and Fe b.c.c in the graph
refer to f.c.c and b.c.c solution model. The details of mass of species at different
temperature calculated using random mixing model for the metallic phase are
given in Table 5.16.
130
Table 5.15 Mass of the Vapour Phase and Condensed Phases from Multistage Condensation Model at Different Temperature (in
gram per 100 moles Mg) Calculated using Ideal Solution for the Metallic Phases
Temp
1160
(C)
GAS ideal
Mg
2376.01
Ca
57.92
Fe
3.23
SiO
0.40
Al
8.310-3
TOTAL
2437.58
Oxide
CaO
MgO
Al2O3
Total
Single Phase
FeSi
Fe_b.c.c
Al2Ca
Mg2Ca
Mg(s)
1100
1050
1000
950
900
850
800
2376.01
57.77
7.6310-1
0.02
7.9610-3
2434.57
2376.01
57.69
2.0710-1
0.01
1.1210-3
2433.92
2376.01
57.69
5.0510-2
2376.01
57.69
1.1010-2
2376.01
57.69
2.0910-3
2376.01
57.69
1.1210-3
2433.75
1.1210-3
2433.71
1.1210-3
2433.70
1.1210-3
2432.70
0.48
1.5710-4
1.0110-3
0.48
0.03
5.5710-6
4.4210-5
0.03
0.02
1.9110-6
2.7510-6
0.02
0.72
1.99
0.04
0.53
0.02
0.14
0.04
0.01
750
700
650
600
2376.01
57.69
2376.01
57.69
2376.01
57.69
2376.01
57.69
2376.01
57.69
2355.01
39.56
2355.01
0.33
1.1210-3
2433.70
2433.70
2433.70
2433.70
2433.70
2394.56
2355.34
40.18
86.81
1.7910-3
550
500
482
87.54
2307.18
131
132
Table 5.16 Mass of the Vapour Phase and Condensed Phases from Multistage Condensation Model at Different Temperature (in
gram per 100 moles Mg) Calculated using Random Mixing Solution model for the Metallic Phases
Temp (C)
GAS ideal
Mg
Ca
Fe
SiO
Al
Total
Monoxide
CaO
MgO
Al2O3
Total
F.C.C phase
Mg
Ca
Al
Fe
Si
Total
B.C.C phase
Ca
Al
Fe
Si
Total
H.C.P Phase
Mg
Ca
Total
Single Phase
Fe_b.c.c
FeSi_solid (s)
Al2Ca
Mg2Ca
1160
2376.01
57.92
3.23
0.40
8.310-3
2437.58
1100
1050
1000
950
900
850
800
750
700
650
600
550
500
2376.01
57.77
0.76
0.02
1.5610-3
2434.56
2376.01
57.71
0.21
1.8410-3
4.3210-4
2434.91
2376.01
57.71
0.05
2376.01
57.71
1.1010-2
2376.01
57.71
2.0910-3
2376.01
57.71
2376.01
57.71
2376.01
57.71
2376.01
57.71
2376.01
57.71
2376.01
57.71
2355.01
39.56
2355.15
0.33
2434.77
2433.73
2433.72
2433.72
2433.72
2433.72
2433.72
2433.72
2433.72
2394.56
2329.80
0.48
1.6210-4
2.0510-4
0.48
0.03
5.7810-6
2.5210-6
0.03
2.1910-3
2.6810-7
2.5510-5
1.6510-5
3.4610-6
11.36
1.36
1.2810-5
8.9710-6
1.0810-6
0.43
0.43
6.6110-3
0.63
2.6210-5
0.64
1.1210-3
0.10
3.0110-6
0.10
482
2.1910-3
3.2410-6
2.8410-2
1.7410-6
2.8410-2
3.2610-4
0.03
5.9110-7
0.03
2328.42
0.33
2328.75
8.9110-3
0.72
0.04
1.7510-3
3.2810-3
40.18
86.80
Fe is predicted to condense between 950 and 1100 C, with the amount between
1.75 mg and 2 g per 100 moles Mg. The amount of condensed Fe, along with FeSi
oxide phase, decreases with the decreasing of temperature.
When the random mixing solution model for the metal phases is applied, iron
makes up most of the f.c.c. and b.c.c phases. Silicon and aluminium precipitated
in the b.c.c solid solution at the temperature range of 1000 and 1100 C.
At the temperature range between 750 and 850 C, there is no solid phase
predicted from the ideal solution model, while the latter model predicts intermetallic Al2Ca which condenses at 750 C. Both models predict that significant
amount of impurities, at approximately 3.706 g per 100 moles Mg (equal to 0.15
wt% of total metal), has condensed prior to temperature of 750 C. The vapour
phase at below 750 C only contains magnesium and calcium. Using the random
mixing solution model, magnesium was predicted to condense with 99.986 wt%
purity. The model that adopts ideal solution model for the metal phase predicts
some purity of 98.331 wt% magnesium.
133
Figure 5.24 shows the mass (in logarithmic value) and mass fraction of
condensed solid over range of temperature, starting from 1300 C to the
condensation temperature of magnesium, while Table 5.18 provides the details
of mass of each phase at specific temperature.
134
Below a temperature of 950 C, the predicted vapour consists of Mg and Ca. The
condensation of Mg2Ca is predicted to take place between 500 and 550 C, with
the total amount of 541 g of Mg2Ca intermetallic. Mg in h.c.p phase is predicted
to condense at 482 C with 99.99 wt% of Mg purity.
135
136
Table 5.17 Mass of the Vapour Phase and Condensed Phases from Multistage Condensation Model at Different Temperature (in gram
per 100 moles Mg) Calculated using Random Mixing Solution model for the Metallic Phases
Temp (C)
GAS_ideal
Mg
Ca
Fe
SiO
Al
Al2O
Si
Total
a-Ca2SiO4
Mg2SiO4
Ca2SiO4
Total
Monoxide
CaO
MgO
Al2O3
Total
F.C.C phase
Mg
Ca
Al
Fe
Total
B.C.C phase
Ca
Al
Fe
Si
Total
H.C.P Phase
Mg
Ca
Total
SinglePhase
Fe_b.c.c
FeSi_solid (s)
Mg2Ca
1360
2407.92
296.41
207.73
108.44
0.71
0.04
4.610-3
3021.27
1300
1250
1200
2408.60
256.49
65.03
20.17
0.18
5.110-3
1.0110-3
2750.48
2408.63
249.35
24.24
4.44
0.04
2408.63
245.81
8.42
0.62
0.02
2686.69
0.08
86.15
86.23
0.02
15.37
15.39
1150
1100
1050
1000
950
2408.63
245.30
2.72
6.8210-2
5.3210-3
2408.63
245.22
0.81
6.3110-3
1.6510-3
2408.63
245.30
0.22
7.510-4
2.9810-4
2408.63
245.28
0.05
2408.63
245.28
0.01
2663.69
2656.72
2654.66
2654.12
2653.91
2653.91
4.86
9.3410-4
3.910-3
4.87
5.57
7.0610-4
1.2310-3
5.58
0.08
6.3610-6
4.2210-6
0.08
7.410-3
3.6510-7
9.1410-4
0.01
0.00
2.3810-5
4.9810-5
9.9810-6
4.28
4.28
6.5210-5
1.4310-4
2.0210-5
8.15
8.15
1.4510-4
3.410-4
3.1310-5
12.27
12.27
2.6610-5
6.7210-5
3.7910-6
1.48
1.48
1.3610-5
3.7310-5
1.210-6
0.48
0.48
6.9310-6
2.0910-5
3.6310-7
0.15
0.15
0.56
58.86
5.8210-3
55.42
0.15
21.31
1.8610-3
21.45
0.02
2.82
1.9510-4
2.84
0.03
3.69
1.9910-4
3.73
3.6610-3
0.35
1.4510-5
0.35
1.1910-3
0.1
3.210-6
0.1
900-600
550
500
2408.63
245.28
2155.03
36.20
2112.32
0.30
2653.90
2191.2
2112.62
482
3.2810-6
1.110-5
0.04
0.04
2112.10
0.18
2112.29
0.01
126.03
22.49
8.35
0.12
0.01
462.67
79.42
5.4 Discussion
5.4.1 Effect of Operating Condition to Magnesium Recovery
Thermodynamic modelling can determine the amount of particular phases or
compounds at equilibrium. In Figure 5.18, thermodynamic modelling prediction
is compared to magnesium recovery from some published data. The percentage
of magnesium recovery from the model and the data increases with the
increasing process temperature. As the Pidgeon process reaction is
endothermic, the increasing temperature will increase the equilibrium constant
of the reaction, which will increase the magnesium recovery.
However, there is some discrepancy between the prediction and the model in
the lower temperature range. For example, between 1100 and 1200 C, the
model predicts 99 wt% conversions; while the data shows some conversion
between 87 and 89 wt%12, 29, 32, 33, 35. This discrepancy becomes smaller with the
increasing temperature.
137
The equilibrium constant (K), which correlates with the Gibbs energy of
',
+
+
/0 ,)*1 ,-.1
' "d @4
]3
(5. 17)
138
The multistage equilibrium model (Model III) aims to study the distribution of
impurities in the magnesium condensation. The thermodynamic modelling
predicts that significant impurities such Fe, CaO and MgO have condensed at a
higher temperature than the condensation temperature of magnesium. This
indicates that the impurities are likely to condense before reaching the main
condenser, where magnesium vapour condensed.
The predicted magnesium purity based on Model III is is higher than 99.98 wt%,
with calcium is the main impurity. Besides forming Mg2Ca intermetallic, calcium
dissolves in the magnesium h.c.p solid solution.
Mg
Ca
Al
Si
Fe
Model II
Single stage Condensation
97.950
1.970
0.0003
0.053
0.031
Model III.
Multistage Condensation.
(Ideal Solution)
98.331
1.669
N.A.
N.A.
N.A.
Model III.
Multistage Condensation
(Random Mixing Solution
Model)
99.985
0.014
N.A
N.A.
N.A.
99.543
99.850
0.02
0.06
0.03
0.07
0.007
0.02
0.0014
0.019
Actual Analyses35
139
The results from this study suggest that higher purity magnesium can be
achieved in a silicothermic reduction system if equilibrium conditions are
approached in the condensation zone of the reactor. There is a possibility that
the impurities begin to condense in the region between the reactants and the
cooled area where magnesium vapour condenses. Examining the predictions
with the experimental data shown in Table 5.18, it is possible that the
impurities are condensed before magnesium, which is advantageous for the
Pidgeon process system. Detail examination is needed to confirm this
hypothesis since there are no commercial or experimental data available on the
distribution of the impurities in a Pidgeon process retort.
140
141
142
Several researchers
The motivation of this study stems from the thermodynamic analysis study in
Chapter 5, which found that thermodynamic analysis over-predicts the
magnesium recovery in the Pidgeon process. This discrepancy, especially at
lower temperature (i.e. at 1100 to 1200 C), leads to a hypothesis that it may be
possible that kinetic barriers prevent the magnesium from evolving from
calcined dolomite ferrosilicon system in the silicothermic process.
This kinetic study will focus on the silicothermic system under flowing inert
atmosphere, which is relevant to the experimental work which will be described
in Chapter 7. This study will concentrate on a small inert gas flow rate in order
to assess the condition of the system, whether it is controlled by mass transfer
or chemical kinetics. This study may also applicable to systems with a flowing
inert atmosphere, such as the new silicothermic processes, i.e. the Mintek
processes which utilising streaming argon gas at atmospheric pressure.
A
Figure 6.1 Schematic of the Experimental Study of the Pidgeon Process
143
of
condensation:
homogeneous
and
heterogeneous
The interests of the phenomena studied in this chapter are (A), kinetics of
reaction, and (B), the kinetics of transfer of magnesium vapour. The general
explanation of condensation phenomena such nucleation and growth of
magnesium vapour will be included in Chapter 8.
145
Value
2X Si
2.5 %
1.6
0.25 L/min
450 MPa
800 C
1 hour
14
5
10
Figure 6.2 Representatives of (a) Diffusion Control and (b) Phase Boundary
Reaction Control
Based on the possibilities of the rate controlling factors, the kinetic models for
mixed powder reaction is categorised into: product layer diffusion control,
control phase boundary reaction control, nuclei growth control and order of
reaction.
146
Mathematical Model
(ii)
Ginstling-Brounshtein156
(iii)
Valensi-Carter157
(iv)
Serin-Ellickson155
1 4 1 4 F $ '
$
r
14 F
$I
KL+
T BT
>: ' +
S
+
I
4 1 4 F ' ++
KL
+
1 4 F ' @+ C + exp @4
For sphere:
<
+ + J
C
+
+ + J
C
+
surface inwards232
(iii)
? ' >?
1 4 F ' @ + C + exp @4
(ii)
? ' >? ;
Contracting cube
The product layer diffusion models can be divided into several models:
a. Jander model154
The rate of thickening of the reaction product was assumed
inversely proportional to its thickness, which is written as
follows:
J
'
(6. 1)
1 4 1 4 F $ '
$I
KL+
147
? ' >?
(6. 2)
A+ BA
(6. 3)
b. Ginstling-Brounshtein model156
Ginstling-Brounshtein model is based on the radial steady-state
diffusion in sphere using a constant reactant concentration on the
phase boundaries. In this model, product thickness is assumed as
a spherical shell.
+
1 4 r F 4 1 4 F '
I+
KL+
? ' >?
(6. 4)
+ + J
+
(6. 5)
148
1 4 F ' @ + C @ + C "d @4
+ + J
+
(6. 6)
(6. 7)
149
The phase boundary reactions models have been developed for different
geometry and corresponding boundary conditions. Some of these models
are as follows:
a. For a sphere reacting from surface inwards, the conversion, X, and
time, t, relates by equation as follow:
>? ' 1 4 1 4 F:/r
(6. 8)
(6. 9)
(6. 10)
(6. 11)
150
6.2.2 Results
Several assumptions applied for the first part of kinetic modelling are as follow:
The particle shape chosen for the phase boundary controlled model is a
sphere reacting from the surface inwards.
The differences between first order model and phase boundary reaction model
to the experimental data at 1300 C are also obvious in Figure 6.4 (b). At
conversion less than 0.8, both models under-predicts experimental data, while
beyond 0.8 conversion, the models over-predicts the data.
151
Figure 6.4 Comparison between Experimental Data34 and Kinetic Models at (a)
1150 C and (b) 1300 C
The nucleation model appears fit with experimental data, which is noted with
high R2, as listed in Table 6.3. The index m obtained from the plot of ln(ln 1/(1X)) and ln t is between 0.6 0.7. From the original theory158, the value for m
should be an integer of 1, 2, or 3. When m ~ 0.5, it is empirically shown that
reaction is controlled by diffusion235, while when m ~ 1.0, nucleation occurs
with front growth direction and the reaction is controlled by phase boundary
reaction235. Thus, for this system, with m = 0.6, it is suggested that the reaction
is controlled by diffusion.
1150
1200
1250
1300
m
k
R2
0.59
0.0667
0.9663
0.64
0.1570
0.9861
0.55
0.4751
0.9695
0.69
0.7722
0.9979
Jander154
First Order
0.9609
0.9841
0.9628
0.9922
0.8142
0.7615
0.7721
0.883
152
Phase
Boundary
0.7639
0.6286
0.5518
0.6289
Nucleation158
0.9663
0.9861
0.9695
0.9979
Since there are a number of diffusion models, the experimental data was also
analysed using different diffusion models. For the case of Serin-Ellickson
model155, the slab condition was chosen for the modelling calculation. The Z
factor chosen for the Carter model was 1.68, which was based on the ratio of the
volumes of spheres of typical powders which have particle sizes below 74 m
particles157.
The analysis of this isothermal kinetics models was carried out sing the
following methods236:
1. Testing the linearity plots of g(X) against time
The deviation from linearity of conversion, X, versus time plots can be
used to determine which equations merit more detailed analysis.
Standard classical criteria include the correlation coefficient, r; the
standard error of slope of the regression line, sb; or the standard error of
the estimate of X from t can be used to quantify the deviation of a
number of experimental data.
Table 6.5 Correlation Coefficient, R2, of Diffusion Models
T
(oC)
1150
1200
1250
1300
Jander154
0.9609
0.9841
0.9628
0.9922
GinstlingBrounshtein156
0.9619
0.9868
0.9560
0.9691
SerinEllickson155
0.9476
0.9743
0.9188
0.9925
ValensiCarter157
0.9619
0.9855
0.9176
0.9336
Table 6.5 provides the correlation coefficient, R2, of the diffusioncontrolled models to the experimental data. No particular models in this
result that have advanced correlation coefficient at all range of
temperature. However, the Jander154 and Ginstling- Brounshtein156
models have the highest correlation coefficients compared to SerinEllickson155 and Valensi-Carter157 models.
?KP ' J
. BJ
(6. 12)
154
The tred in the current study was calculated using equation ?KP ' J
, where
.2 BJ
t0.4 is the time required to obtain 40% conversion. The result of this testing is
shown in Figure 6.6. All models fit well to experimental data.
The activation energy of this reaction was calculated by plotting ln k with 1/T,
based on the formula:
[,
155
(6. 13)
Figure 6.7 Arrhenius Plot of Natural Logarithm Natural of the Rate Constant and
Reciprocal Temperature (in K)
The intercept corresponds to ln A, which the slope corresponds to Ea/R. The
results are shown in Figure 6.7. The activation energy of the silicothermic
reaction under flowing argon gas is found to be between 299 and 322 kJ/mol.
The activation energy for the bulk diffusion in a solid-solid diffusion is typically
in the range of 40 to 400 kJ/mol39. Activation energy of silicothermic under
flowing argon is higher than activation energy of silicothermic reduction in a
vacuum, which is 226.6 kJ/mol16.
On the interface between reactants, such as CaO, MgO, and Si, and Ca2SiO4
product, the vapour pressure of produced magnesium corresponds to the
equilibrium vapour pressure of magnesium from silicothermic reaction at
conditions temperature.
156
Figure 6.9 Schematic of (a) Pore Diffusion and (b) Gas-Film Mass Transfer
Control
When the kinetics is limited by pore diffusion, the pressure of magnesium at the
surface of the pellet is decreased, as shown schematically in Figure 6.9(a). At
this condition, the rate of gas-film mass transfer is high enough compared to the
pore diffusion, so the magnesium vapour pressure in the bulk is similar to the
vapour pressure at the surface of pellet. Conversely, when the kinetics is limited
by gas film mass transfer only, the rate of pore diffusion is high compared to
gas-film mass transfer, as shown in Figure 6.9 (b).
157
Conversion
0.08
0.25
0.5
0.7
1
0.36
0.56
0.56
0.59
0.59
Table 6.7 Magnesium Conversion at 0.25 L/min Argon Gas Flow Rate34
Time (hour)
0.5
1
2
3
4
5
1150 C Conversion
0.14
0.26
0.34
0.40
1300 C Conversion
0.40
0.57
0.75
0.84
0.88
0.92
158
(6. 14)
q ' VI
(6. 15)
P = PS PB
where
kc depends on the system. The convective mass transfer from sphere to a free
flowing gas can be calculated using the Ranz and Marshall correlation237 which
is a function of Reynold number, NRe, and Schmidt number, NSc,:
:/$
:/r
as cT '
where
$bK
(6. 16)
159
In this study, the Warner relation238 was used to determine mass transfer
relationship in a tube where gas passed through annulus form by briquette and
tube in the silicothermic process, which is expressed by:
:/$
:/r :.:;
$K
(6. 17)
Magnesium molecular diffusivity, D, can be calculated using the ChapmanEnskog equation for monoatomic gas based from kinetic theory of gas239:
'
.:;r3 /+
(\| + z,\|
V V
\
(6. 18)
The viscosity of gas was calculated from the formula based on the kinetic theory
of gas239:
V3
(6. 19)
' 9700i
(6. 20)
The mass transfer equation of Knudsen diffusion is similar to the Ficks law,
which is:
' 4
A\
(\
' 4 ]3
(6. 21)
6.3.2 Results
This study examines the effect of some parameters to the mass transfer of
magnesium vapour from the briquette to the bulk gas phase. Based on the
available data, effect of inert gas, time, and temperature to the mass transfer of
magnesium vapour from the briquettes will be examined.
161
v
(m/s)
density
(kg/m3)
0.007
0.022
0.044
0.062
0.088
0.309
0.309
0.309
0.309
0.309
viscosity
(
10-5
kg/ms)
Nre
7.14
7.14
7.14
7.14
7.14
0.4298
1.3430
2.6860
3.7603
5.3719
D
(
10-4
m2/s)
5.1725
5.1725
5.1725
5.1725
5.1725
NSc
0.045
0.045
0.045
0.045
0.045
kc
(
10-2
m2/s)
9.09
9.55
9.98
10.25
10.59
From the mass transfer coefficient, partial pressure of magnesium vapour in the
surface of briquette and in the bulk gas phase can be estimated. Table 6.9 shows
the magnesium vapour pressure at the surface and the bulk gas phase calculated
using Equation (6.15) using mass transfer coefficient from Table 6.8. These
results are also illustrated in Figure 6.10.
Table 6.9 Magnesium Vapour Pressure at 1300 C at Surface and Bulk Gas
Flow Rate
(
10-3 m3/min)
kc (
10-2
m2/s)
N (
10-8
kg/s)
V (
10-5
Mol/s)
Pb (kPa)
P
(kPa)
Ps (kPa)
0.08
0.25
0.5
0.7
1
9.09
9.55
9.98
10.25
10.59
3
5
5
6
6
1
3
6
9
13
12.41
6.58
3.40
2.58
1.82
0.19
0.28
0.27
0.27
0.27
12.60
6.86
3.67
2.86
2.09
162
Figure 6.10 shows the pressure of magnesium vapour at 1300 C at the bulk gas
phase (straight line) and the briquette surface (dash line). The calculated
pressure drop is between 186 and 266 Pa.
Table 6.10 Magnesium Vapour Pressure at 1150 C at Surface and Bulk Gas
(Argon Gas Flow Rate: 0.2510-3 m3/min)
Time (h)
1
2
3
5
kc
(cm/s)
9.61
9.61
9.61
9.61
N (10-6 g/s)
13
12
11
8
V (10-6
Mol/s)
32
32
32
32
163
Pb (kPa)
P (kPa)
Ps (kPa)
1.68
1.58
1.39
0.99
0.07
0.06
0.06
0.04
1.75
1.64
1.45
1.03
Table 6.11 Magnesium Vapour Pressure at 1300 C at Surface and Bulk Gas
(Argon Gas Flow Rate: 0.2510-3 m3/min)
Time (h)
kc
(cm/s)
N (10-6 g/s)
V (10-6
Mol/s)
Pb (kPa)
P (kPa)
Ps (kPa)
0.5
1
2
3
4
5
9.55
9.55
9.55
9.55
9.55
9.55
77
55
36
27
21
18
32
32
32
32
32
32
9.18
6.69
4.48
3.42
2.69
2.25
0.40
0.28
0.19
0.14
0.11
0.09
9.58
6.98
4.67
3.56
2.80
2.35
These results are plotted in Figure 6.11, which shows the profile of partial
pressure of magnesium at different reduction time. In general, the partial
pressure of magnesium vapours on the surface of briquette and bulk phase
decreases over time. For example, the partial pressure of magnesium vapours in
the bulk gas phase at 1150 C is 1.68 kPa at an hour reduction time and
decrease to 0.99 kPa after five hour. The partial pressure of magnesium vapours
in the bulk gas phase at 1300 C is 9.18 kPa at a half hour reduction time and
decrease to 2.25 kPa after five hour.
At reaction temperature of 1150 C, the pressure at the surface and bulk gas
phase at one hour is 1.75 and 1.68 kPa, respectively. As a comparison, the
equilibrium vapour pressure of magnesium over calcined dolomite-ferrosilicon
system at 1150 C is 2.4 kPa27.
At reaction temperature of 1300 C, the pressure at the surface and bulk gas
phase at one hour reaction time is 6.98 and 6.69 kPa, respectively. The
equilibrium vapour pressure of magnesium over calcined dolomite-ferrosilicon
system at temperature of 1300 C is 14.73 kPa27. These shows that at both
reaction temperatures, the partial pressure of magnesium at the surface at an
hour reaction time is lower than their corresponding equilibrium vapour
pressure.
164
6.4 Discussion
6.4.1 Kinetics of Reaction
Based on kinetic analysis, it is concluded that the kinetics of solid-solid reaction
is controlled by diffusion of reactant in the product layer. The result also shows
that diffusion models, although was derived from different assumption on the
shape of the product layer, can be applied to describe experimental data. Jander
model154, for example, as described in Figure 6.12 (a), which was based on the
diffusion in the product layer for a sphere particle and assumes the thickness of
product layer as a plane sheet, represents experimental data well especially at
lower conversion. The GinstlingBroushtein model156, which is based on
diffusion in the sphere and consider the thickness of product layer as a sphere
shell, can also be applied to this experimental data, even though the shape of
briquette is a short cylinder (Figure 6.12 (b)).
165
Thickness, as shell, in
Ginstling-Brounshtein156
(b)
(a)
When the models are expanded to the 100% conversion, the estimated
conversion between each model becomes different, as shown in Figure 6.13.
Thus, two models are unreliable. More experimental data should be required,
specifically to predict the completion time for silicothermic reduction at 1150
C.
This behaviour of Jander model has been commented by Szekely et al134. The
behaviour of the diffusion models is readily explained by the fact that, when the
conversion is small, the product layer around sphere or cylinder approximates
an infinite slab reasonably well. However, as conversion increases, this
approximation becomes inaccurate134.
6.5 Conclusion
The kinetics study conducted in this chapter suggests several conclusions:
1. The rate of silicothermic reduction of calcined dolomite under flowing
gas is predicted to be limited by solid state diffusion. The Jander154 and
Ginstling-Brounshtein156 models can represent the kinetics of the
process, but are only valid within the range of experimental data
available.
168
4. Current analysis on the the gas-film mass transfer based on Morsi et als
data34 shows that the gas-film mass transfer is not limiting the kinetics of
the process. The pressure difference between magnesium pressure at the
briquette surface and at the bulk gas flow at 1150 C is found to be 66 Pa.
5. The pressure of magnesium at the surface of briquette at initial
reactionat 1300 C is estimated to be 12.2 kPa. Considering the
difference between equilibrium vapour pressure of the reaction and the
pressure of magnesium at the surface of briquette, which is 2530 Pa, the
pore diffusion could also play a crucial role in the process. However,
because of limited properties data from Morsi et al34, detail analysis on
effect of pore diffusion is not analysed in the current study.
169
170
34
on determining the
171
The reaction tube was made from mullite (Al6Si2O13). The length of the tube was
1000 mm, which was situated symmetrically with reference to the tube furnace
(the tube position of 200 to 800 mm is situated inside the tube furnace). The
tube is both open at the end. The tube had an outside diameter of 45 mm and
internal diameter of 35 mm. The ends of the retort were closed by using an endcap fitting fabricated from brass.
The reduction process was carried out inside the reaction tube. The reactant
charge was placed in an alumina boat (2.1 cm 10.4 cm 1.4 cm) inside the
mullite tube, which is schematically shown in Figure 7.2. The steel wire was
attached to a piece of steel at the end and placed inside a borosilicate tube. In
order to move the reactant charger, a ring-type neodymium magnet was placed
outside the borosilicate tube. The steel piece and steel wire as well as the
reactant charge were moved along with the movement of the magnet. In this
way, the reacted charge can be moved by dragging the magnet attached to the
steel wire without necessities to open the left-end.
173
heating element
before reaction
heating element
during reaction
Figure 7.2 Schematic of Sample before and During Reaction
Ar gas inlet
Ar gas inlet
Thermocouple
Condenser
Wire to move
sample
Thermocouple
174
In this experimental study, the condenser was made from copper which has
6.35 mm inside diameter and 13 mm of outside diameter. The schematic and the
picture of water-cooled condenser are shown in Figures 7.4 and 7.5,
respectively. The length of condenser was 500 mm. Cooling water flows through
the 6.35 mm inlet to the edge of condenser then distributes inside 12.7 mm
diameter copper tube. The condenser was situated at the centre of the furnace
tube radius.
In addition to copper condenser, a quartz tube was inserted to the cooler part of
tube furnace. The purpose of quartz tube was to collect condensates in the
cooler part of furnace.
175
Condenser edge
Water outlet
water inlet
Manufacturer
Purity
Alfa Aesar
99.95 %
Sigma Aldrich
99+ %
Ferrosilicon(75% Si)
Goodfellow
99.9+ %
Fluorspar
Alfa Aesar
99+ %
Calcium Oxide
Magnesium Oxide
Form
Fine white powder,
-20 mesh (< 10m)
Fine white powder,
-325 mesh
Fine dark grey
powder, < 45 m
Fine white powder,
-20 mesh
176
The procedures to prepare samples are shown in Figure 7.6. CaO and MgO were
dried separately at 800 C for two hours in a muffle furnace to remove hydrate
and carbonate. The average weight loss of CaO and MgO due to the presence
hydrate and carbonate was found to be approximately 14.5 and 10.26 wt%,
respectively.
CaO, MgO, FeSi, and CaF2 were weighed and combined based on its
stoichiometric composition to a total mass of 60 gram and put into a
polyethylene jar. The polyethylene jar was rotated for 48 hours on a ball mill to
mix the powder homogeneously. The absorbed moisture during handing and
mixing was checked by heating a sample of powders at 800 C. The typical
absorbed moisture is approximately 2.3 wt%.
The homogeneous powder was weighed at about 1.07 g each and put into a
small container. The powder was put inside a pellet die set and pressed for two
minutes at pressures between 13 and 94 MPa using a laboratory scale hydraulic
press. The produced pellets were put inside a desiccator. During this process, it
is unavoidable that some moisture from the atmosphere will enter the sample.
For this reason, the pellets were heated again at 800 C in inert atmosphere
prior to the reduction process.
Each experiment requires 15 grams of raw materials. The pellet has diameter of
13 mm and height of 5 mm each. For the reduction process, the pellets were
placed on a ceramic boat (100mm long, 24mm wide and 15mm high). The
sample arrangement in ceramic boat is shown in Figure 7.7.
The temperature profile also was measured at the end of the tube furnace
parallel to the water-cooled probe condenser in order to characterise the
temperature distribution. The complete profiles of the temperature distribution
are shown in Appendix C.
The schematic of experimental rig has been shown at Figure 7.1. About 10 to 15
g of pellets were put into alumina boat. The charged boat was inserted to the
furnace at the end of the mullite tube at room temperature and the system was
sealed. Some silicon sealants were applied to the edge of tube in order to
prevent any leaking. The furnace temperature was brought to the reaction
temperature (between 1135 and 1180 oC) with the heating rate of 9 to 11 C per
minute. When the furnace temperature reached the reaction temperature, the
charged boat was pushed into the reaction zone using a magnet system. The
position of reaction had been identified using temperature profile experiment to
determine the position of the isothermal zone in the furnace. After the charged
boat was inserted into the reaction zone, the temperature would drop and
gradually increased to the reaction temperature after few minutes. The starting
179
reaction time was referred when the temperature reached the reaction
temperature after the charged boat was inserted. The reduction process was
performed between 1 to 18 hours.
The produced vapour (Mg and impurities) were transported by the carrier gas
to the condenser section in the direction of decreasing temperature. After the
reduction reaction time was finished, the charged boat was pulled back into its
position using the magnet system. The furnace was brought to cool under
flowing argon atmosphere. Post-oxidation of magnesium metal condensate was
carried out by passing carbon dioxide gas in order to passivate magnesium for
safety reason. After the reactor reached room temperature, left-end cap was
opened and the remaining pellets were weighed and stored in a closed
container.
To recover condensates, the right-end cap was opened and the quartz tube was
removed. Condensates were observed on the surface of copper condenser and
in the inner wall of quartz tube. The condensates from the copper condenser
were removed for further analysis and characterisation. The quartz tube was
sectioned horizontally in order to recover the condensates which were
deposited inside the inner wall. Since the amount of condensate is very small (<
0.1 g), the condensate at different position of the quartz tube or copper
condenser were analysed using XRD analysis to determine the major phase of
condensate and by using EDS for semi-quantitative analysis of condensate
composition.
180
The variables measured in the experimental study included the initial weight of
pellet sample, the final weight of sample after reduction, temperature (based on
the calibration), and elemental bulk analysis by using ICP-AES.
In most cases, the prepared sample was sputtered with a deposit layer of gold in
vacuum condition. This technique prevents a build-up of charge, which can
distort the image on the sample and reduces any effects the beam might have on
the solid sample242. Highly sculptured specimens need more coating material
than flat specimen. The average time required to coat the sample using the
vacuum evaporation method was about three hours.
EDS analyses the sample using semi-quantitative analysis based on relative line
intensities. The semi-quantitative analysis is a standardless analysis. The steps
in semi-quantitative analysis of EDS are as follows:
1. Comparing between the peaks found in the spectrum and the atomic data
2. Removing backgrounds intensity under peaks
3. Deconvolution to correct peak intensities especially at overlap lines
4. Element concentrations are calculated from deconvolved line intensities
using standardless P/B-ZAF method. ZAF correction method counts for
effect of atomic number, effect of absorbed X-Ray, and x-ray induced
fluorescence within the sample.
The accelerating voltage used for EDS analysis was between 15 and 20 keV. The
EDS analysis comprises the following analysis:
1. Localised elemental information from point analyses
2. Spatial gradient information of elements, which based on the electron
beam analysis that follow a line drawn from the sample image
3. Element mapping distribution, which is a relative intensity of defined
elements over the scanned area.
183
184
The analysis of XRD pattern was carried out using DIFFRAC software to match
XRD pattern of sample with the reference data from ICDD. Any small peak that
did not match with main phases indicates there were secondary phases in the
sample.
185
186
Figure 7.10 SEM of MgO (Signal: Secondary Electron, EHT: 3.00 kV, Working
Distance: 6 mm)
Figure 7.11 SEM of CaO (Signal: Secondary Electron, EHT: 8.0 kV, working
distance: 4 mm)
187
Figure 7.12 SEM of FeSi (Signal: Secondary Electron, EHT: 3.0 kV, working
distance: 6 mm)
Pellets fabricated for reactants were characterised by means of XRD and
SEM/EDS analysis. Figure 7.13 shows the XRD pattern of preheated pellet in the
inert atmosphere. The major phases identified in the reactant were CaO, MgO,
FeSi2, Fe2Si, and CaSi2.
188
189
190
Misra et al 32
Yucel et al 33
(50% excess
FeSi)
Current
Work
(15% excess
FeSi)
Particle
Sizes
CaO.MgO:
< 0.25 mm
FeSi: <
0.15 mm
CaO.MgO:
fine
powders
FeSi 74%:
< 75m
CaO: <
152 m
MgO: <
152 m
FeSi: < 66
m
Calcined
dolo-mite,
FeSi, CaF2
: N.A.
CaO: <
10m
MgO: < 44
m
FeSi 75%:
< 75m
Compaction
Pressure
2 tonne/inch2
= 27.4 MPa
Temperature
Pressure
(C)
1045 1160
0.006 Pa
3000 psi =
20.68 MPa
1165 1545
13 Pa
2000 - 3000
psi = 13.33 to
20.68 MPa
1000 1200
13 133
Pa
80 % at
1200 C, 2
hour
N.A.
1200 1350
101.3 Pa
80% at 1200
C, 4 hour
94.5 MPa
1140
200 Pa
(based on
fix output
of
pressure),
0.1 L/min
Ar
1140 C, 4
hour, 15%.
Condensates
on quartz
condenser
191
Magnesium
conversion
80% at 1160
C with 25%
excess
calcine
50 % at
1165 C for
70 minutes
192
(c)
(a)
(b)
Figure 7.20 Magnesium Condensates at (a) Condenser, (b) Wire Attached to
Sample Boat,
193
The following figures show the detail of XRD analysis of condensate collected
from different experiments.
Figure 7.24 XRD of Magnesium Condensates Run III (3 hour). Red line: MgO;
Blue Line: Ca2SiO4
195
196
Figure 7.29 SEM of Snow Condensate Collected from Inside Mullite Tube (left:
SE image, right: QBSD image) (1,500 magnification)
197
Figure 7.30 SEM of Dense Condensate Collected from Copper Condenser left:
SE image, right: QBSD image) (1,500 magnification)
The condensates were scraped at different regions and collected into different
container. From each sample container, a sufficient amount (< 0.01 g) was
analysed using XRD technique to determine the phase and subsequently
analysed using SEM/EDS to determine the morphology, and elemental analysis
and mapping.
Position
all
0-5 cm
6-15 cm
all
Mg
99.34
95.99
98.11
99.99
Ca
0.65
3.72
1.89
N.A
Si
N.A
0.3
N.A.
N.A
Fe
N.A
N.A.
N.A.
N.A.
Figure 7.31, calcium and silicon were localised at different position, while in
Figure 7.32, calcium was uniformly distribution throughout the condensate.
Si
Mg
Ca
Samples
199
Sample
Mg
Ca
200
201
202
203
1400
Temperature (C)
1200
1000
800
600
400
200
0
30
35
40
45
50
55
position (cm)
Thermocouple 1
Thermocouple 2
Classical Nucleation Theory (CNT) 169 had been used for predicting the effect of
homogeneous nucleation of vapour to liquid/solid phase. The development of
this theory was based on thermodynamics and kinetics arguments. CNT had
been criticised due to the use of simplifying assumptions, such as the
inappropriateness of using bulk surface tension values to predict behaviour of
clusters and assuming steady state at the liquid/solid-gas interface175. Aside of
this criticism, CNT had some considerable successes to describe and capture
critical aspects of homogeneous nucleation of vapours.
204
$ :/$
:$ "d @
B:< +
rI 3 Mc+
(8. 1)
Where is the surface free energy of molecule, m is the mass of the condensing
molecule, V is the volume of condensing molecule, N1 is the number density of
the molecule, and k is Boltzmanns constant (1.38010-23 J K-1).
The critical radius of nucleus is obtained when the free energy formation of
nucleus reaches maximum. By setting dG/dr = 0 for a spherical nucleus, the
critical radius of nucleus is defined as follows:
$
iT ' I3Mc
(8. 2)
r/$
(8. 3)
I+/
species176, while a recent study has revised the value of specifically for liquid
205
Hale176 noted that for fluxes larger than 1 cm-3 s-1, supersaturation can be
defined as follows:
(8. 4)
where ln(JCr) is equal to 72 + 3 and Q is the term in bracket. This implies that
based on the SNT, supersaturation has in the form of (lnS)2/3 has linear
relationship with the inverse of temperature, i.e. (ln S)2/3 ~ 1/T.
According to the SNT, the critical radius of nucleus, rc, is defined as follows:
iT '
$r</ @ - B:C
rMc
(8. 5)
206
2.2410-29
Number density
of molecule, N1
(1/m3)182
4.461028
Surface
Energy,
(N/m)
0.30 0.32
6.6510-26
4.0710-29
2.461028
0.470
Fe
9.2710-29
1.1610-29
8.641028
1.92
SiO
7.3210-26
2.410-29
4.171028
0.58 0.6
Atomic/ Molecular
Mass, m (kg)128
Molecular
Volume (m3)
Mg
4.0410-26
Ca
Species
The effective surface energy of Mg was obtained from Ferguson et al183, which
was based on the analysis of homogeneous nucleation of Mg using the SNT. The
surface energy of liquid Ca was obtained from Metal Handbook245. The surface
energy of Fe was obtained from Wille et al246, which was based on the
measurement of surface tension of containerless liquid iron.
References
Mg
0.531 2.26510-4 T
Ferguson et al183
Ca
0.472 110-4 T
Metals Handbook245
Fe
2.403 2.8510-4 T
Wille et al246
SiO
0.820 2.210-4 T
207
247.
energy of silicon is 0.728 Nm-1 245. Hale and Kemper243 analysed the effective
surface energy based on the SNT using homogeneous nucleation data of SiO184
and found that the effective surface energy of SiO was found between 0.58 and
0.60 N/m at a temperature between 800 and 700 C. As this value is in the
ranges value of the surface energy of Si and SiO2 (between 0.273 and 0.728
N/m), it will be used for the surface energy of SiO in this study.
8.1.2 Supersaturation
Supersaturation is defined as the ratio of partial pressure of vapour to its
equilibrium vapour pressure:
'
(0
(,0
(8. 6)
where Pi is the partial pressure of species i in the system and Peq,i is the
equilibrium vapour pressure of species i in the system. The equilibrium vapour
pressure of species i is assumed to be correlated to the temperature inside the
horizontal tube furnace. The equilibrium vapour pressure for species was
calculated based on the published pressure data, as seen in Table 8.3, based on
the following empirical relationship:
208
(8. 7)
Table 8.3 Equilibrium Vapour Pressure Constants (as per Equation 8.7)
Species
T (K) range
Magnesium248
7780
7550
10300
9600
13.29 + 0.39
11.41
12.79
14.97
12.55
17740 + 550
-0.855
-1.41
-1.76
-1.21
0
298-923
923-1363
713-1115
1115-1484
1301-1529
13.25 + 0.89
17900 + 1300
1433-1608
11.7 + 0.3
21000 + 500
1573-1973
Calcium248
SiO (over
amorphous
SiO) 194
SiO (over
equimolar Si
and SiO2)249
Fe195
P is in mmHg and T is in K
Partial pressure of SiO had been measured over amorphous SiO194 and
equimolar Si and SiO2249. In this study, the partial pressure of SiO used in this
study is over amorphous SiO194 was preferred.
Several assumptions were made to determine supersaturation of species, which
comprises the following:
1. The partial pressure of Mg vapour in the system was calculated on the
basis of the amount of magnesium evolved during silicothermic reaction.
q ' :V/
(8. 8)
where PB was the partial pressure of magnesium in the bulk gas phase, PT
was the total pressure of the gas phase, V was the molar rate of carrier
gas (mol min-1), M was the atomic mass of magnesium (in g), and was
The partial pressure of other species, such as Ca, SiO, and Fe were
calculated based on the molar ratio of the species to magnesium in the
vapour phase:
V0
q ' qV& d V
)*
210
(8. 9)
where Pi was the partial pressure of species i, Mi and MMg were the molar
fraction of i and Mg in the vapour phase, respectively. The ratio of molar
fraction of vapour phase species was predicted using equilibrium
calculation at the process temperature and pressure, which are
presented in Table 8.4.
Molar Fraction
P = 1 atm
P = 200 Pa
Mg
0.99823
0.99402
Ca
0.00174
0.00572
SiO
1.061810-5
2.506310-4
Fe
5.701610-9
3.277510-8
8.2 Results
8.2.1 Condensation of Magnesium
Figure 8.4 (a) shows the profile of supersaturation of magnesium vapour with
temperatures. At the argon gas flow rate of 2.510-4 m3/min at atmospheric
pressure and 75 wt% conversion of magnesium being produced from the
silicothermic reaction, the partial pressure of Mg over Mg-Ar system was
estimated to be 1.15 kPa. At temperature of 713 C, supersaturation reaches
one.
211
(a)
(b)
Figure 8.4 (a) Supersaturation of Mg Vapour Versus Temperature, (b) Plot of (ln
S)2/3 vs T for Mg Homogeneous Nucleation
Figure 8.4 (b) shows the plot of (ln S)2/3 with the decreasing temperature. This
data was compared to nucleation data of previous work of magnesium smoke at
0.32 atm of static hydrogen pressure183. The data showed a good agreement at
212
;;$
78$/r '
:rr<.;
4 3.7393 6 604
4 13.377 6 604
(8. 10)
(8. 11)
Figure 8.5 shows the nucleation rate of Mg vapour and the estimated radius of
nucleus/cluster formed from homogeneous nucleation predicted by the CNT
model. The nucleation rate of Mg vapour was calculated using the CNT in
Equation (8.1). The radius of nucleus/cluster was calculated from Equation
(8.2). It was predicted that growth of cluster from homogeneous nucleation of
Mg vapour occurs at temperature below 545 C, with the critical cluster radius
of less than 0.75 nm.
Figure 8.5 Plot of Nucleation Rate (/m3.s) and Radius of Cluster ( 10-9 m) of Mg
Homogeneous Nucleation
213
The nucleation rate of Mg vapour was predicted to increase with the decreasing
temperature. The nucleation rate of Mg vapour was found to be 1028/m3s at 400
C with a cluster radius of 0.4 nm.
The correlation of the predicted homogeneous nucleation to the observation of
the current experimental study is shown in Figure 8.6. Figure 8.6 shows the plot
of measured temperature profile along the experimental rig, which is compared
to the nucleation rate and critical radius of Mg cluster predicted from the CNT.
Mg vapour was predicted to condense at about position of 55 cm and beyond on
the experimental rig.
Figure 8.6 Temperature Profile, Nucleation Rate of Mg, and Critical Radius of
Nucleus along the Position
214
:==
4 13.807 6 825
(8. 12)
78$/r '
$;$$
4 25.088 6 825
(8. 13)
The homogeneous nucleation of SiO predicted by SNT gave some insight when
the nucleation of SiO occurred. This prediction was sensitive to some the
quantities included in the calculation, such vapour pressure and surface tension
of SiO.
Figure 8.8 Temperature Profile, Nucleation Rate of SiO, and Critical Radius of
Nucleus along the Position
216
The measured temperature profile along the experimental rig was plotted
against the nucleation rate critical radius of cluster predicted from CNT of SiO
homogeneous nucleation in Figure 8.8. The nucleation rate of SiO cluster was
predicted to occur at temperatures below 850 C, which corresponded to
supersaturation of 12 ((ln S)2/3 is 1.8) and the position of 39 cm in the
experimental rig. The critical radius of SiO cluster was predicted between 0.3
to 0.9 nm.
<$$.<
4 5.3886
T < 490 C
(8. 14)
(78$/r '
::r;%
4 12.227
T > 490 C
(8. 15)
The plot of supersaturation, nucleation rate, and critical radius of cluster from
Ca homogeneous nucleation with corresponding to the position in the
experimental rig is shown in Figure 8.10. The nucleation rate of Ca cluster was
predicted to occur at temperature of 620 C, which corresponded to position of
52.3 cm in the experimental rig. The critical radius of Ca cluster was predicted
to between 0.1 to 0.6 nm.
217
Figure 8.10 Temperature Profile, Nucleation Rate of Ca, and Critical Radius of
Nucleus along the Position
218
(78$/r '
:;$:
3
$%%
3
4 10.754
4 19.549
T < 822 C
(8. 16)
T > 822 C
(8. 17)
219
Figure 8.12 Temperature Profile, Nucleation Rate of Fe, and Critical Radius of
Nucleus along the Position
8.3 Discussion
The analysis of condensation behaviour of species using the CNT enables us to
predict the temperatures and degree of supersaturation /supercooling
condensation will occur. The extent of nucleation rate and particle size radius
can also be predicted from this theory.
220
T* (C)
Mg
650
604
SiO
1702
825
Ca
842
490
Fe
1538
822
Mg:
SiO:
Ca:
Fe:
78$/r '
78$/r '
78$/r '
(78$/r '
;;$
3
4 3.7393 6 604
:==
3
<$$.<
3
:;$:
3
4 13.807 6 825
4 5.3886
4 10.754
T < 490 C
T < 822 C
Mg
Predicted
Condensation
Temperature (C)
550
SiO
815
ln S = 2.5
39
Ca
610
ln S = 1.5
53
Fe
731
ln S = 9.28
36
Species
Supersaturation
Position in the
rig (cm)
ln S = 3.5
55
221
CNT predicts that homogeneous nucleation for the species occurs at different
temperature, which corresponds to different position in the horizontal tube.
While SiO and Fe are predicted to condense at higher temperature, the amount
of these species is very small. This is due to low vapour pressure of the species,
as shown in Figure 8.13. Thus, the segregation of these impurities would not to
be expected to be observed in the experimental study.
8.4 Conclusion
Nucleation model of Mg, SiO, Ca and Fe had been developed using the Classical
Nucleation Theory. It was predicted that Mg, SiO, Ca and Fe condenses at
different temperatures and different location inside the experimental rig. Mg
was predicted to condense at around temperature of 550 C, which was
corresponded to position of 55 cm on the horizontal tube. This was consistent
with the observation from the experiment where MgO phase was observed that
the positions between 50 and 60 cm on the horizontal tube.
Ca was predicted to condense around position of 53 on the horizontal tube,
while Fe and SiO were predicted to condense at the positions of 36 and 39 cm
on the horizontal tube, respectively. However, due to very low vapour pressure
of these species at the temperature ranges, these species would not to be
expected to be observed in the experimental study, which in fact was the case.
223
224
9 Discussion
Magnesium is dominantly produced via the Pidgeon process, which involves a
solid-solid reaction of calcined dolomite and ferrosilicon at temperature ranges
between 1100 and 1200 C5,
11, 12.
simple operation, the productivity of this process is very low. Other processes
attempt to increase the productivity of the silicothermic reduction process by
carrying out the reduction at higher temperatures in a liquid phase, such as the
Magnetherm process7, 52, 56 which operates at 1550 C and the Mintek process68,
74, 75
The literature on magnesium production has been focused on the kinetics of the
Pidgeon process in an attempt to improve the productivity of the process. While
a number of parameters affecting the process have been examined12,
there is no general conclusion what really controls the kinetics of the process.
The knowledge on the behaviour of impurities in magnesium produced by
silicothermic process is also quite limited. In the current practice, the impurities
in magnesium metal produced from the silicothermic processes are removed by
a refining operation, which causes 5 to 8% loss in magnesium59.
This
not sensitive to the initial composition of the vapour and operating condition of
the system, i.e. if Mg, Fe, Si, and Ca are present in the vapour; this sequence is
predicted to occur.
and
obtained
from
various
published
studies.
comprehensive assessment of this data was not carried out in this study.
The assessment and optimisation of this set of thermodynamic solution
model should be required in order to be fully confident in the predictions
made.
4. The thermodynamic solution model for the metallic phases only
considered the binary interactions between the metals, e.g. Mg-Ca, Mg-Si,
and Mg-Al.
227
Kinetic analysis of Pidgeon process was carried out to address the first
hypotheses, as the thermodynamic modelling over-predicts the magnesium
recovery in the actual experiment and industrial data. As the condition that
approaches equilibrium is required to represent the condition described in
thermodynamic modelling, the kinetic analysis used the data on a study of
silicothermic process in argon gas atmosphere34. For this analysis, different
kinetics models based on various assumption was considered, as well as the
mass transfer of magnesium vapour from the briquette to the bulk gas phase.
The kinetic study shows that the kinetic model based on solid state diffusion
best represents the kinetics of the process, as illustrated in Figure 6.4. In
general, the solid state diffusion models (e.g. Jander154, Ginstling-Brounshtein156,
Serin-Ellickson155, and Valensi-Carter model157) can represent the kinetics of the
process in the range condition where the experimental data are available.
Analysis of isothermal kinetic models carried out using linearity testing as well
as reduced-time testing236 showed that Jander model and Ginstling-Brounshtein
model were among the best models that can be applied to describe the kinetics
of the process at various temperatures.
The condensate from silicothermic processes was found at the cooler part of the
furnace. The condensate was spread along the wall of quartz tube in a grainy
form. SEM analysis showed that the diameter of agglomerates is in order of 10
to 70 m. The agglomerates contained a number of smaller grains. XRD results
showed that the typical condensate contained MgO as the major phase. The
condensate was mainly magnesium oxide, which was formed by the oxidation of
magnesium metal during cooling, storage, and handling prior to analysis. The
XRD pattern had also a broadening peak, which implies a secondary phase with
smaller grain. The experiment results did not indicate any obvious variation of
concentration of elements along the position of condensate in the condenser.
231
232
234
235
236
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D. Turnbull and J. C. Fischer: Journal of Chemical Physics, 1949, vol. 17, pp.
71.
172.
173.
J. Lothe and G. M. Pound: Journal of Chemical Physics, 1962, vol. 26, pp.
2080.
174.
175.
176.
177.
178.
179.
180.
181.
182.
183.
184.
185.
186.
187.
188.
189.
190.
191.
192.
193.
253
194.
195.
196.
197.
198.
199.
200.
C. W. Bale, E. Belisle, P. Chartrand, S. A. Decterov, G. Eriksson, K. Hack, I.H. Jung, Y.-B. Kang, J. Melancon, A. D. Pelton, C. Robelin, and S. Petersen:
"FactSage
thermochemical
development",
Computer
software
Coupling
and
of
databases
Phase
Diagram
recent
and
202.
203.
254
204.
'Database
Documentation
http://www.crct.polymtl.ca/fact/documentation/',
FactSage(TM).
1976
2010
206.
207.
208.
209.
D. K. Smith, A. Majumdar, and F. Ordway: "The Crystal Structure of Dicalcium Silicate", Acta Crystallica, 1965, vol. 18, pp. 787-795.
210.
211.
M. Aljarrah and M. Medraj: "Thermodynamic Modelling of the Mg-Ca, MgSr, Ca-Sr, and Mg-Ca-Sr Systems using the Modified Quasichemical
Model", Computer Coupling of Phase Diagram and Thermochemistry,
2008, vol. 32, pp. 240-251.
212.
213.
214.
N. Chakraborti and H. L. Lukas: "Thermodynamic Optimization of the MgAl-Si Phase Diagram", Calphad, 1992, vol. 16(1), pp. 79-86.
215.
H. Feufel, T. Godecke, H. L. Lukas, and F. Sommer: "Investigation of the AlMg-Si System by Experiments and Thermodynamic Calculations", Journal
of Alloy and Compounds, 1997, vol. 247, pp. 31-42.
216.
217.
218.
I.-H. Jung, D.-H. Kang, W.-J. Park, N. J. Kim, and S.-H. Ahn:
"Thermodynamic Modeling of the Mg-Si-Sn", Computer Coupling of Phase
Diagram and Thermochemistry, 2007, vol. 31, pp. 192-200.
219.
220.
221.
222.
223.
A. A. Nayeb-Hashemi, J. B. Clark, and L. J. Swartzendruber: 'Fe-Mg (IronMagnesium)', in 'Phase Diagram of Binary Iron Alloys', (ed. H. Okamoto),
pp. 200-202; 1993, Materials Park, OH, ASM International.
224.
225.
'The
FACT
FTLite
Light
Metal
Alloy
Database
227.
228.
229.
230.
231.
232.
233.
234.
235.
236.
237.
W. E. Ranz and W. R. Marshall. Jr: Chem. Eng. Prog. , 1952, vol. 48, pp.
141-146, 173-180.
238.
239.
240.
241.
242.
243.
244.
245.
J. R. Davis, ed. Metals Handbook, Desk Edition 1985, Metals Park, Ohio,
The American Society for Metals.
246.
247.
T. B. King: Trans. Soc. Glass Technol. , 1951, vol. 35, pp. 241.
248.
258
249.
250.
251.
252.
253.
254.
255.
256.
257.
258.
259.
260.
261.
259
262.
260
Figure A.1 The CaO-MgO Phase Diagram after Doman et al 253. The dashed lines
is the assessment results of Hillert and Wang 254.
A-1
The large difference in cation size, i.e. 1.00 for CaO and 0.70 for MgO, imply a
limited miscibility in CaO and MgO, especially at a temperature between 1100 to
2200 C. Limited solid solution of CaO and MgO exist at a temperature above
1600 C. The maximum solid solution of MgO in the CaO lattice is approximately
17 wt% at 2370 C, while the maximum solid solution of CaO in the MgO lattice
is approximately 7.8 wt% at 2370 C 253.
Besides CaO and MgO as the major constituent, calcined dolomite has impurities
such as FeO, Al2O3. Below is the thermodynamic description of the binary
system involved in the calcined dolomite:
-
FeO MgO system: solid solution exist in FeO and MgO system, and the
phase are completely miscible at high temperature255.
CaO-FeO system: CaO and FeO rich solid solution exist in CaO-FeOwith
miscibility gap102
MgO Al2O3 system: This binary compounds form spinel solid solution
(Mg2+, Al3+)(Mg2+, Al3+, Va)2O4 206
A.2. Ferrosilicon
Ferrosilicon is an alloy of iron of iron and silicon. Ferrosilicon alloys are
produced by carbothermic reduction of silica or quartzite in submerged electric
arc smelting furnace in the range 700 to 1300 C 256, 257. Phase diagram of Fe-Si
system is illustrated in Figure A.2. At 75 wt% Si and 1200 C, the Fe-Si system
contains FeSi2 compounds and pure Si. The melting point of ferrosilicon is 1200
to 1250 C, while the boiling point of this compound is 2355 C26.
A-2
A.3. Flux
In some processes, flux is added to increase the rate of reaction or to modify the
phases present in the system. CaF2 is added as the cataltyst to increase the
reaction rate of silicothermic process. Al2O3 flux is added to reduce the liquidus
temperature of the slag. Al2O3 is originally from bauxite (AlO(OH)4 or
Al2O3.2H2O).
A-3
Dicalcium silicate has five polymorphs, which are: - Ca2SiO4, - Ca2SiO4, Ca2SiO4, and - Ca2SiO4
209.
260
Figure A.4 shows the phase diagram of Ca2SiO4-Mg2SiO4 system119. This system
is essential for the silicothermic process, as MgO-CaO-SiO2 compounds are
prominent in this process. Dicalcium silicate forms a limited solid solution with
Mg2SiO4. Gutt
261
A-4
A-5
A-6
200, 262
83.
finished, the result window will provide the equilibrium products of the
reaction.
B-1
User enters the amount of input data in the Reactants Menu, as displayed in
Figure B.2. The thermodynamic data of defined species are retrieved from the
chosen database. The database of particular species has a certain temperature
range. In the case of calculation is carried out outside its temperature range, the
thermodynamic data is extrapolated. FactSage contains pure and solution
databases. The pure databases are FACT53 element database and ELEM
database. There is a number of solution database available, for example FTOxid
for oxides database, FTLite for metal database, FTSalt for salt database, etc.
Figure B.3 shows the list of database in the FactSage program. These databases
have been all developed FactSage developer through valuation and
optimisation of thermodynamic data from the primary literature. The
description of each solution model has been clearly described in the manual.
However, the user cannot retrieve the model parameters used in the solution
models. Instead, the user can develop their own solution database using their
data or literature in the Solution Module.
B-2
B-3
There are several types of solution model that can be employed, which are:
1. Polynomial (Kohler/Toop)
2. Wagner Interaction Formalism
3. Quasichemical
4. Sublattice (Kohler/Toop)
5. Sublattice (Muggianu)
6. Pitzer
7. Polynomial (Muggianu) in Redlich-Kister or Legendre polynomial
8. Sublattice (Quasichemical)
9. Compound Energy Formalism
B-4
B-5
B-6
B-8
+ 1.3765E-04
+ 2.1205E-05
+ 4.5508E-07
Fe
SiO
Al
FACT53
FACT53
FACT53)
a=1.0000)
FToxid
FToxid)
System component
Mole fraction Mass fraction
Fe
1.1623E-10 2.6413E-10
Ca
0.28377
0.46278
Si
0.14286
0.16326
Mg
1.9471E-03 1.9257E-03
O
0.57143
0.37203
+ 10.446 mol AMonoxide
(586.12 gram, 10.446 mol)
(1100.00 C, 6.5794E-05 atm,
( 0.99683
CaOFToxid
+ 1.7901E-03 MgOFToxid
+ 1.3786E-03 Al2O3
a=1.0000)
FToxid)
System component
Mole fraction Mass fraction
Fe
7.1758E-09 1.4313E-08
Ca
0.49739
0.71198
Al
1.3757E-03 1.3258E-03
Mg
8.9321E-04 7.7538E-04
O
0.50034
0.28592
+ 7.0854 mol FeSi_solid
T FACT53
(594.68 gram, 7.0854 mol)
(1100.00 C, 6.5794E-05 atm, S1, a=1.0000)
+ 4.6809 mol Fe_fcc
FACT53
(261.41 gram, 4.6809 mol)
(1100.00 C, 6.5794E-05 atm, S2, a=1.0000)
+ 0.39558 mol Ca3Al2O6_solid
(106.88 gram, 0.39558 mol)
(1100.00 C, 6.5794E-05 atm, S1, a=1.0000)
FACT53
FToxid
FACT53
B-9
Figure B.12 Solution Species and Final Conditions for the Vapour Condensation
B-10
The results are shown below. The phase resulted from equilibrium of vapour at
1050 C are:
1. 99.649 mol of ideal gas (vapour phase), which contains 99.62% Mg
2. 6.810-3 mol of fcc phase, which contains 99.99% Fe
3. 1.1810-3 mol of bcc phase, which contains 99.99% Fe
4. 1.910-3 mol of Amonoxide phase, which contains 99.84% CaO
5. 1.910-3 mol of pure FeSi
9.9277E+01 Mg + 3.7034E-01 Ca + 1.3718E-02 Fe + 2.1134E-03 SiO +
(1100,6.57E-05,g-FACT53,#1) (1100,6.57E-05,g-FACT53,#1) (1100,6.57E-05,g-FAC
4.5355E-05 Al =
(1100,6.57E-05,g-FACT53,#1)
99.649 mol gas_ideal
(2427.9 gram, 99.649 mol, 1.6444E+08 litre, 1.4764E-08 gram/cm3)
(1050.00 C, 6.5794E-05 atm, a=1.0000)
( 0.99626
Mg
FACT53
+ 3.6969E-03 Ca
FACT53
+ 3.7315E-05 Fe
FACT53
+ 1.6472E-06 SiO
FACT53
+ 1.6108E-07 Al
FACT53)
+ 6.8986E-03 mol FCC
(0.38524 gram, 6.8986E-03 mol)
(1050.00 C, 6.5794E-05 atm,
( 6.8475E-05 Mg
+ 5.1558E-06 Al
+ 0.99992
Fe
+ 6.8615E-06 Ca
a=1.0000)
T PIDG
T PIDG
PIDG
PIDG)
System component
Mole fraction Mass fraction
Fe
0.99992
0.99996
Ca
6.8615E-06 4.9244E-06
Si
4.8065E-11 2.4174E-11
Al
5.1558E-06 2.4911E-06
Mg
6.8475E-05 2.9803E-05
+ 1.9478E-03 mol AMonoxide#1
(0.10922 gram, 1.9478E-03 mol)
(1050.00 C, 6.5794E-05 atm,
( 0.99849
CaOFToxid
+ 1.1328E-03 MgOFToxid
+ 3.7910E-04 Al2O3
a=1.0000)
FToxid)
System component
Mole fraction Mass fraction
Fe
1.1016E-09 2.1953E-09
Ca
0.49896
0.71362
Al
3.7889E-04 3.6481E-04
Mg
5.6609E-04 4.9099E-04
O
0.50009
0.28553
+ 0.00000 mol AMonoxide#2
(1050.00 C, 6.5794E-05 atm,
a=0.33100)
B-11
( 6.0862E-04 CaOFToxid
+ 0.99939
MgOFToxid)
+ 1.1802E-03 mol BCC
(6.5105E-02 gram, 1.1802E-03 mol)
(1050.00 C, 6.5794E-05 atm, a=1.0000)
( 2.3525E-02 Al
T PIDG
+ 0.97641
Fe
PIDG
+ 6.0737E-05 Si
PIDG)
System component
Mole fraction Mass fraction
Fe
0.97641
0.98846
Ca
9.9692E-11 7.2428E-11
Si
6.0737E-05 3.0923E-05
Al
2.3525E-02 1.1506E-02
+ 0.00000 mol a'Ca2SiO4
(1050.00 C, 6.5794E-05 atm,
( 5.3846E-03 Mg2SiO4
+ 0.99462
Ca2SiO4
+ 0.00000 mol hcp
(1050.00 C, 6.5794E-05 atm,
( 0.35860
Mg
+ 1.9045E-02 Ca
+ 5.9848E-02 Al
+ 0.56250
Si
a=0.32340)
FToxid
FToxid)
a=2.2781E-04)
T PIDG
PIDG
T PIDG
PIDG)
+ 1.9492E-03 molFeSi_solid
T FACT53
(0.16359 gram, 1.9492E-03 mol)
(1050.00 C, 6.5794E-05 atm, S1, a=1.0000)
a=1.0000)
FToxid
FToxid)
System component
Mole fraction Mass fraction
Fe
1.1608E-10 2.6381E-10
Ca
0.28368
0.46267
Si
0.14286
0.16327
Mg
2.0297E-03 2.0075E-03
O
0.57143
0.37205
+ 95.078 gram AMonoxide#1
(95.078 gram, 1.6945 mol)
B-12
FToxid
B-13
System component
Mole fraction Mass fraction
Fe
3.2848E-06 7.7346E-06
Ca
0.22404
0.37861
Si
7.6533E-02 9.0631E-02
Al
9.8241E-02 0.11177
Mg
3.8352E-02 3.9303E-02
O
0.56283
0.37969
+ 0.00000 gram ASlag-liq#2
(1550.00 C, 4.9346E-02 atm, a=1.0000)
( 21.118 wt.% Al2O3
FToxid
+ 19.389 wt.% SiO2
FToxid
+ 52.975 wt.% CaOFToxid
+ 9.9437E-04 wt.% FeOFToxid
+ 7.6155E-07 wt.% Fe2O3
FToxid
+ 6.5175 wt.% MgOFToxid)
Site fraction of sublattice constituents:
Al
0.22472
Si
0.17506
Ca
0.51248
Fe2+
7.5085E-06
Fe3+
5.1743E-09
Mg
8.7726E-02
----------------------------------O
1.0000
System component
Mole fraction Mass fraction
Fe
3.2848E-06 7.7346E-06
Ca
0.22404
0.37861
Si
7.6533E-02 9.0631E-02
Al
9.8241E-02 0.11177
Mg
3.8352E-02 3.9303E-02
O
0.56283
0.37969
+ 448.37 gram a-Ca2SiO4
(448.37 gram, 2.6200 mol)
(1550.00 C, 4.9346E-02 atm,
( 2.8808 wt.% Mg2SiO4
+ 97.119 wt.% Ca2SiO4
+ 2.5905E-05 wt.% Fe2SiO4
a=1.0000)
FToxid
FToxid
FToxid)
System component
Mole fraction Mass fraction
Fe
6.2159E-08 1.4199E-07
Ca
0.27570
0.45197
Si
0.14286
0.16411
Mg
1.0012E-02 9.9534E-03
O
0.57143
0.37396
+ 0.00000 gram Fe-liq
(1550.00 C, 4.9346E-02 atm,
( 87.890 wt.% Fe
+ 0.22754 wt.% Al
+ 6.7019E-05 wt.% Ca
+ 7.1394E-06 wt.% O
+ 11.864 wt.% Si
+ 1.5764E-02 wt.% Mg
+ 8.2907E-04 wt.% MgO
+ 5.7283E-04 wt.% CaO
+ 3.4171E-04 wt.% AlO
+ 1.2874E-05 wt.% SiO
+ 8.4567E-04 wt.% Al2O
a=0.94899)
FACT
FACT
FACT
FACT
FACT
FACT
FACT
FACT
FACT
FACT
FACT)
B-14
FToxid
FToxid
Mn
System component
Mole fraction Mass fraction
Fe
1.7265E-07 3.9933E-07
2.7400E-10 6.2347E-10
Ca
0.25277
0.41959
Si
9.3431E-02 0.10868
Al
6.6062E-02 7.3825E-02
Mg
2.4502E-02 2.4665E-02
O
0.56323
0.37323
FToxid
FToxid
a=1.0000)
FACT
FACT
FACT
FACT
FACT
C FACT
C FACT
B-15
Mn
FACT
FACT
FACT
FACT
FACT)
System component
Mole fraction Mass fraction
Fe
0.18060
0.30756
3.8090E-06 6.3815E-06
Ca
3.2658E-02 3.9915E-02
Si
0.50357
0.43130
Al
0.14931
0.12285
Mg
0.13052
9.6737E-02
O
3.3480E-03 1.6335E-03
FToxid
FToxid
FToxid)
FToxid
T FACT
B-16
1200
Temperature, C
1000
800
600
400
Measurement without Condenser
200
0
0
10
20
30
40
50
60
70
80
Position, cm
Condenser position
1400
condenser position: 60 cm
1200
condenser position: 40 cm
Temperature ( C)
1000
800
600
400
200
0
30
35
40
45
50
Position, cm
55
60
C-1
65
1200
1000
800
600
400
200
0
-10
10
Position, cm
20
30
40
50
60
70
80
Position, cm
Condenser position
1000
800
600
400
200
0
5
15
Thermocouple 1
25
35
45
position (cm)
Thermocouple 2
55
65
C-2
10
1130 C
15
20
25
1145 C
1160 C
30
35
15
18
1130 C
21
1145 C
24
27
30
1160 C
C-3
1150
1145
R = 0.9891
1140
1135
1130
1125
1120
1125 1130 1135 1140 1145 1150 1155 1160 1165
Series1
Linear (Series1)
C-4
' t
'
t
t
D-2
K ' 3.418 _$ /j
:
|,)*\
| 3
'
|,)*
|,\
' 443.607
' 3.5459
Diffusivity of Mg-Ar:
'
.:::;r3
(\| + z,\|
V V
\
(6.18)
:/r :.:;
$K
(6.17)
2hi
cT '
'
20.3090.070.007
' 0.4298
7.14d10B;
V&BK
'
7.14d10B;
' 0.045
0.3095.1725
By substituting NRe, NSc, and DMg-Ar to Equation (6.17), mass transfer coefficient
can be calculated to be : A ' 9.09 _/j
E-1
= 112.1548 g
= 81.6088 g
= 28.0855 g
= 37.4775 g
When 10% excess of FeSi75 is incorporated into the samples, the ratio of
reactant becomes:
Ratio of CaO: MgO: FeSi75 = 47.728 % : 34.729 % : 17.545 %
When 2.5% CaF2 is added into the reactants, the ratio of reactants becomes:
Ratio of CaO: MgO: FeSi75: CaF2 = 46.518 % : 33.848 % : 17.100 % : 2.5 %
E-2