A Kinetic Model of The Peirce-Smith Converter

A KINETIC MODEL OF THE
PEIRCE-SMITH CONVERTER
By
ANDREW KEVIN KYLLO

B.A.Sc., The University of British Columbia, 1986
M.A.Sc., The University of British Columbia, 1989
A THESIS SUBMITTED IN PARTIAL FULFILLMENT OF THE

REQUIREMENTS FOR THE DEGREE OF
DOCTOR OF PHILOSOPHY
in
THE FACULTY OF GRADUATE STUDIES
METALS AND MATERIALS ENG]NEERING
We accept this thesis as conforming

to the required standard
THE UMVERSITY OF BRITISH COLUMBIA

August 1994
Andrew Kevin Kyllo, 1994
______________
In presenting this thesis in partial fulfilment of the requirements for an advanced

degree at the University of British Columbia, I agree that the Library shall make it
freely available for reference and study. I further agree that permission for extensive
copying of this thesis for scholarly purposes may be granted by the head of my
department or by his or her representatives, It is understood that copying or
publication of this thesis for financial gain shall not be allowed without my written
permission.
(Signature)
Department of NeIz 1
L
2 i, (4tJev:alc
t
J
The University of British Columbia

Vancouver, Canada
Date
DE-6 (2/88)
ABSTRACT
The Peirce-Smith converter, as used for copper and nickel converting, has changed
little in the eighty years since its introduction. Over this time other metal production
techniques have been developed, including considerable improvements to non-ferrous
smelting. These improvements have had only a small effect on non-ferrous converting.
The tenacity of the Peirce-Smith converter can be attributed to its simplicity of operation,
however, it is not an efficient process. While the converter itself is limited primarily by
its overall heat balance, process improvement has been limited by the belief that it
operated at thermodynamic equilibrium.
A kinetic model has been developed to gain a better knowledge of the operation of
the Peirce-Smith converter. The model consists of two parts; a model of the gas flow in
the bath, and an overall model considering both the heat and mass flows around the
converter. The gas flow model calculates the bubble growth on the tuyere to detachment,
and its subsequent rise through the bath. A combination of Kelvin-Helmolz and
Rayleigh-Taylor instability theories is used to determine the stability of the bubble, both
during growth and while rising through the bath. This allows the calculation of bubble
breakup, which can be used to determine the total gas/liquid interfacial area.
The gas flow model calculates the amount of oxygen reacting within each phase, as
well as the heat lost to the gas and the total interfacial area. These values are applied to
the overall model which then calculates the heat and mass balances within the converter.
Material flows are based on mass-transfer considerations, with each phase being
considered separately. Both mass and heat-transfer occur between all phases present, and
each phase is assumed to be in internal equilibrium. As well as calculating the behaviour
11
of the more abundant elements within the converter, the behaviour of the more important
minor elements is considered. The model is validated using published physical
modelling results, as well as measurements made on operating converters.
The model results indicate that the efficiency of the Peirce-Smith converter may be
improved by a number of methods, provided that some means of controlling the bath
temperature is available. Increasing the tuyere submergence and decreasing the tuyere
size are predicted to provide a substantial improvement in operation efficiency, without
adversely affecting the minor element removal. The use of low levels of oxygen
enrichment also improves efficiency, but tends to reduce the extent of minor element
removal. Higher levels of oxygen enrichment are predicted to alter the overall process
chemistry, with the amount of iron reacting being controlled by liquid-phase
mass-transfer. This improves both the overall process efficiency and the extent of minor
element removal.
111
TABLE OF CONTENTS
Abstract ii
Table of Contents iv
Table of Tables viii
Table of Figures xii
Acknowledgments xx
1 INTRODUCTION 1
1.1 Development of the Copper Converter 1
1.2 Development of Ferrous Converting 4
1.3 Comparison of Ferrous and Non-Ferrous Converting 5
2 LITERATURE REVIEW 8
2.1 Introduction 8
2.2 Converter Modelling 8
2.2.1 Converter Operation 8
2.2.2 Impurity Distribution 10
2.3 Process Kinetics 12
2.3.1 Copper Converting Kinetics 13
2.3.2 Kinetics of Gas/Liquid Reactions 14
2.3.3 Kinetics of Liquid/Liquid Reactions 15
2.4 Process Thermodynamics 16
2.4.1 Matte Thermodynamics 16
2.4.2 Slag Thermodynamics 18
2.4.3 Internal Phase Equilibrium 18
3 OBJECTIVES AND SCOPE 19
4 INDUSTRIAL DATA 21
4.1 Copper Converter Trials 21
4.2 Nickel Converter Trials 26
4.3 Analysis 33
4.3.1 Oxygen Efficiency 33
4.3.2 Material Deportment 36
4.3.2.1 Major components 36
4.3.2.2 Minor elements 40
iv
4.3.3 Converter Dusts . 44
4.3.3.1 Flue dust 45
4.3.3.2 Cottrell dust 52
4.3.3.3 Baghouse dust 57
5 GASFLOWINTHEBATH 59
5.1 Basic Bubble Growth 59
5.2 Bubble Detachment Criterion 67
5.3 Bubble Break-up During Growth 71
5.4 Bubble Rise 77
5.5 Bubble Recombination 79
6 MODEL DEVELOPMENT 81
6.1 Introduction 81
6.2 Preliminary Considerations 81
6.2.1 Bath Velocity and Gas Holdup 81
6.2.2 Converter Geometry 84
6.3 Mass Balance 90
6.3.1 Equilibrium Within Phases 90
6.3.1.1 Blister copper 90
6.3.1.2 Matte 90
6.3.1.3 White metal 91
6.3.1.4 Slag 91
6.3.1.5 Gas 91
6.3.1.6 Calculation technique 92
6.3.2 Gas-Liquid Mass-transfer 92
6.3.2.1 Gas flow 92
6.3.2.2 Mass transfer from liquid to gas bubbles 95
6.3.3 Mass Transfer Between Liquid Phases 98
6.4 Energy Balance 100
6.4.1 Energy Loss 100
6.4.2 Energy Consumption 102
6.4.3 Energy Generation 104
6.4.4 Interphase Heat-transfer 105
v
6.5 Data. 105
6.5.1 Physical and Thermal Properties 105
6.5.2 Thermodynamic Data 107
6.5.2.1 Free energy 107
6.5.2.2 Enthalpy of reaction 111
6.5.2.3 Activity coefficients 112
6.5.2.4 Equilibrium vapour pressures 118
6.5.3 KineticData 119
6.5.3.1 Diffusivities 119
6.5.3.2 Mass-Transfer coefficients 121
6.5.3.3 Heat-Transfer coefficients 122
7 MODEL VALIDATION 123
7.1 Bubble Model Validation 123
7.1.1 Bubble Growth 123
7.1.2 Bubble Rise 124
7.2 Copper Converter Validation 128
7.2.1 Bath Temperature 128
7.2.2 Slag Composition 130
7.2.3 Matte Composition 133
7.3 Nickel Converter Validation 136
7.3.1 Bath Temperature 137
7.3.2 Slag Composition 140
7.3.3 Matte Composition 143
7.4 Discussion 146
7.4.1 Phase Compositions 146
7.4.1.1 Error in assays 146
7.4.1.2 Sulphur in slag 147
7.4.1.3 Oxygen in matte 148
7.4.1.4 Minor element distribution 149
7.4.2 Copper Blow 153
8 MODEL PREDICTIONS AND DISCUSSION 157

8.1 Gas Flow Model 157
vi
8.2 ConverterModel. 166
8.2.1 Introduction 166
8.2.2 Copper Converter Charge 167
8.2.3 Sensitivity Analysis 171
8.2.4 Converter Operation 186
8.2.4.1 Gasflowrate 186
8.2.4.2 Oxygen enrichment 188
8.2.4.3 Tuyere submergence and diameter 197
8.2.4.4 Slag skimming procedure 202
8.2.5 Minor Element Removal 204
8.2.5.1 Introduction 204
8.2.5.2 Minor element behaviour in the base charge 205
8.2.5.3 Model predictions 213
8.2.5.3.1 Gasflowrate 213
8.2.5.3.2 Oxygen enrichment 214
8.2.5.3.3 Tuyere submergence and diameter 229
8.2.5.4 Summary 233
8.2.6 Comparison with Previous Work 234
8.2.6.1 Overall model 234
8.2.6.2 Minor element distribution 235
9 MODEL APPLICATION 238

9.1 Introduction 238
9.2 Converter Optimization 238
9.3 New Process Development 242
10 CONCLUSIONS AND FURTHER WORK 247
11 NOMENCLATURE 250
12 REFERENCES 255
13 APPENDIX 266
vi
TABLE OF TABLES
Table IV-I Details of copper charges followed 22

Table IV-ll Material assays, copper converter charge 586, Feb. 1, 1994.
Nunbers in parentheses refer to the blow number in Table TV-I 23
Table TV-HI Material assays, copper converter charge 588, Feb. 2, 1994.
Table TV-TV Material assays, copper converter charge 595, Feb. 4, 1994.
Table TV-V Flux assay, copper converter plant trials, Feb., 1994 25
Table TV-VT Methods of detennination for each assay 26
Table IV-Vll Details of nickel converter charges 29

Table IV-VllI Material assays, nickel converter charge 105, May 2, 1988. Slag
samples numbers correspond to the blow they were skimmed after. Nunbers in
parentheses refer to the blow number in Table TV-VU 31
Table IV-IX Material assays, nickel converter charge 106, May 24, 1988. Slag
Table IV-X Material assays, nickel converter charge 107, May 25, 1988. Slag
parentheses refer to the blow number in Table IV-Vll 32
Table IV-XT Material assays, nickel converter charge 108, May 26, 1988. Slag
Table IV-Xll Overall oxygen efficiencies for copper converter charges

followed in plant trials 34
Table IV-XllI Oxygen efficiencies calculated from matte samples 34
Table IV-XTV Calculated nickel converter oxygen efficiencies 35
Table TV-XV Distribution of major components between output streams of the

copper converter 37
Table IV-XVT Distribution of major components in nickel converting 38
Table IV-XVTI Compositions of converter dust samples 44
viii
Table V-I Tpical copper converting conditions used for bubble size
calculations 60
Table V-TI Bubble size at detachment calculated from different models 61
Table VT-I. Reacting components of the matte 90
Table VT-fl Reactions required to calculate the equilibrium composition of the

matte 91
Table VT-HI Integrated values of C. for use in equation 6.73. 103
Table VT-TV Enthalpies of reaction required for energy generation

36
calculation. 104
Table VT-V Physical and thermal properties of the gas and condensed phases. .. 106
Table VT-VT Coefficients for gas viscosity equation (air).

42 107
Table VI-VIl Free energy of formation of matte compounds.

142 107
Table VT-VIIT Free energy of reaction for matte-slag reactions.

35 108
Table VT-TX Free energy of reaction for slag and gas reactions.
135 108
Table VI-X Activity coefficients of the major constituents of the matte and
slag 112
Table VT-XT Minor element activity coefficients used in the model 117
Table VI-Xll Equilibrium vapour pressures of the minor elements 119
Table VT-XIIT Atomic/ionic/molecular radii of matte, slag and bullion

36
constituents. 121
Table VTT-T Comparison of measured and predicted gas penetration in

mercury 123
Table VTT-IT Comparison of measured and predicted gas fraction, bath velocity,
and spout height in vertical injection systems 126
Table VTT-TTT Comparison of model predicted slag compositions with assays,

(weight percent), #1 converter charge 586, Feb., 1994 131
Table VH-TV Comparison of model predicted slag compositions with assays,

Table VTI-V Comparison of model predicted slag compositions with assays,

x
Table Vu-VT Comparison of model predicted matte and blister copper
compositions with assays, (weight percent), #1 converter charge 586, Feb.,
1994 134
Table Vu-Vu Comparison of model predicted matte and blister copper
compositions with assays, (weight percent), #1 converter charge 588, Feb.,
1994. Asterisk indicates combined matte and slag to bring the matte silica
content up to assayed value 134
Table VIT-VITI Comparison of model predicted matte compositions with
assays, (weight percent), #1 converter charge 595, Feb., 1994. Asterisk
indicates combined matte and slag to bring the matte silica content up to assayed
value 135
Table Vu-TX Comparison of model predicted slag compositions with assays
taken at the end of the blow, (weight percent), #3 converter charge 105, May
1988 141
Table VuT-X Comparison of model predicted slag compositions with assays
1988 141
Table VIT-XI Comparison of model predicted slag compositions with assays

1988 142
Table VII-XII Comparison of model predicted slag compositions with assays

1988 142
Table VIT-XITI Comparison of model predicted matte compositions with
assays, (weight percent), #3 converter charge 105, May 1988 144
Table VII-XTV Comparison of model predicted matte compositions with

Table VTT-XV Comparison of model predicted matte compositions with assays,

(weight percent), #3 converter charge 107, May 1988 144
Table VuT-XVT Comparison of model predicted matte compositions with

Table VII-XVII Comparison of slag assays obtained using TCP and wet assay
techniques 147
Table VuuT-T Parameters tested in the sensitivity analysis 172
Table Vu-TI Predicted distribution of minor elements to the blister copper and
dust after 400 minutes of charge 586 (72 tonnes of blister copper produced) 205
x
Table VIJI-ifi Comparison of equilibrium and kinetic model predicted minor
element distributions with commercially observed ranges 237
Table IX-I Conditions used in the improved charge 240
Table IX-il Conditions used in the new process 244

Table TX-HI Composition of matte added in the new process 244
xi
TABLE OF FIGURES
Figure 1.1 Schematic of the Peirce-Smith converter 4

Figure 2.1 Comparison of reported values of FeS activity coefficient in copper
59
9
mattes. 17
Figure 4.1 Variation in measured bath temperature and air rate in a nickel
converter, (#3 converter, charge 105, May 23, 1988) 28
Figure 4.2 Variation of total copper, nickel, and cobalt in slag with nickel
converter matte grade 39
Figure 4.3 Variation of total copper, nickel, and cobalt in slag with slag oxygen
potential 40
Figure 4.4 Minor element distribution in Hudsons Bay Mining and Smelting
copper converters, charges 586, 588, and 595, February 1994 41
Figure 4.5 Antimony and bismuth distribution in Hudsons Bay Mining and
Smelting copper converter charge 595, February 1994 42
Figure 4.6 Minor element distribution in Inco nickel converter (#3 converter,
charges 105, 107, and 108, May 1988) 43
Figure 4.7 Schematic of the dust collection system at Hudsons Bay Mining
and Smeltings Fun Flon smelter. Numbers indicate approximate position from
which Cottrell dust samples were taken 45
Figure 4.8 Copper converter flue dust, x25 47
Figure 4.9 Copper converter flue dust, a. coated particle, x150, b. particle with
pore, x300 48
Figure 4.10 Copper converter flue dust, mounted and sectioned, x25 49
Figure 4.11 Copper converter flue dust, mounted and sectioned, a. particle
containing entrained slag and copper droplets, xl 25, b. particle containing
copper droplets, xlOO, c. fractured particle containing copper, x125, d. slag
particle containing copper droplet, x80 51
Figure 4.12 Copper converter Cottrell dust, a. sample 1, xl 00, b. sample 2,

xlOO, c. sample 4, x160. Numbers refer to sample positions shown in
Figure 4.7 54
Figure 4.13 Copper converter Cottrell dust with matrix removed, a. sample 1,
xlOO, b. sample 2, x160, c. sample 3, x160. Numbers refer to sample positions
shown in Figure 4.7 55
xii
Figure 4.14 Copper converter Cottrell dust, a. sample 2, x300, b. sample 1,
agglomerated fume, x2000. Numbers refer to sample positions shown in
Figure 4.7 56
Figure 4.15 Smelter baghouse dust, x1500 58
Figure 5.1 Schematic of high Froude number injection of air into water.

11 62
Figure 5.2 Ellipsoidal bubble growth 64
Figure 5.3 Comparison of horizontal and vertical injection conditions 65
Figure 5.4 Bubble detachment process 68
Figure 5.5 Bubble detachment geometry 69
Figure 5.6 Variation of the height of the bubble centre above the tuyere
centreline (h) and the distance of the bubble centre from the tuyere centre (s)
with bubble radius at detachment 70
Figure 5.7 Variation of bubble position at detachment with bubble diameter 71
Figure 5.8 Schematic illustration of flow around a bubble.

18 73
Figure 5.9 Variation of maximum bubble diameter and wavenumber with bath
velocity 77
Figure 6.1 Schematic cross-section of an idle converter 85

Figure 6.2 Schematic cross-sections of an operating converter: a. no gas flow
through the slag, b. gas flow through matte and slag, c. gas flow through slag
only 87
Figure 6.3 Schematic of emulsion formation during submerged injection
27 89
Figure 6.4 Comparison of reported values of free energy of reaction 109
Figure 6.5 Comparison of reported values of free energy of formation of SbS

and SbO 110
Figure 6.6 Comparison of reported values of free energy of formation of AsS

andAsO 111
37 and predicted spout height

Figure 7.1. Comparison of measured 125
Figure 7.2 Variation of fraction sulphur dioxide reacted with gas flow rate
including the fitted effect of surface reaction 127
Figure 7.3 Variation of fraction sulphur dioxide reacted with tuyere

submergence including the fitted effect of surface reaction 128
xiii
Figure 7.4 Comparison of measured and predicted copper converter
temperatures charge 586, February, 1994 129
Figure 7.7 Comparison of measured and predicted iron and silica contents in
copper converter slags, charges 586, 588, and 595, Feb. 1994 132
Figure 7.8 Comparison of measured and predicted a. iron and b. copper
contents in copper converter mattes, charges 586, 588, and 595, Feb. 1994 136
Figure 7.9 Comparison of model predicted matte and slag temperatures with
plant data, #3 converter charge 105, May 1988 138
nickel converter slags, #3 converter, charges 105, 106, 107, and 108, May 1988.
143
Figure 7.14 Comparison of measured and predicted iron, nickel, and copper
contents in nickel converter mattes, #3 converter, charges 105, 106, 107, and
108, May 1988 145
Figure 7.15 Calculated variation of mole fractions of Fe

4 and FeO in matte.
0
3 ... 149
Figure 7.16 Comparison of model predicted lead, zinc and arsenic distributions
with measured values, copper converter charges 586, 588, and 595 Flin Flon,
February 1994. Solid lines indicate commercially observed range. 1 151
Figure 7.17 Comparison of model predicted antimony and bismuth

distributions with measured values, copper converter charge 595, Flin Flon,
February 1994 152
with measured values, nickel converter charges 105, 107, and 108, Copper Cliff,
May 1988 153
xiv
Figure 7.19 Predominance area diagrams for the iron-copper-sulphur-oxygen
system; a. 1300 K, b. 1500 K. Dashed lines indicate partial pressure of sulphur
dioxide 155
Figure 8.1 Variation of primary bubble temperature with time for injection
conditions given in Table V-I 158
Figure 8.2 Effect of ellipse eccentricity on surface area at constant volume,
shaded area indicates eccentricity range predicted by the model 160
Figure 8.3 Variation of primary bubble volume with time for injection
Figure 8.4 Variation of average oxygen partial pressure with tuyere

submergence for injection conditions given in Table V-I 161
Figure 8.5 Variation of average oxygen partial pressure with tuyere diameter,
all other conditions given in Table V-I 161
Figure 8.6 Variation of primary bubble volume with tuyere diameter, all other
Figure 8.7 Variation of total oxygen reacted with inlet gas oxygen content, all
other conditions given in Table V-I 164
Figure 8.8 Variation of primary bubble temperature with bath material, all other
Figure 8.9 Variation of number of bubbles formed with bath material, all other
Figure 8.10 Effect of tuyere interaction on average oxygen partial pressure all ,
other conditions given in Table V-I 165
Figure 8.11 Effect of tuyere interaction on primary bubble volume, all other
Figure 8.12 Predicted matte temperature, charge 586. F-flux addition, M-matte
addition, I-idle period start, I*idle period end, S-slag skimmed, Sc-scrap added,
C-copper blow start 168
Figure 8.13 Predicted variation of oxygen use with time 170
Figure 8.14 Predicted variation of tuyere submergence (including spout) with

time 170
Figure 8.15 Predicted variation of oxygen use with tuyere submergence

(including spout), charge 586, Feb. 1994 171
Figure 8.16 Effect of model time step on the predicted variation of matte
temperature and iron content (weight percent) with time 173
xv
Figure 8.17 Effect of gas flow calculation frequency on the predicted variation
of matte temperature and iron content (weight percent) with time 174
Figure 8.18 Effect of initial bath temperature on the predicted variation of
matte temperature and iron content (weight percent) with time 175
Figure 8.19 Effect of initial bath temperature on the predicted variation of
matte oxygen content (weight percent) with time 176
Figure 8.20 Effect of slag emissivity on the predicted variation of slag
temperature with time 177
Figure 8.21 Effect of liquid-phase diffusivity on the predicted variation of
matte zinc content (weight percent) with time 179
Figure 8.23 Effect of liquid-phase diffusivity on the predicted variation of slag
oxygen content (weight percent) with time 180

oxygen use with time 180
Figure 8.25 Effect of gas-phase mass-transfer coefficient on the predicted

variation of matte temperature and iron content (weight percent) with time 182
Figure 8.26 Effect of gas-phase mass-transfer coefficient on the predicted

variation of slag oxygen content (weight percent) with time 183
Figure 8.27 Effect of weight of matte in a ladle on the predicted variation of

Figure 8.28 Effect of gas flow rate on the predicted variation of matte
Figure 8.29 Effect of gas oxygen content, with total oxygen input constant, on
the predicted variation of matte temperature and iron content (weight percent)
with time 190
Figure 8.30 Effect of gas oxygen content, with total oxygen input constant, on
the predicted variation of matte iron content with iron as magnetite removed
(weight percent) with time 191
Figure 8.31 Effect of gas oxygen content, with increased oxygen input, on the
predicted variation of matte temperature and iron content (weight percent) with
time 192
Figure 8.32 Effect of gas oxygen content on the predicted variation of matte
iron content (weight percent) with time at 1400 K 195
xvi
Figure 8.33 Effect of gas oxygen content on the predicted variation of oxygen
use with time at 1400 K 195
Figure 8.34 Variation of the predicted amount of iron and copper suiphides
reacting, as a percentage of the total reaction in the matte, with time at 1400 K
and 84% oxygen in the injected gas 196
Figure 8.35 Effect of gas oxygen content on the predicted variation of copper
produced with time at 1400 K 196
Figure 8.36 Effect of gas oxygen content on the predicted variation of sulphur
potential with time at 1400 K 197
Figure 8.37 Effect of tuyere submergence on the predicted variation of matte
Figure 8.38 Effect of tuyere diameter on the predicted variation of matte
Figure 8.39 Effect of a combined reduction in tuyere diameter and increase in
tuyere submergence on the predicted variation of matte temperature and iron
content (weight percent) with time 201
Figure 8.40 Effect of skimming procedure on the predicted variation of matte
Figure 8.41 Effect of skimming procedure on the predicted variation of oxygen
use with time 204
Figure 8.42 Predicted variation of minor element concentrations in blister
copper with time, a. lead and zinc, b. arsenic, antimony, and bismuth 207
Figure 8.43 Variation of surface area-to-volume ratio of blister copper with
depth 208
Figure 8.44 Predicted variation of minor element concentrations in matte with
time, a. lead and zinc, b. arsenic, antimony, and bismuth 210
Figure 8.45 Predicted variation of minor element concentrations in slag with

Figure 8.46 Predicted variation of minor element partial pressures in gas with
Figure 8.47 Predicted variation of minor element distribution to the dust with
gas flow rate, a. lead b. zinc, c. arsenic, d. antimony, and e. bismuth 214
gas oxygen content with constant total oxygen input, a. lead b. zinc, c. arsenic,
d. antimony, and e. bismuth 216
xvii
Figure 8.49 Predicted variation of minor element distribution to the blister
copper with gas oxygen content with constant total oxygen input, a. lead b. zinc,
c. arsenic, d. antimony, and e. bismuth 217
gas oxygen content, with increased total oxygen input, a. lead b. zinc, c. arsenic,
d. antimony, and e. bismuth 218
Figure 8.51 Effect of gas oxygen content, with increased total oxygen input, on
the predicted variation of arsenic partial pressure in the off gas with time 219
copper with gas oxygen content, with increased total oxygen input, a. lead
b. zinc, c. arsenic, d. antimony, and e. bismuth 220
the predicted variation of arsenic content in blister copper with time 221
the predicted variation of antimony content in blister copper with time 222
copper with gas oxygen content, with constant total oxygen input and
temperature, a. lead b. zinc, c. arsenic, d. antimony, and e. bismuth 225
Figure 8.56 Effect of gas oxygen content, with constant total oxygen input, on
the predicted variation of arsenic content in blister copper with time at 1400 K.
226
gas oxygen content, with constant total oxygen input and temperature, a. lead
b. zinc, c. arsenic, d. antimony, and e. bismuth 227
the predicted variation of arsenic partial pressure in the off gas with time at
1400 K 228
the predicted variation of moles of arsenic and mole fraction of copper sulphide
in matte with time at 1400 K 228

copper with tuyere submergence, a. lead b. zinc, c. arsenic, d. antimony, and
e. bismuth 231
tuyere submergence, a. lead b. zinc, c. arsenic, d. antimony, and e. bismuth 232
Figure 8.62 Effect of tuyere submergence on the predicted variation of arsenic

content in blister copper with time 233
xviii
Figure 9.1 Effect of modifications given in Table DC-I on the predicted
variation of matte temperature and iron content (weight percent) with time 241
Figure 9.2 Effect of modifications given in Table DC-I on the predicted
variation of oxygen use with time 242
Figure 9.3 Predicted variation of matte temperature and iron content (weight
percent) with time for the new process 245
Figure 9.4 Predicted variation of oxygen use with time for the new process. ... 246
Figure 9.5 Predicted variation of weight of blister copper produced with time
for the new process 246
Figure 13.1 Simplified flow chart of the overall model 267
Figure 13.2 Flow chart of the gas flow calculation 268
Figure 13.3 Flow chart of the mass balance calculation 269
Figure 13.4 Flow chart of the heat balance calculation 270
xix
ACKNOWLEDGMENTS
I would like to acknowledge the financial support for this project from The National
Science and Engineering Council and Hudson Bay Mining and Smelting Ltd. I would
also like to thank Kevin Scott and Dominic Verheist for their assistance during the plant
trials, and my supervisor, Dr. Greg Richards. Finally, I should thank my wife for her
continued patience and assistance and my children for allowing me to work.
xx
1.1 Development of the Copper Converter
1 INTRODUCTION
The pyrometallurgical production of copper from sulphide concentrates is a
complex procedure which at present requires a number of steps before the refining stage.
Although some modernization of the process has been carried out, most smelters use
techniques which have changed little in eighty years. In the last forty years important
innovations have been made in copper smelting technology, but only a small amount of
research has been carried out on copper converting. Thus the Peirce-Smith converter has
changed little in this period, and has not taken advantage of many innovations which
have benefitted other industries. In order to demonstrate the extent of the problem the
development of the copper converter can be compared with that of the ferrous converter.
Copper converting originated at the same time as steel converting with Bessemers
introduction of the pneumatic converter. However, there are problems associated with
copper mattes which do not arise in the converting of pig iron. The most important of
these are the relative densities of three phases involved, (slag, matte and blister copper)
and the volume of slag produced.
The blister copper is the most dense of the phases produced, and so forms the
bottom layer in the converter. This leads to two operating difficulties for the
Bessemer-type converter: the heat generated by the reaction of air with copper is
insufficient to prevent tuyere blockage and the air oxidizes the copper rather than the
matte. Although both of these difficulties are experienced only after the formation of
blister copper, they proved to be a serious impediment to the development of the copper
converter. The corrosive nature of the matte and slag on the acidic refractories also posed
1
a problem. The large volume of slag produced required intermediate slag skimming and
matte charging before the finishing blow. This was not a serious problem, but it did
require extra cranes, longer overall charge times, and frequent relining.
The problems relating to bottom blowing were overcome in 1880 by Pierre Manhs.
His solution was to move the tuyeres to the side of the converter and place them a few
inches above the base to give a quiescent zone for the copper to collect in. This form of
converter was introduced into the United States four years later, where it was developed
further, first as the Parrot converter, and then as the Great Falls converter. It is no longer
in use.
Manhs had also worked with the idea of using a horizontal converter, although he
gave this up in favour of the Bessemer style upright converter. However, others in the
industry preferred the use of the barrel converter, apparently due to the lower injection
pressures which could be used with it.

2 Both types of converters used a sacrificial lining
of siicious material, which had to be replaced after only a few charges. It was not until
1909 that this problem was solved by Peirce and Smith who developed the basic
magnesite lining which allowed, with a change in fluxing, a much longer refractory life.
3
The horizontal, basic lined converter then became known as the Peirce-Smith converter.
Over the last 80 years the size of the Peirce-Smith converter has increased, the
quality of the refractory has improved and automatic tuyere punching has been added.
Some smelters have introduced oxygen enrichment of up to 30% in the injected air.
Otherwise there has been little change.
The present form of the Peirce-Smith converter is shown in Figure 1.1. It is a
horizontal cylinder with lengths from seven to eleven metres. Chrome-magnesite
refractory is used in most operations, but the proportions of the components varies. A
2
copper converter charge consists of a number of slag blows followed by the copper or
finish blow. Before each slag blow molten matte is charged to the converter. Air is then
blown through the matte causing the iron to be removed by the reaction
3 ...[l.1]
FeS +O2 = FeO+ SO
2
The iron oxide is removed to the slag, where it reacts with the silica in the flux to form
fayalite,
=iO
2FeO-i-Si0
S
2
4 Fe
Blowing then continues until almost all of the iron has been removed. The slag is then
skimmed, more matte is added, and blowing continues. After the last slag blow, slag is
skimmed, but no more matte is added. During the copper blow the oxygen in the injected
gas reacts with the copper sulphide to produce copper,
S
Cu
=
2 2Cu+S0
+0
Nickel converting is similar to copper converting, except that the copper blow is
replaced with miss and dry-up blows. The procedure for these is the same as for the
copper blow, in that no matte is added, but the purpose is to ensure that the iron levels in
the matte are sufficiently low for further processing. The slag formed in the dry-up
blow is very viscous, and contains a large amount of nickel. It is generally termed
mush, and remains in the converter to be cleaned and to provide the flux for the first
slag blow of the following charge.
Recently new methods for the pyrometallurgical processing of copper suiphides
have been developed. Although the majority of these are new smelting techniques, there
has been some advance in converting technology. Flash smelting has been found to be
able to produce a high grade matte or blister copper, but the slag losses under the
3
1.2 Development of Ferrous Converting
BUSTLE
PIPE
Figure 1.1 Schematic of the Peirce-Smith converter.
conditions required for direct blister production are quite high.

4 The Noranda Process, a
side blown bath smelting technology can also be used to produce copper directly, but this
mode of operation is avoided due to impurity and refractory problems.

5 The Mitsubishi
continuous converter uses a top lancing system in which oxygen enriched air is generally
6 Most recently Inco has developed a modified Peirce-Smith converter which

employed.
allows oxygen top lancing.

7
1.2 Development of Ferrous Converting
Shortly after the introduction of the Bessemer converter a basic lining for ferrous
converting was developed by Gilchrist and Thomas in 1877, primarily to allow the
removal of phosphorous from the steel. The use of tonnage oxygen was first introduced
in Austria in 1948. This was in a top blown Bessemer converter, and has become known
as the L-D process.
4
1.3 Comparison of Ferrous and Non-Ferrous Converting
Since then further innovations include the combined-blowing converter, which uses
oxygen lancing with inert gas stirring, and the introduction of the shrouded tuyere which
allows oxygen to be introduced either through the bottom or the side of the converter.
These recent improvements all make use of high pressure injection, either in the lance or
through the tuyeres.
From the outlines of converter development given above it is evident that
technologically the non-ferrous industries are considerably behind the ferrous. While the
use of high pressure gas has been tested,

8 it is not yet used in any installation. The main
concern which is preventing its use is that the increased energy input to the bath will be
more likely to cause bath slopping and increased splashing. Physical modelling studies
of slopping in the Peirce-Smith converter have shown that it is directly related to the
9 These studies also indicate that increasing

bouyant power per unit mass of the bath.
tuyere submergence allows a greater gas flow rate to be used,

9 and that for an
intermediate range of tuyere submergences there is a range of gas flow rates, in some
cases quite high, at which no waves are formed.

This suggests that higher flow rates
1
could be used. In the steel converter, the vessel shape and tuyere arrangement allows a
considerably higher flow rate to be used. The vessel shape also allows an increased
tuyere submergence.
The batch nature of the copper converter can lead to it being idle for over 50% of
The steel converter is also a batch process, but the differences

the total charge time.
1
between the processes allow the steel converter to operate more efficiently. The main
difference between the two processes is the final form of the material being removed
from the bath. In steel converting carbon is removed as a mixture of CO and CO

2 gas,
5
while in the slag blows of a copper converter iron must be removed as an oxide contained
in a liquid slag. This results in a large volume of slag which must be removed from the
copper converter. It is interesting to note that there is a considerable amount of research
being carried out to develop a continuous steel making process.

4 It is possible that the

1
development of a continuous copper converting process would be preferable to altering
the present process.
Oxygen lancing has recently been introduced in a modified converter,

7 and oxygen
enrichment of the blast air is a fairly common practice.
The use of oxygen gives a
1
higher converting rate and gives an off gas high in SO

, which is more economical to
2
clean than the low concentrations presently obtained. However, the use of tonnage
oxygen, as in steel converting has not been used. There are three main reasons for
limiting the oxygen content of the blast air. The first of these is that at high oxygen
contents the tuyere life is reduced dramatically. The solution to this problem is already
available, in the form of shrouded tuyeres, as used in bottom blown steel converters. The
second problem relates to the heat balance. It has been determined that the off gas
accounts for the majority of heat removal from the converter.

5 Reducing the nitrogen
content and, therefore, total gas throughput will cause a large increase in bath
temperature and a related decrease in refractory life. However, improved refractory and
changes in slagging practices may allow higher temperatures to be used. Also, the higher
matte grades available from the new smelting furnaces produce considerably less heat
due to their lower iron contents, and any increase in available heat could be used to
increase scrap recycling. The other potential problem relating to the use of tonnage
oxygen in the copper converter is the removal of minor elements. It has been determined
that a large proportion of lead, arsenic and bismuth are removed from the converter by
6
volatilization, and it has been suggested that the use of oxygen will result in a much
16 This problem, along with obtaining a better overall
lower removal of these elements.
understanding of the Peirce-Smith converter through the use of a kinetic model, will be
the focus of this study.
7
2.2.1 Converter Operation
2 LITERATURE REVIEW
2.1 Introduction
The development of a kinetic model of the Peirce-Smith converter requires a wide
range of background information. This chapter will cover previous models of the
converter and related technology, as well as the general kinetics and overall
thermodynamics required. The literature relating to other aspects of the modelling will
be introduced where appropriate.
2.2 Converter Modelling
The majority of models relating to the copper converter deal with the distribution of
impurities between matte, metal, and slag. Three models attempt to reproduce the overall
material balances and of these only one attempts to reproduce the heat balance as well. A
recent model of the nickel converter reproduces both the material and heat balances. All
of these rely on the assumption that the converter is in thermodynamic equilibrium.
A model of the copper converter, developed by Goto, has been gradually improved
over the last fifteen years, most recently being applied to the copper flash smelter.

72
The first part of the model to be developed considered only the mass balance.
7
Assuming that the converter is in thermodynamic equilibrium, a set of simultaneous
equations was formed and solved using a modified form of the Newton-Raphson
22 The activity coefficients required in these equations

technique formulated by Brinkley.
were derived from published data and experimental work by the authors. The model
considered nine elements and nineteen compounds, to give a representation of the
distribution of most of the important elements present in copper concentrates in Japanese
smelters. Of the minor elements of interest here only lead was considered.
8
The second development was the addition of a heat balance to complete the
8 The model applied a heat balance to the

representation of the entire converter.
converter, using the mass balance calculations to derive a heat generation term. An
iterative technique was used to calculate the temperature change caused by any net heat
production during a given interval. Calculations were carried out over a two minute time
step throughout the converting cycle, allowing for charging and skimming. It was
claimed that the model was able to predict temperature variations fairly well,
18 but no
direct comparison with plant data was published, and no comparison of matte or slag
composition was given. More recent developments of the model have included its
9 and the addition of a calculation of oxygen

extension to cover the copper flash furnace,
consumption using kinetic considerations.

2
A model of the heat and mass balances in the nickel converter has recently been
It is based on the work of Goto et al., and has been found to be able to
14
produced.
predict both the bath temperature and composition fairly accurately.
A model of the Noranda continuous converting process has been developed which
concentrates primarily on the minor element distribution. This model calculates the
equilibrium phase compositions at a given temperature, partial pressure of sulphur
dioxide, magnetite activity, and, in the case of matte-making, matte grade. It does not
attempt to model the entire process. The most important findings of these papers with
respect to the present project relate to impurity removal, particularly removal to the gas
phase. The majority of volatilization occurs during matte-making and the removal rates
of arsenic and antimony are very slow during copper-making. Increasing temperature
was found to have only a slight effect on the removal rates, but calculations were not
done above 1250C. Oxygen enrichment was found to be detrimental to impurity
9
2.2.2 Impurity Distribution
volatilization due to the reduction in gas throughput. The slag composition was found to
have no significant effect. More recently the model has been extended to the flash
furnace and converting with high oxygen enrichment and calcium ferrite slags by Sohn et
al. 16,29-3 1 The results of these calculations will be discussed below. The modelling
technique used in these papers appears to have some problems. In particular, the
prediction that oxygen partial pressure is independent of the 0/Fe ratio in the slag is
suspect.
The other model which assumes a constant temperature appears to be more a
demonstration of a possible use for the Solgasmix program than a bone fide model.
32 A
more recent extension of this model using a modification of Solgasmix has been written
to simulate a concentrate injection smelting technique.

32 It does not include a heat
balance as the process is assumed to be isothermal and the important minor elements
were not considered.
The more recent papers on modelling of the Noranda Process and other new
processes are primarily concerned with the distribution and volatilization of impurities,
263 The distribution of
which are of particular importance in direct smelting
16
systems.
minor elements between copper, matte and slag is calculated assuming that there is only
monatomic dissolution of arsenic, antimony and bismuth in the slag, and that the oxides
25 However, the model significantly underpredicts the amount

and sulphides are unstable.
of each of these elements reporting to the slag. Although the value of L (% As in
copper/% As in slag) is brought close to the industrially reported value using mechanical
10
suspension indices, the calculated values of 14 and 14 remain very high.

25 This indicates
that the oxide form of these minor elements may be an important factor in their
dissolution in slags.
A technique to calculate the relative amount of impurities lost to the off-gas is also
26 The technique calculates the partial pressure of the minor elements and
formulated.
their compounds from various thermodynamic variables, and in particular the partial
pressures of oxygen and sulphur. It should be reiterated that this is an equilibrium model
calculating steady-state volatilization. The overall minor element removal is directly
related to the volume of gas passing through the bath and the final equilibrium
composition of the constituent phases. As such it is not valid for a batch process with a
continuously changing composition. In fact its validity can be questioned for any
submerged injection process, including the Noranda process for which it was written, as
it is not likely that the gas leaving the bath close to the charging end of the reactor will be
in equilibrium with the final products. The equilibrium calculations do give an indication
of which compounds are likely to be the most important with respect to minor element
removal to the gas. However, when this model is compared to industrial observations
from the Noranda process it significantly under predicts the amounts of arsenic and
antimony reporting to the off-gas during copper-making, although it is closer for
27 The under prediction during copper-making is the result of the

slag-making.
equilibrium assumption. Both arsenic and antimony have very low activity coefficients
in copper. Under equilibrium this causes the activities of these elements to drop
significantly in all phases when copper is present in the system. This lower activity
causes a reduction in the volatilization rate and, hence, an under prediction of the
amounts of these elements reporting to the off gas.
11
2.3 Process Kinetics
The same model has been applied to copper converting by considering the process
as a series of microsteps Overall it is a simplistic model which does not allow for
changing temperatures or charging to and skimming from the bath. The results of the
model agree with industrial data to a certain extent, but the amount of data available is
very limited. The effects of increasing the oxygen enrichment were also studied,
and
3
found to have a very detrimental effect on minor element removal. This result is
expected due to the reduced gas throughput. The effects of oxygen enrichment and the
use of a calcium ferrite slag on the overall minor element distribution have also been
predicted with this model.

31 In general it was predicted that increasing oxygen

6
enrichment reduced the amount of volatilization due to the reduced volume of off gas
produced. However, the amount of minor elements reporting to the slag was increased.
The overall result was an increased minor element content in the copper.
The use of a
3
calcium ferrite slag was predicted to have little effect on the elimination of lead and
bismuth, but to be extremely detrimental in the removal of arsenic and antimony due to a
large reduction in the extent of volatilization.

6
An attempt to theoretically model the distribution of impurities between matte and
blister copper in the copper converter using the Temkin model has been carried out.
34
The model gives good results for some of the impurity elements, but is quite poor for
predicting arsenic and antimony distributions.
2.3 Process Kinetics
The kinetics of some of the processes involved are important, particularly with
respect to the minor element removal. Therefore, a review of a variety of aspects relating
to the process kinetics is required.
12
2.3.1 Copper Converting Kinetics
2.3.1 Copper Converting Kinetics
The kinetics of copper converting have undergone little study. This is due to the
apparently high oxygen efficiency which suggests that it operates close to equilibrium.
Calculations by Ashman et al.

35 have shown that the reactions in both the slag and copper
blows are under gas-phase mass-transfer control. The high oxygen efficiencies
suggest,therefore, that the gas residence time in the bath is sufficient to allow the
reactions to come close to or attain equilibrium.
A more recent study of the oxidation of molten iron sulphide assumed that the rate
was under mixed control through the gas and liquid boundary layers around a bubble.
36
A physical model of mass transfer in the copper converter has shown that kinetic
calculations cannot be limited to the bubbles after detachment from the tuyere, as a
significant portion of the reaction occurs during bubble growth.

37 Unfortunately, this
study neglected the effect of mass-transfer at the bath surface, which can be considerable,
especially at low tuyere submergences.

38
Other kinetic studies related to copper converting are of limited practical use. They
either demonstrate that the process is controlled by gas-phase mass-transfer,

or
4

39
concern the controlling stage of the chemical reaction,

42 which is not relevant, since the

41
reaction is considerably faster than the mass-transfer in the system.
Although it does not concern the converter directly, a study of the removal of
bismuth and lead from copper during vacuum induction melting does highlight a factor
which could be of considerable importance in converting.

43 It was determined that the
removal rates of these elements were controlled by liquid-phase mass-transfer and
evaporation. This suggests that the removal of the minor elements during converting will
13
2.3.2 Kinetics of Gas/Liquid Reactions
also be controlled by liquid-phase mass-transfer and evaporation and will not be well
represented by equilibrium calculations. This conclusion is supported by a study of
impurity removal from copper mattes.
2.3.2 Kinetics of Gas/Liquid Reactions
There have been some studies relating to the mass-transfer around submerged gas
3
37 8 These were primarily low temperature physical models, a majority dealing
jets.
4
55
with the reaction of CO

2 with an NaOH solution.
4648 Two studies have considered the
kinetics of the deoxidation of copper by carbon monoxide.
The first determined that
5

49
the deoxidation rate was controlled by gas-phase mass-transfer down to an oxygen
concentration of 0.1%, below which it was under liquid-film control.

48 The second study
found that liquid-phase control remained in effect down to 0.005% oxygen, below which
the reaction rate became significant.
A model of mass-transfer between a horizontal jet and a liquid was combined with a
physical model injecting a mixture of air and SO

2 into a bath containing 2
H
4
.
0 5 The
experimental work was designed to ensure that the process was limited by gas-phase
mass transfer. For this work it was assumed that the gas flow could be represented by an
expanding jet, so the results are given as k, where x is the interfacial area per unit
length of the jet. Unfortunately, the lowest modified Froude number used in this study
was 88, which is considerably higher than that found in the copper converter.
Another study combining mathematical and physical modelling used the absorption
2 in water during vertical injection. In this case the rate of absorption was
of CO
controlled by liquid-phase mass transfer, which was represented in the model using
Higbie s penetration theory. One of the more interesting results of this study was the
14
2.3.3 Kinetics of Liquid/Liquid Reactions
determination of the effect of surface reactions. In particular, it was found that at low
flow rates and low tuyere submergences surface reactions could account for well over
50% of the total CO

2 absorbed.
38
2.3.3 Kinetics of Liquid/Liquid Reactions
A number of studies have been carried out to determine the rates of mass transfer
between two immiscible phases under gas stirred conditions, and those prior to 1989 are
51 All of these are studies related to bottom injection, particularly ladle

reviewed by Mon.
refining, and have determined that the rate of mass-transfer is dependent upon the gas
flow rate. There are three mass-transfer regimes, depending upon the gas flow rate:
I. at low flow rates there is a slow increase in the mass-transfer coefficient with
increasing gas flow, probably related to the increase in bath mixing velocity,
II. above a critical gas flow rate there is a rapid increase in mass-transfer rates, due
to the formation of droplets of slag in the metal, and
Ill, with further increases in gas flow the increase in mass-transfer rate is reduced,
since the entire slag has been emulsified.

5254
The values of the critical flow rates are dependent upon the slag depth, reactor
dimensions, and tuyere position, as well as the physical properties of the phases
54 As such, the values obtained in physical modelling studies are not

involved.
transferable directly to the copper converter, however the three mass-transfer regimes are
likely to be found in the converter. Also, the observation that off-centre tuyeres have a
considerably greater critical velocity for emulsion formation than central tuyeres,
suggests that the conditions in a Peirce-Smith converter are far from ideal for matte-slag
15
2.4.1 Matte Thermodynamics
mass-transfer. A large stagnant region of slag was also observed in a two-phase
physical model with an off-centre tuyere,

55 again suggesting that the mass-transfer
conditions in the Peirce-Smith converter are far from ideal.
2.4 Process Thermodynamics
Industrial mattes are usually a complex mixture of a number of different
components. However, most of these are only present in small amounts, so mattes are
generally considered as ternary Cu-Fe-S systems. The use of a Cu-Fe-S-O quaternary
system appears to be an unnecessary complication, since the oxygen appears to be present
as dissolved iron oxides. The first reported thermodynamic measurements on this system
were carried out by Krivsky and Schuhmann in 1957.56 They determined that the
S-FeS pseudobinary deviated negatively from ideality. Later researchers determined

2
Cu
that the Temkin

57 or Flood
58 models could be used to calculate activities within the
psuedobinary system, but that the addition of oxygen invalidated their use.
58 Work
carried out by Sinha and Nagamori determined the activity coefficients of cobalt, iron,
and their suiphides in copper-saturated mattes.

59 The authors also determined that the
results of Krivsky and Schuhmann were a factor of 1.32 too high, due to uncertainties in
the free energy data when the original experiments were made.
In developing a mathematical model of the converter, Goto et al. 17-20 derived a set of
4 in the matte. These were

equations for the activity coefficients of FeS, FeO, and Fe
0
3
Rosenqvist and Hartvig,

derived from the data of Korakas,
6 and Kuxmann and Bor,
6 62
7 The relationship obtained for the activity

and relate to mattes saturated with magnetite)
coefficient of FeS
16
= exp((
18
J ln(O.54 +1 4XFeS logX + 0.52XFeS)J
is plotted in Figure 2.1. The same figure shows the experimental points of Sinha and
59 in copper saturated matte. It is evident that the agreement is very poor,

Nagamori
demonstrating the extreme difficulty which exists in characterizing the solution
thermodynamics of mattes.
1.1
Kemori et al. [20]

1400 K
- 1500 K
0.9 Sinha and Nagamori [59]
1400K
x 1500K
0.8
*
U) 0.7
cj
U
xx
0.6
0.5
0.4
0.3
0 0.2 0.4 0.6 0.8
X FeS
Figure 2.1 Comparison of reported values of FeS activity coefficient in copper

mattes.
Attempts to represent copper and nickel mattes using the associated solution model
6377 These models appear to have a good predictive capability in

have been carried out.
binary and ternary systems, but require a large number of fitted parameters, and have not
been extended sufficiently to allow their use for industrial mattes.
17
2.4.2 Slag Thermodynamics
2.4.2 Slag Thermodynamics
There has been a considerable amount written regarding slag thermodynamics, and
an extensive review was produced by Mackey in 1980.78 More recent studies appear to
have concentrated on ferrite slags, as are used in the Mitsubishi process.

7983 The activity
coefficients for the major constituents in fayalite slags have been calculated by Goto
17
from the data of Muan,

84 Michal and Schuhmann,
85 and Korakas.
An associated
6
solution model of the Fe-O-Si0

-CaO system has also been produced.
2 86

85
2.4.3 Internal Phase Equilibrium
The distribution of various elements between the matte and the slag at equilibrium
is an important topic, since it relates both to the extent of valuable metal losses and of
slagging of unwanted components of the matte. The importance of copper losses to the
slag is evidenced by the large body of papers written about the subject.
8895
The form of the copper in the slag appears to depend primarily upon the matte
88 At low matte grades dissolution as a sulphide predominates, while oxidic

grade.
dissolution becomes important as the matte grade increases. It would probably be more
correct to consider the form of dissolution as a function of oxygen potential, with oxidic
dissolution being favoured by the high oxygen potentials which exist with high matte
96 In fact, measurements made in ferrite slags show a large variation in

grades. with
82 In order to deal with this the Temkin or Herasymeriko models

oxygen partial pressure.
95 The Herasymenko model has been shown to represent
have been applied to the slag.
copper slags well, including the transition between sulphidic and oxidic dissolution of
copper.
18
3 OBJECTIVES AND SCOPE
3 OBJECTIVES AND SCOPE
The persistence of the copper converter indicates that it fulfils its function
satisfactorily. However, it has a number of drawbacks. All the elements required to
develop a new, efficient process are in existence, yet little has been done. One of the
most important problems which has to be overcome before oxygen can be effectively
utilized in a coppermaking process is that of minor element removal. In the Peirce-Smith
converter most of the arsenic, antimony, bismuth and lead are removed under present
practices, however it has been found that under direct coppermaldng conditions there is
insufficient removal of these elements. Also, previous models of minor element removal
indicate that using oxygen injection will exacerbate the problem.
The main objective of this work is to develop an improved understanding of the
operation of copper and nickel converters. In particular, a better understanding of the
mechanism by which minor elements are removed from the converter is to be obtained,
and so aid in the development of an improved overall process. The emphasis is to be
placed on the behaviour of the more important minor elements: arsenic, antimony,
bismuth, lead, and zinc. To aid in attaining this goal a kinetic model of Peirce-Smith
converter operation will be developed and validated. The model may then be used to
predict the effects of altering process variables on overall converter operation, as well as
minor element behaviour.
Equilibrium models of both the copper and nickel converters have been previously
developed, and appear to successfully represent converter operation. However, oxygen
potential measurements carried out in an operating converter indicated that the three
condensed phases were not in equilibrium.

96 It has been determined that the rates of the
primary converting reactions are controlled by gas-phase mass-transfer. This is dealt
19
3 OBJECTWES AND SCOPE
with in the thermodynamic models by assuming that a certain proportion of the oxygen
reacts with the bath. However, the actual amount of oxygen reacting may vary
considerably within the course of a charge, and possibly even within a blow, so assuming
a single value may lead to incorrect conclusions. Finally, when considering the
behaviour of the minor elements, the kinetics are likely to become more important due to
the relatively low concentrations in the liquid phases.
Validation of the model will be carried out using data obtained from operating
converters. Validation will cover nickel converting operation, using data obtained during
plant trials at Incos Copper Cliff smelter, and copper converting using data obtained
from plant trials at Hudsons Bay Mining and Smeltings Fun Flon smelter. Following
validation, the model will be applied to determining the effects of process variables on
converter operation. These will concentrate primarily upon factors which can be changed
directely in converting practice, as well as simulating conditions which are not normally
obtainable in a standard converter, but may result in a significant improvements in overall
operation. The effects of these variables on the distribution of the minor elements will
also be considered. A comparison with a previous equilibrium model of the nickel
converter will also be made.
20
4.1 Copper Converter Trials
4 INDUSTRIAL DATA
To obtain further information regarding converter operation, and data for use in
model verification, in-plant sampling was carried out at Hudsons Bay Mining and
Smeltings Fun Flon smelter between January 31 and February 5, 1994. Two complete
charges and the slag blows of a third charge were followed in detail, taking samples of
most materials added to and removed from the converters. Occasional tuyere samples
were also taken throughout each charge. The times of all sampling, as well as blowing
and idle periods were recorded, along with the amount of air blown. Since this particular
installation does not routinely monitor the bath temperature, temperature measurements
were also carried out, using disposable thermocouples inserted into a tuyere. Off gas
compositions were not measured, as facilities for this were not present, and the prescence
of leakage air makes accurate interpretation of such measurements difficult.
Details of the charges followed are given in Table IV-I, and the assays of the
samples obtained are given in Tables IV-II to IV-V. The assay techniques used to obtain
these values are given in Table IV-VI. Approximate magnetite contents of all samples
were measured using an Inspiration Consolidated Copper Company Magnetite Meter,
which is based on magnetic inductance.The magnetite meter was calibrated using
standard samples. None of the charges followed can be considered normal. This is
because the other operating converter was in its final charges before relining, so the
white metal was transferred to the test converter before the copper blow. This provided
an unusual input stream for the two full charges followed, leading to shorter overall
charge lengths. The final charge followed, charge 595, was the second charge in a newly
relined converter. While no material was transferred to the converter during this charge,
21
charge 586 588 595

nitial Contents Matte 132+80(1) vlatte 48 Vlatte 148
tonnes) Slag 12 Slag 8 Slag 8
Scrap 4 Scrap 4 Scrap 4
ilow 1 2 C 1 2 C 1 2 3 4 5
otal Time 113 100 241 118 128 254 126 92 64 164 84
(mm)
Eime Idle (mm) 50 34 28 44 66 22 78 60 46 56 14
fldle Periods 7 5 3 5 5 5 4 4 1 9 3
vlatte Added 16 32 - 16 32 - 16 48 32 32 32
tonnes) 72(1)
1ux Added 5.5 7.7 - 6.6 9.9 - 6.6 4.4 - 9.9 8.25
tonnes)
Scrap Added - - 15 - - 15 12 25(2) - - -
tonnes)
Slag Skimmed 31.25 37.5 25 31.25 43.75 18.75 0 18.75 12.5 62.5 25
tonnes)
(1) Transferred matte
(2) Copper slag
Table TV-I Details of copper charges followed.
the amount of flux added in the first blows was insufficient, as can be seen from the first
two slag assays in Table TV-TV. The low silica and corresponding high magnetite content
of the slag caused it to become very viscous. This can also be seen in the high copper
and sulphur contents of the slag samples, indicating a large amount of matte entrainment.
The fluxing problems are also the main cause of the large amount of slag in the
first matte samples and their correspondingly high magnetite contents. While the matte
samples taken in the first blow of the other charges followed do contain a higher silica
content than the other mattes, they are still considerably lower than the values from
charge 595, and are caused by the lower volume of material in the bath, which drops the
slag level close to the tuyereline. It should be noted that the average converter slag
22
composition at the Fun Ron smelter is 26% silica and 38% iron, with magnetite ranging
between 20 and 30%. Only one of the slag samples taken during the trials is close to this
(charge 595, slag 3), but even this slag had a high magnetite content.
Sample Cu Fe Zn Pb S 2
Si0 4
0
3
Fe As
(Blow)
Initial Matte 42.8 25.2 2.78 1.08 24.5 .21 9.0 0.05
Matte 1 (1) 70.9 4.1 0.83 2.89 20.2 2.33 2.5 0.03
Matte 2 (2) 71.0 3.09 0.59 2.63 21.6 0.28 1.5 0.02
Matte 3 (2) 74.7 1.1 0.3 0.65 19.8 0.5 1.2 0.01
Transfer Matte 65.6 7.3 1.01 1.13 17.9 2.25 11.0 0.03
Metal (C) 90.1 0.49 0.13 0.23 5.55 0.22 0.0 0.04
Blister Copper 99.04 0.08 0.002 1 0.0072 - - - 0.0073
Slag 1 (1) 7.13 41.6 3.97 0.7 2.2 17.6 66.0 0.04
Slag 2 (2) 6.46 39.2 3.89 0.73 2.07 22.0 53.0 0.04
Slag 3 (2) 6.13 37.4 4.00 1.28 1.66 22.8 52.0 0.04
Copper Slag 38.2 21.8 2.16 2.84 0.6 12.1 21.5 0.04
Table TV-il Material assays, copper converter charge 586, Feb. 1, 1994. Numbers
in parentheses refer to the blow number in Table IV-I.
23
Sample Cu Fe Zn Pb S 2
Si0 4
0
3
Fe As
(Blow)
Initial Matte 42.2 23.7 2.81 0.91 25.1 0.29 8.0 0.05
Matte 1 (1) 23.2 38.6 4.82 0.47 7.7 14.3 24.2 0.03
Matte 2 (2) 70.3 2.87 0.66 0.51 20.8 0.19 1.4 0.03
Matte 3 (2) 74.0 1.43 0.28 0.4 19.7 0.25 1.5 0.02
Transfer Matte 71.2 2.88 0.54 0.67 20.0 0.31 1.9 0.03
Blister Copper 97.89 0.67 0.0044 0.0072 - - - 0.0096
Slag 1 (1) 5.35 45.1 4.51 0.67 1.54 21.8 44.0 0.05
Slag 2 (2) 7.04 36.5 3.82 0.95 2.39 23.2 37.0 0.05
Copper Slag 1 31.4 22.3 2.48 3.21 0.64 18.3 44.5 0.05
Copper Slag 2 41.5 20.1 2.16 2.55 0.33 14.0 47.0 0.04
Table IV-ffl Material assays, copper converter charge 588, Feb. 2, 1994. Numbers
in parentheses refer to the blow number in Table TV-I.
24
Sample Cu Fe Zn Pb S 2 Fe
SiC) 4
0
3 As Sb Bi
(Blow)
Initial Matte 42.2 20.8 2.59 1.35 22.5 0.53 7.5 0.034 .0045 .0032
Matte 1 (1) 37.7 23.3 2.75 1.00 15.1 7.43 23.2 0.022
Matte 2 (1) 31.2 25.6 2.95 0.8 11.1 9.62 28.5 0.019
Matte 3 (1) 57.1 11.8 1.6 1.17 17.9 4.33 10.0 0.014 .0028 .0013
Matte 4 (2) 49.8 14.5 1.83 1.01 17.1 4.24 12.0 0.02
Matte 5 (2) 58.4 9.01 1.31 1.13 18.4 2.96 6.0 0.014
Matte 6 (3) 63.2 7.43 1.33 1.21 20.1 0.83 3.8 0.018 .0022 .0014
Matte 7 (4) 58.5 8.89 1.48 1.18 20.0 0.72 3.0 0.016
Matte 8 (4) 59.0 8.45 1.45 1.32 21.2 0.45 4.0 0.017
Matte 9 (4) 62.7 7.87 1.3 1.15 20.3 1.03 3.2 0.015 .0019 .0002
Matte 10 (5) 65.7 4.15 0.75 0.89 19.9 1.06 2.2 0.012
Matte 11 (5) 62.8 4.39 0.82 0.73 17.3 2.55 3.6 0.01
Slag 1 (2) 8.1 39.8 3.93 0.8 2.54 18.8 47.0 0.015
Slag 2 (3) 12.4 38.3 3.8 0.7 4.71 17.8 41.5 0.022 .0058 .0007
Slag 3 (4) 4.16 38.2 4.38 1.45 1.19 25.5 34 0.012
Slag 4 (5) 3.52 40.6 4.44 2.06 0.67 24.3 48.5 0.016 .0057 .0002
Table IV-IV Material assays, copper converter charge 595, Feb. 4, 1994. Numbers
in parentheses refer to the blow number in Table IV-I.
2
Si0 Fe CaO 3
0
2
A1 0
2
H
Flux I 75.6 2.2 1.4 8.2 I 7.0
Table TV-V Flux assay, copper converter plant trials, Feb., 1994.
25
4.2 Nickel Converter Trials
Sample Element Assay Method

Matte, White Metal, Cu, Zn, Fe, -NaCO fusion with LC.P. finish
0
2
Na
3
Slag, Dusts S, Si0
2
As 4 digestion with AAS finish
HC1O
Sb, Bi High: Distillation and I.C.P.
Low: Digestion with graphite furnace
analysis
Blister Copper Cu Digestion, interference removal and
electroplating finish
Zn Acid digestion with AAS finish
Pb, As, Fe, Digestion, hydroxide precipitation,
Bi, Sb separation, redigestion with AAS finish
Flux 2
Si0 0 fusion with Si0
2
NaOH-Na 2 dehydration
Fe NaOH-Na fusion, Fe
0
2 3 precipitation and
concentrated 4
SO titration
NH
CaO, A1
3
0
2 HF, HC1O
4 and HC1 digestion with AAS
Table IV-VI Methods of determination for each assay.
Data similar to that obtained from the copper converters is also available for a total
of four complete charges of a nickel converter. These data were obtained during a
previous study at the Copper Cliff smelter of Inco Ltd.

97 In this case both the air rate and
bath surface temperature were measured constantly, and recorded on the smelter
computer at one minute intervals. These two variables are plotted for one charge in
Figure 4.1. This figure shows that there is considerable variation of both temperature and
air rate throughout a charge. Through a single blow there is usually an initial temperature
drop corresponding to flux addition, followed by a relatively continuous rise up to the
end of the blow. Interruptions to the steady temperature increase may be due to matte or
26
scrap additions, or enforced idle times required by environmental considerations. The air
rate usually follows a similar pattern through a blow, with a rapid initial drop related to
flux addition, followed by a steady increase.
Details of the charges followed are given in Table IV-Vll, and assays of the primary
components are given in Tables IV-VIll to IV-XI. It can be seen from a comparison of
these tables with Tables TV-IT to IV-IV that there is more composition data available from
the copper converter, while the continuous temperature measurements in the nickel
converter gives considerably more information regarding the heat balance.
Table TV-VU shows that there is considerable variation between charges, with a
number of different sources of converter inputs. The relatively large number of operating
converters at Copper Cliff increases the potential for inter-converter transfers of both
matte and slag, as well as transfers of material with a high copper content from the
copper converters which are situated in the same converter aisle. It is also evident that
considerably more scrap is used in nickel converting than in copper converting. This is
due to the larger amount of iron present in the nickel reverberatory furnace matte, which
causes an increased amount of heat generation.
27
1550
1500
w
D
1450
Ui
I
1400
700
600
z
Ui
500
400
0 200 400 600 800
TIME (mm)
Figure 4.1 Variation in measured bath temperature and air rate in a nickel
converter, (#3 converter, charge 105, May 23, 1988).
28
H
- D
c.
.-.- C)
!
CD CD
CD C
0 a CD
I-i) 0
E
a CD c C,
C,) s _- C,, -
1
CD
u IIIIIiH
CD
0

CD

C i
z

CD
,,
---
00 C
I I I I I I
I-
%__
1:3
I I
00 i
Ji C C
cc)

%
I
Charge 105 106 107 108

5 total time (mm) 126 74
time idle (mm) 30 30
# of idle periods 3 2
matte added (tonnes) 20+40(1) 36(2)
flux added (tonnes) 18.2 18.2
scrap added (tonnes) 10 4.5
slag skimmed (tonnes) 36 36
time idle (mm) 22 18
# of idle periods 1 1
matte added (tonnes) - -
flux added (tonnes) 18.2 7.3

scrap added (tonnes) - -
slag skimmed (tonnes) 36 18

time idle (mm) - -
# of idle periods - -
matte added (tonnes) - -
flux added (tonnes) 20 20

scrap added (tonnes) 15 10
slag skimmed (tonnes) - -
(1) Transferred Matte

(2) Copper converter washout
Table IV-Vll Details of nickel converter charges (continued).
30
Sample Cu Ni Co Fe S 2
Si0 Pb Zn As
(Blow)
F. Matte 1 8.32 25.6 1.16 33.9 28.0 0.0894 0.104 0.0272 0.0202
F. Matte 2 8.47 21.8 0.85 37.5 27.9 0.0638 0.11 0.0414 0.0139
C. Matte 1 (1) 13.8 38.8 1.6 16.9 25.2 0.181 0.080 0.0116 0.0202
C. Matte 2 (4) 15.4 42.5 1.45 11.4 24.9 0.0618 0.071 0.0043 0.0218
Bess. Matte 23.5 48.3 0.949 0.792 22.4 <.0079 0.0625 0.003 0.0252
Slag 1 0.568 0.972 0.591 51.1 1.95 24.4 0.0419 0.0555 <.0115
Slag 2 0.487 0.77 0.536 51.7 1.75 24.1 0.0352 0.0574 <.0113
Slag 3 0.496 1.02 0.605 50.6 1.39 26.7 0.0414 0.0552 <.0116
Slag 4 0.444 0.90 0.675 49.7 1.01 29.5 0.0497 0.052 <.0114
Slag 5 1.43 3.39 1.14 48.6 1.39 26.0 0.0585 0.0467 <.0115
Slag 6 1.07 3.35 1.55 44.6 0.619 30.0 0.07770.0401 <.0119
Table TV-Vu Material assays, nickel converter charge 105, May 2, 1988. Slag
samples numbers correspond to the blow they were skimmed after. Numbers in
parentheses refer to the blow number in Table IV-Vll.
Si0 Pb Zn As
F. Matte 1 8.52 27.7 1.19 33.8 28.4 0.0519 0.0957 0.0242 0.0133
F. Matte 2 7.25 27.5 1.04 33.2 27.4 0.0918 0.114 0.0224 0.0181
C. Matte 1 (2) 18.4 42.5 1.27 9.83 24.1 0.165 0.0693 <.0024 0.0165
C. Matte 2 (3) 21.7 46.8 1.03 5.79 22.5 0.0591 0.0853 <.0025 0.0206
Bess. Matte 24.1 51.4 0.789 0.956 21.8 0.0247 0.058 <.0023 0.0225
Slag 1 1.1 2.28 0.788 49.8 1.56 24.2 0.0494 0.054 <.0118
Slag 2 0.863 2.6 1.37 51.1 .55 26.9 0.0607 0.0442 <.0118
Slag 3 0.712 1.17 0.515 55.6 2.15 20.4 0.0363 0.0792 <.012
Slag 4 1.23 3.95 1.56 46.0 0.581 26.8 0.0833 0.0418 <.0111
Table IV-IX Material assays, nickel converter charge 106, May 24, 1988. Slag
parentheses refer to the blow number in Table IV-Vll.
31
Si0 Pb Zn As
F. Matte 1 6.6 25.9 1.06 34.6 27.6 0.0994 0.0976 0.0246 0.0168
F. Matte 2 8.34 24.1 0.943 34.5 27.4 0.136 0.0922 0.0337 0.0154
C. Matte (2) 14.7 42.8 1.53 14.6 25.5 0.0726 0.085 0.0040 0.02
Bess. Matte 21.9 51.7 1.1 1.17 23.0 0.13 0.0634 <.0024 0.0352
Slag 1 0.759 1.39 0.545 55.2 2.62 21.1 0.0334 0.0611 <.0105
Slag 2 0.54 0.99 0.602 52.6 1.57 24.8 0.0346 0.0505 <.0113
Slag 3 1.72 4.37 0.754 48.6 3.02 23.9 0.0375 0.0442 <.012
Slag 4 1.32 3.46 0.787 48.0 1.97 26.2 0.042 0.047 <.012
Slag 5 1.85 4.79 1.09 42.7 2.23 29.9 0.0637 0.0362 <.012
Slag 6 2.22 6.00 1.36 39.3 1.96 31.9 0.0671 0.0328 <.0116
Table IV-X Material assays, nickel converter charge 107, May 25, 1988. Slag
parentheses refer to the blow number in Table IV-Vfl.
Si0 Pb Zn As
F. Matte 1 6.62 27.4 1.27 32.8 27.8 0.108 0.101 0.0176 0.0176
F. Matte 2 9.48 24.2 0.833 34.1 27.8 0.08 14 0.138 0.0435 0.0148
C. Matte 1 (1) 14.8 45.5 1.53 12.5 25.5 0.083 0.0916 0.005 0.0263
C. Matte 2 (3) 14.9 44.9 1.39 12.4 25.2 0.253 0.0813 0.0074 0.0243
Bess. Matte 19.5 55.6 1.05 1.1 23.0 0.0606 0.0613 <.0025 0.0326
Slag 1 0.952 2.27 0.663 50.4 1.72 24.1 0.0464 0.0501 <.0119
Slag 2 0.637 1.54 0.778 49.2 1.07 28.1 0.0543 0.0469 <.0119
Slag 3 0.862 2.82 1.31 46.8 0.716 28.8 0.064 0.0426 <.0118
Table IV-XI Material assays, nickel converter charge 108, May 26, 1988. Slag
samples numbers correspond to the blow they were skimmed after.
32
4.3.1 Oxygen Efficiency
4.3 Analysis
The oxygen efficiency of non-ferrous converters is usually thought to be very high,
but reported values show a wide variation. In fact, it has been found that there is a
considerable variation within a single operation.

98 Also, there is no way to calculate an
accurate value of oxygen efficiency. Johnson et al. give the equation
% 0 efficiency = 100 x
Theoretical 02 Required to Convert Matte to Blister .. .[4. 1]
02 Blown into Converter
which appears straightforward, but is far from accurate. There are a number of
complicating factors, including an imprecise knowledge of the amount of matte and other
materials which are added to the converter.
Values of oxygen efficiency can be derived from the data collected in the plant
trials by calculating the total amounts of iron removed between matte samples and
comparing it with the amount of air blown during that period. While this procedure may
still suffer from the same problems, especially for cases where the matte samples were
separated by material charging, better values should be obtained where the samples were
taken close together.
Overall oxygen efficiencies calculated from the assays for the copper converter
charges followed are given in Table IV-Xll. Separate values are also given for the
combined slag blows and the copper blow. It is evident that oxygen efficiencies are
considerably lower than generally thought, and that efficiencies are higher in the copper
blow. This has been reported previously,

98 but no explanation has been given.
The oxygen efficiencies calculated from the matte assays are shown in
Table IV-XllI. Not all of the matte assays could be used, due to the high silica contents,
33
Charge Oxygen Efficiency (%)

Overall Slag Blows Copper Blow
586 76 55 82
588 69 63 72
595 - 68 -
Table IV-Xll Overall oxygen efficiencies for copper converter charges followed in
plant trials.
indicating a large slag content in the samples. The first oxygen efficiency reported for
each charge in the table is for the period between charge up and the given matte sample.
In all cases the first matte sample taken contained too much slag to allow it to be used.
Charge Matte Oxygen Efficiency (%)

586 2 94
3 48
588 2 75
3 59
595 6 70
7 50
8 67
9 65
10 78
Table IV-XllI Oxygen efficiencies calculated from matte samples.
It can be seen in charges 586 and 588, that there is considerable variation
throughout the charges, with a generally lower efficiency when the iron contents are low.
The lower oxygen efficiencies at low iron contents suggest that the iron removal rate may
come under liquid phase mass-transfer control, with the oxygen beginning to react with
copper sulphide. This does not reduce the overall efficiency, and may cause the
34
calculated efficiency in the copper blow to be too high. This is not apparent in charge
595; however, the iron content in these mattes did not drop below 4%, so the reduction in
efficiency is not likely to be seen.
As mentioned above, the values calculated for oxygen efficiency in the nickel
converter can only be approximate, since weights of the mattes at the time of sampling
are not known. Also, both the weights and compositions of other materials added
between sampling were not measured accurately. To determine approximate weights for
the sampled mattes, copper and nickel balances can be carried out using the required
weights as unknowns. The balances provide two equations which can be solved
simultaneously to give the required weights. An iron balance can then give the amount of
iron reacted. Table IV-X1V gives the values of oxygen efficiency calculated in this
manner as well as the overall efficiencies for the charges where inter-sample values could
not be determined.
Charge Matte Oxygen Efficiency (%)

105 - 93
106 1 66
2 98
107 - 90
108 1 88
2 55
Table IV-XIV Calculated nickel converter oxygen efficiencies.
Generally, the calculated oxygen efficiency is higher than in the copper converter.
The most likely explanation for this is the greater tuyere submergence in this nickel
converter, due to its larger size. However, the amount of magnetite in the charged
materials is not considered in the calculations. This increases the calculated values of
35
4.3.2 Material Deportment
iron oxidized, and hence the calculated oxygen efficiencies. The magnitude of this effect
could be large, since the magnetite content in the reverberatory matte can be over 8%.
Unfortunately, insufficient magnetite assays were carried out at the time of the testing to
allow the inclusion of this in the oxygen efficiency calculations.
4.3.2.1 Major components
There are four major components in the copper converter; copper, iron, sulphur, and
silica. These materials are distributed between the slag, blister copper, dust, and gas in
the proportions given in Table IV-XV. From the table it can be seen that the removal of
iron and sulphur from the matte is almost complete, with the majority of the iron being
removed in the slag, and the sulphur reporting to the gas. It appears that almost all of the
silica added is also removed in the slag, but the amount of flux added is not known with
any accuracy, so the input silica was calculated based on the outputs to the slag and dust.
This does not include the flux which is collected in the dusts beyond the flue, or is blown
out to the atmosphere as the converter turns into stack after flux addition.
Between 80 and 85% of the copper fed to the converters reports to the blister
copper, with the majority of the remainder being removed in the slag. Of the copper in
the slag, about 60% is in the slag removed at the end of the copper blow. This material is
recycled directly to another converter, while the remaining slags and dust are returned to
the reverberatory furnace. The amount of copper in the skimmed slag is relatively
constant, due to the practice of blowing to copper high before skimming. Since the
copper content in the matte is approximately the same at each skim, the copper in the slag
is also. However, the sulphur content of all slags sampled, with the exception of the
copper slags, was more than sufficient to allow all the copper to be present as suiphide,
36
Charge Stream Cu Fe S 2
Si0
Blister Copper 85.2 0.2 - -
Slag Total 12.0 99.1 4.1 99.4

586 Slag Blows 3.9 82.6 3.7 81.7
Copper Blow 8.1 16.5 0.4 17.7
Dust 2.8 0.6 2.5 0.6
Gas - - 93.4 -
Slag Total 12.3 97.9 4.8 99.8

588 Slag Blows 5.2 86.3 4.5 84.1
CopperBiow 7.1 11.6 0.3 15.7
Dust 3.9 0.6 2.9 0.2
Gas - - 92.3 -
Slag Total 17.8 98.7 4.4 99.0

595 Slag Blows 6.3 86.0 4.0 85.6
Copper Blow 11.5 12.7 0.4 13.4
Dust 2.6 1.2 1.9 1.0
Gas - - 93.7 -
Table IV-XV Distribution of major components between output streams of the

copper converter.
either dissolved or entrained. An indication of the amount of entrainment can be seen
from the slags with a low silica content in charge 595. In these slags the copper content
is close to double the usual amount. This will be almost entirely due to entrainment, and
is caused by the high slag viscosity.
In nickel converting there are two major output streams, the slag and the Bessemer
matte, and one minor stream, the dust. Ideally, all the copper, nickel, and cobalt will
report to the Bessemer matte, while the iron will be removed to the slag. The results of
37
an analysis of the data collected from the nickel converter are shown in Table IV-XVI.
This shows that the recovery of nickel and copper to the matte is over 90%, while over
95% of the iron reports to the slag.
Charge Phase Cu Ni Co Fe
Slag 4.9 5.3 58.2 97.7
105 Bessemer Matte 91.7 91.1 39.2 0.9
Dust 3.4 3.6 2.7 1.4
Slag 2.8 3.2 48.6 95.4
106 Bessemer Matte 94.4 93.9 48.2 2.2
Dust 2.8 2.9 3.2 2.4
Slag 6.0 6.0 44.3 96.9
107 Bessemmer Matte 91.4 91.2 53.2 1.9
Dust 2.6 2.8 2.5 1.5
Slag 4.8 4.6 49.4 96.0
108 Bessemmer Matte 91.2 92.1 47.6 1.8
Dust 4.0 3.3 3.0 2.2
Table IV-XVI Distribution of major components in nickel converting.
Figure 4.2 shows that the amount of valuable metals lost to the slag increases with
matte grade. The usual explanation for this relates to increased oxidic dissolution of the
valuable metals at higher oxygen partial pressures, which is seen in equilibrium
experiments. However, when the total mole fraction of copper, nickel and cobalt in the
slag is plotted against the oxygen potential of the slag calculated from the 3
/Fe ratio,
2
Fe
the result is Figure 4.3, which does not show any evidence that oxygen potential has an
effect. This suggests that there is another explanation for the increased metal losses. It is
possible that, at lower concentrations of iron in the matte, liquid-phase mass-transfer
becomes important. As the amount of iron decreases there will be a point at which the
mass-transfer rate of iron to the gas-liquid interface becomes less than the rate of oxygen
38
mass-transfer to the interface. Below this concentration cobalt and nickel will begin to
react, and since both cobalt and nickel oxides are thermodynamically favoured over the
metals, they will report to the slag. Table IV-XVI also shows that close to half of the
cobalt is lost to the slag. However, the relatively small amounts of cobalt present may
lead to considerable errors in these numbers.

.08
.07
z
0
I
.06
U
I
I
o .05
Ui
0
.04
Li)
z
.01
.5 .55 6 .65 .7 .75
Cu+Ni+Co IN MATtE (WEIGHT FRACTION)
Figure 4.2 Variation of total copper, nickel, and cobalt in slag with nickel
converter matte grade.
39
0.13
0.12
j 0.11
W 01
.
0.09
1
0.08
0.07
LI.
o 0.06
z
Q 0.05
.
I. I
0.04
0.03
0.02
0.01
0 ,. . .,
11 -9 -7 -5
LOG(PARTIAL PRESSURE OF OXYGEN)
Figure 4.3 Variation of total copper, nickel, and cobalt in slag with slag oxygen
potential.
4.3.2.2 Minor elements
The most important minor elements present at the Fun Flon smelter are lead and
zinc. Of the other minor elements usually associated with copper ores, arsenic is the only
one which is present in any appreciable amount. While antimony and bismuth are
present, their concentrations are not sufficient to cause any problems.
The distributions of lead, zinc, and arsenic between the three output streams are
given in Figure 4.4. These values are calculated from the overall mass balances of the
separate charges. For the minor elements, it is assumed that all of the input materials
which are not accounted for in the blister copper or the slag, report to the dusts. In this
case the dusts include those collected in the cottrell precipitators and the baghouse. Both
lead and zinc are removed effectively, with less than 0.5% of the lead and 0.1% of the
zinc reporting to the blister copper. Approximately 10% of the zinc and up to 35% of the
40
_____

lead are removed in the dusts, with the remainder reporting to the slag. The arsenic
distribution is notably different, with about 10% of the input arsenic reporting to the
blister copper, and 60% being concentrated in the dusts. A similar distribution can be
seen for bismuth in Figure 4.5, while the same figure shows that the proportion of
antimony reporting to the gas is considerably lower, with a correspondingly larger
proportion reporting to the slag.
100
Zn Pb As
90 CHARG
586
+
80 + 588
Lii 0 595
70 +
:i:
40
0.
Ui

30
20
1-
10 10
0 I I I I I I
SLAG BLISTER DUST SLAG BLISTER DUST SLAG BLISTER DUST
Figure 4.4 Minor element distribution in Hudsons Bay Mining and Smelting
copper converters, charges 586, 588, and 595, February 1994.
41
100
90 ELEMENT
+ Bi +
80 Sb
uJ
70
20
0
10 +
0
SLAG BLISTER DUST
Figure 4.5 Antimony and bismuth distribution in Hudsons Bay Mining and
Smelting copper converter charge 595, February 1994.
As is the case of copper converting at Flin Flon, the only minor elements present in
appreciable quantities in the Copper Cliff nickel converters were lead, zinc, and arsenic.
Of these, lead is the most abundant, but in many cases the concentration of the minor
elements is close to, or below, the lower threshold of the assay technique. The
distributions of these elements between the output streams are given in Figure 4.6. Only
three of the four charges could be used in this case, due to problems with the mass
balance on charge 106. These problems relate to a complete lack of knowledge of the
weight and composition of the mush which is initially present in the converter.
Normally the mass balances can be carried out by assuming that the weight and
composition of the mush is essentially the same after each charge. However, for
charge 106 the amount of every element removed from the converter was considerably
42
higher than the amount charged, leading to the conclusion that an unusually large
quantity of mush was present at the beginning, or an unusually small quantity remained
at the end.
90
- Pb CHARGE Zn As
80
70 -
+ 107
1
Lu 0 108 +
0
4:
I
0.
o .
1 50
0
z
40
0
.
30 +
20 -
10 .
0
I
0 I I I I
SLAG MATTE DUST SLAG MATTE DUST SLAG MATTE DUST
Figure 4.6 Minor element distribution in Inco nickel converter (#3 converter,
charges 105, 107, and 108, May 1988).
Figure 4.6 shows that the distribution of the lead is relatively even between the
three output streams, with a slightly higher proportion reporting to the dust and a slightly
lower proportion reporting to the slag. This is similar to the distribution in the copper
converter at the end of the slag blows. The zinc distribution is also similar to the copper
converter, with the majority of the zinc being removed in the slag. The arsenic
distribution, however, is quite different, with between 50 and 70% reporting to the matte,
while under 20% is removed with the dust. This is the reverse of the copper converter
distribution, and may suggest that arsenic has a greater affinity for nickel mattes than for
copper mattes. Unfortunately, the accuracy of the assays is not sufficient to allow any
firm conclusions to be drawn.
43
4.3.3 Converter Dusts
The analysis of the minor element distribution in the copper converter indicates that
they are concentrated to a certain extent in the converter dusts. During the plant trials a
set of dust samples was obtained. Flue dust samples were taken after each charge, and
during charge 590 four samples were taken from different points along the length of the
bank of Cottrell precipitators, and a sample of baghouse dust was also obtained.
Figure 4.7 shows a schematic of the dust collection system at Flin Flon, and indicates the
approximate location where the Cottrell samples were taken. The assays of these
materials are given in Table IV-XVII. Some interesting trends can be seen in this table.
The concentration of copper drops continuously with distance from the converter, while
those of zinc, lead, arsenic, antimony, and bismuth all increase. The silica content of the
dusts increases initially, with a peak in the two samples taken from the middle of the
Cottrells.
Sample Cu Fe S 2
5i0 Zn Pb As Sb Bi
Flue Dust (c586) 66.7 4.13 18.6 2.19 1.18 1.72 0.03 - -
Flue Dust (c588) 70.5 3.9 20.0 0.97 1.63 0.78 0.05 - -
Flue Dust (c595) 53.6 12.4 19.1 5.12 2.18 1.94 0.019 - -
Flue Dust 62.6 4.81 16.8 5.1 0.95 1.16 0.023 .0081 .0026
Cottrell Dust 1 51.1 4.43 13.1 17.7 1.68 2.0 0.059 .0039 .0027
Cottrell Dust 2 35.5 4.17 10.4 28.7 2.23 5.4 0.12 - -
CottrellDust3 22.2 3.55 8.4 31.8 3.78 5.37 0.145 .0108 .0141
CottrellDust4 20.5 5.52 11.3 15.0 8.72 5.33 0.33
Baghouse Dust 8.28 4.26 14.2 4.0 16.4 12.3 1.01 .0294 .064
Table IV-XVII Compositions of converter dust samples.
44
Since a large proportion of some of the minor elements report to the dusts, it is
important to gain a better understanding of how the dusts are formed. It has been
reported that there are four mechanisms by which dusts can be formed in a steelmaking
99 vapourization, metal and slag ejection due to bubbling, and solids entrainment.
vessel;
To this should be added mechanical ejection due to slopping in the converter. Different
mechanisms will be responsible for the removal of different elements. The dust samples
have been analyzed using optical and scanning electron microscopy to aid in determining
which mechanisms are responsible for the removal of the various elements.
FLUE DUST COTTRELL DUST BAGHOUSE DUST
CONVERTER
Figure 4.7 Schematic of the dust collection system at Hudsons Bay Mining and
Smeltings Flin Flon smelter. Numbers indicate approximate position from which
Cottrell dust samples were taken.
4.3.3.1 Flue dust
The wide variation in the flue dust assays shown in Table IV-XVII is related to the
stage of the charge they were formed at. The large amount of flue dust generated does
45
not allow the collection of a sample representative of the entire charge, but the separate
samples show the differences which occur during the charge. Generally, samples with
low iron and silica contents will have been produced during the copper blow, while those
with higher silica contents will have been produced during the slag blows.
The converter flue dust is primarily composed of spherical particles mixed with a
few grains of flux. Figure 4.8 is a micrograph of the flue dust and shows a number of
interesting features. It is evident that there is a wide range of particle sizes present, but
most of the particles have diameters between 0.25 and 1 mm. Also, some of the particles
can be seen to have a coating of a white powder, while another shows evidence of a pore.
These features become more evident at higher magnifications. Figure 4.9a shows a
particle coated with what appears to be a layer of condensed fume, while Figure 4.9b
shows a pore in a lightly coated particle. If the particles are mounted and sectioned,
(Figure 4.10) it can be seen that the majority of the spheres are, in fact, hollow. These
pores are most likely caused by dissolved gas coming out of solution during freezing, but
may also be a coating held on small bubbles by surface tension.
46
Figure 4.8 Copper converter flue dust, x25.
47
a.
b.
Figure 4.9 Copper converter flue dust, a. coated particle, x150, b. particle with
pore, x300.
48
Figure 4.10 Copper converter flue dust, mounted and sectioned, x25.
At higher magnifications, the polished sections show some other features.
Figure 4.11 a shows a non-porous particle which contains entrained particles of flux and
what appears to be copper droplets which may have separated out as the material cooled.
Figures 4.1 lb and 4.1 ic also show particles which contain copper. In Figure 4.1 lb. the
copper forms a single droplet at the edge of a larger particle. This is probably a particle
ejected during the copper blow. Figure 4.1 ic shows a slightly porous particle which
appears to be fractured. The central pore and the fractures contain copper, which
probably separated out during solidification. The primary material in this particle also
appears to be a different colour from the particles around it. Wavelength dispersive x-ray
(WDX) analysis of a similar particle (Figure 4.11 d) shows that the darker phase is slag
49
with an iron-copper ratio of 3.91. This is considerably higher than is found in the slags
from the slag blows, and lower than slags from the copper blows. However, the
contained particle is almost pure copper, with trace amounts of lead, zinc, and sulphur,
and no measurable iron. This suggests that the material is slag ejected during the copper
blow.
In general, this analysis indicates that the flue dusts are predominantly material
ejected from the bath. The assays show that it is primarily matte, with smaller amounts
of slag, copper and white metal. The differences in the compositions shown in
Table IV-XVII are caused by variations in the proportions of each of these materials
present. The relatively low zinc assays and the lead assays which are slightly higher than
found in matte, suggest that the fume seen is lead based. X-ray diffraction analysis of the
flue dusts showed the presence of lead sulphate, which thermodynamics predicts to be the
predominant phase.
50
- .4
s.
.,
..e ,&.
S., -
1
SI .1
a. b.
c. d.
Figure 4.11 Copper converter flue dust, mounted and sectioned, a. particle
containing entrained slag and copper droplets, x125, b. particle containing copper
droplets, xlOO, c. fractured particle containing copper, x125, d. slag particle containing
copper droplet, x80.
51
4.3.3.2 Cottrell dust
The Cottrell dust assays indicate that there is an increase in minor element content
with distance from the converter. Figure 4.12 shows samples of the dust from three
positions along the bank of Cottrells. The dust appears to be a mixture of spherical
particles and angular flux particles surrounded by a matrix of fine, powdery material.
The samples taken farther away from the converter show an increase in the proportion of
fine material present, as well as a decrease in the size of the larger particles. This last
point can be seen more clearly in Figure 4.13, which shows the samples with the fine
material removed. While all samples contain small diameter particles, the maximum
particle diameter decreases from 0.5 to 0.1 mm with distance from the converter. The
larger number of angular flux particles in the second Cottrell sample, corresponding to
the increased silica assay, can also be seen in Figure 4. 13b. X-ray diffraction analysis of
the Cottrell dusts shows a predominance of silica and lead sulphate, with a small amount
of As
3 possibly present.
0
2
A previous analysis of Cottrell dusts from the Kidd Creek Mines copper smelter
showed a much higher proportion of lead and zinc than were found in the present case.
These dusts were produced by the Mitsubishi process, so may be considerably different
from converter dusts, however there may still be some similarities, particularly in the
4 was the primary form of lead present,

mineralization. It was determined that PbSO
while zinc was present as oxide, sulphide, and a ferrite. Copper was present in oxide,
ferrite, and arsenide forms. It is possible that the ferrites are present in the copper
converter dusts, although the measured magnetite content of the dusts was below 4% in
all cases. The iron content of the dusts is also low, and, since the zinc and copper ferrites
are also magnetic, they would increase the value of magnetite measured. The sulphur
52
contents of the converter Cottrell dusts also indicates that the copper is primarily
combined with sulphur, and x-ray diffraction indicates that it is present as copper
sulphide, which was not found in the Mitsubishi process dusts. It is probable that the
converter dusts contain a much higher proportion of ejected and entrained material than
the Mitsubishi process dusts, which contain more condensed fume leading to higher
minor element contents.
Scanning electron microscopy of the converter Cottrell dusts shows that all of the
particles are coated with the fine material, (Figure 4.14a). As well as the spherical and
angular particles, other small, irregular particles are present. Figure 4. 14b shows one of
these at high magnification. It appears to be an agglomeration of the fine material. WDX
dot-mapping of the Cottrell dusts shows that the majority of the dusts are covered with
zinc oxide, with some areas also showing high concentrations of lead and sulphur. This
confirms that the matrix material is condensed vapour, which has formed on the larger,
ejected particles. The increased amount of fine material with distance from the converter
is caused by a combination of the reduction in gas temperature, causing more material to
condense, and the reduced number of ejected particles which are small enough to remain
entrained in the gas. This conclusion is supported by the assays, and indicates that
vapourization is the primary mechanism for removal of both lead and zinc. The similar
trends in arsenic, antimony, and bismuth concentrations suggests that they are removed
by the same mechanism.
53
C.
Figure 4.12 Copper converter Cottrell dust, a. sample 1, xlOO, b. sample 2, xlOO,
c. sample 4, xl 60. Numbers refer to sample positions shown in Figure 4.7.
54
C.
Figure 4.13 Copper converter Cottrell dust with matrix removed, a. sample 1,
xlOO, b. sample 2, x160, c. sample 3, x160. Numbers refer to sample positions shown in
Figure 4.7.
55
b.
Figure 4.14 Copper converter Cottrell dust, a. sample 2, x300, b. sample 1,
agglomerated fume, x2000. Numbers refer to sample positions shown in Figure 4.7.
56
The form of the silica present in the Cottrell dusts indicates that it is removed by the
solids entrainment mechanism. This is also evident from observations of converter
operation. At Fun Flon, flux is added by ladle through the mouth, and a portion of it can
be seen to be blown out of the converter as it turns back into the blowing position. The
distribution of the silica along the Cottrell bank can be attributed to the variation in flux
size fraction.
4.3.3.3 Baghouse dust
The baghouse dust is very similar to the Cottrell dusts in appearance, and follows
the same pattern as was seen in the Cottrells. In fact, the baghouse dust is almost entirely
made up of the fine condensed vapour, with only a very small proportion of silica and
ejected bath material. This can be seen in Figure 4.15. It should be noted that the dust
collected in the baghouse comes from the reverberatory furnace as well as the converters.
However, there does not appear to be a considerable difference between the dusts
reaching the baghouse. Both x-ray diffraction and WDX indicate that the predominant
materials present in the baghouse dust are zinc oxide and lead sulphate, with some silica
stifi present.
57
Figure 4.15 Smelter baghouse dust, x1500.
58
5.1 Basic Bubble Growth
5 GAS FLOW j THE BATH
In order to properly model the gas/liquid reaction and mass-transfer it is essential to
have a reasonable representation of the average bubble surface area present at any time.
Unfortunately, little information is available on this subject, particularly with respect to
horizontal injection. While some experimental work has been carried out, in all cases the
lumped parameter kA is the end result. This value is not transferable between systems,
so can only be used to give an idea of trends. However, there is a large body of
theoretical work available concerning vertical injection which can be modified to
represent horizontal injection. This chapter will develop the theory required to give an
adequate representation of the bubble growth and rise in the bath.
In past mathematical models, the gas has been assumed to form either a jet or
bubbles at the tuyere tip. The simplest modelling technique is to assume the gas flows in
a specific, calculable trajectory, and from that derive an average surface area.
2

101
Unfortunately, the assumption upon which it is based is not valid at the gas flow rates in
copper converters. It also neglects the period of bubble growth on the tuyere which
accounts for a considerable portion of the

103 and does not deal well

37
mass-transfer,
4
with jet break-up.
A number of theoretical equations have been developed to represent bubble growth
and
105 and the basic principles of these can be transferred to the situation
35
detachment,

1
of the copper converter. In almost every case the models are developed for vertical
injection, so a direct transfer to this process may not be valid. These models consider
only isothermal and non-reactive conditions so the validity of their direct use would be
59
questionable. A modification of a force-balance type model to the copper converter has
been developed by Ashman et al.

35 which does include both the reaction and heating
effects.
A comparison of the predicted bubble size at detachment and bubble frequency
from a number of different models is given in Table V-TI. The bubble sizes are
calculated for the typical copper converter conditions used by Ashman et al.
35 and are
given in Table V-I.
Air flow rate per tuyere (m

sj
3 0.25
Inlet air temperature (K) 298
Tuyere diameter (m) 0.04
Tuyere submergence (m) 0.4
Bath velocity (m s) 1.8
Bath temperature (K) 1450
Matte density (kg m
)
3 4200
Matte surface tension (N m
)
1 0.4
Gas velocity (m s) 198.94
Fr(-) 2.83
Table V-I Typical copper converting conditions used for bubble size calculations.
35
Physical modelling, however, has shown that for the conditions prevalent in the
converter neither the jet nor the single bubble assumptions are valid. Instead, a
combination of the two appears to be more correct. A schematic of the process observed
for the injection of air into water, with a high Froude number, is shown in Figure 5.1
The figure indicates that there is a short jet formed, from which a bubble breaks off
periodically, as well as bubbles forming above the jet at the tuyere tip. Physical
60
Bubble Bubble Bubble Ref.

volume diameter frequency
(ms) (m) (s)
Ashman et al. (with heating) 0.045 0.441 10.78 35
Ashman et al. (without heating) 0.019 0.331 13.16 35
Davidson et al. 0.066 0.502 3.77 105
Mersmann (K=10) 0.026 0.370 9.46 107
Mersmann (K=26) 0.042 0.433 5.87 107
Wraith 0.052 0.465 4.76 108
Wraith et al. 0.074 0.52 1 3.38 109
Calderbank 0.0125 0.288 20 110
Table V-TI Bubble size at detachment calculated from different models.
modelling studies at lower Froude numbers also show an elliptical gas volume fraction
distribution in the horizontal plane. To allow the modelling of this process the simple
bubbling assumption must be modified. At low Froude numbers it is unlikely that the gas
will have sufficient momentum to form a significant jet. However, there should be
sufficient to distort the bubble to an ellipsoidal shape.

112 Thus in the following
development it will be assumed that the bubble is an ellipsoid, with the axes
perpendicular to the tuyere being equal.
To calculate the penetration of the bubble into the bath (2b) a simple force balance
may be carried out:
61
1=0 O.013s.
0.026s. 0.039s.
0.078s. O.091s.
Figure 5.1 Schematic of high Froude number injection of air into water.

11
d db
PgQo =(Mv)+6ivjir--
where
db
V
dt
2
and
+3a
2
a(8b
) ...[5.31
M PBQt
(3b a)
2
8b
Combining these results in the second order differential equation
62
t+(KpBQ+6i_P-_o ...[5.4]
2 dt1
dt KPBQ ) PBK
where
+3a
2
a(8b
)
K
(3b a)
2
8b
is assumed to be constant. If it is also assumed that the viscosity term is negligible, the
general solution
pvt
b lnt+k
1
k
2
= .
is obtained, where k
1 and k
2 are integration constants. Unfortunately this solution is not
valid at t=O, so is not very useful.
To provide a useful solution to equation 5.4 a numerical approach may be used.
Figure 5.2 shows the calculated growth of a bubble under the conditions given in
Table V-I, neglecting the effects of temperature and buoyancy.
To include temperature and buoyancy, the model of Ashman et al.

35 provides a
good basis. Although the model was developed assuming spherical bubbles it may be
altered to reflect the variation in bubble shape. Other modifications will also be required
to give a more accurate representation of bubble growth.
In the original model it was assumed that the drag coefficient was a constant with
the value 0.4. This was based on correlations for a solid sphere at a high Reynolds
number. In the case of the copper converter this choice of correlation is not valid.
However, the sensitivity analysis did indicate that the drag coefficient had little effect on
the bubble size at detachment, so the assumption may not be important. What is more
63
5 cm
Figure 5.2 Ellipsoidal bubble growth.
important is the main implication of this; that the drag term in the overall equation is
negligible. This result is probably caused by the high value of bath circulation velocity
used in the model. In the equation used by Ashman et 35

al.
Vg + CD VB) = K- [V(vb 1
yB)
the overall drag term is a function of (yb-yB)

2 which will be very small at high bath
velocities. Measurements of fluid flow in a 1:4 scale water model of the Peirce-Smith
converter using Laser Doppler Velocimetry have determined that the maximum flow rate
occurs at the bath surface, with the flow rate close to the tuyere being approximately half
of the maximum value.

113 In the water model, the highest reported velocity was
.163 ms, with a gas velocity at the tuyere of 79.2 ms

. This indicates that, while the
1
bath velocity in the actual converter will be higher than the measured value, it is unlikely
to reach the 3.6 ms required to give a velocity of 1.8 ms at the tuyereline.
64
Other aspects of the model which must be modified are the apparent lack of
consideration of horizontal motion, and the bubble detachment criterion. In particular,
the absence of horizontal motion results in the erroneous equation
ds
where s is the distance from the centre of the tuyere tip to the centre of the bubble. This
equation is valid for vertical injection, where the bubble rises directly above the centre of
the tuyere, but this is not the case in horizontal injection, particularly with an ellipsoidal
bubble. Figure 5.3 compares the two cases, and it is evident that for a rapidly expanding
bubble equation 5.8 cannot be used, unless it is only considering the vertical component
of the velocity in which case s should be replaced by h, the height of the bubble centre
above the tuyere centreline. While this differentiation may appear trivial, it may cause
considerable errors in the determination of the bubble height, which will affect the bubble
detachment calculation.
A. B.
Figure 5.3 Comparison of horizontal and vertical injection conditions.
65
If the above considerations are taken into account the model of Ashman et at.
35 can
be used as a basis for a more complex model. In doing so a number of the assumptions
made in the original model must be carried through to the new one, however, some may
be discarded or altered. Those which are still required are:

4

35
1) the bubbles are not affected by those forming on adjacent tuyeres;
2) there is no coalescence of bubbles from the same tuyere;
3) the gas flow through the tuyeres is constant;
4) at detachment a volume of gas equal to a hemisphere of diameter d remains on the
tuyere;
5) the bath viscosity and turbulence result in a drag force on the bubble;
6) gas surface tension effects are negligible;
7) the gas is ideal;
8) the bubble wall is a black body and
9) only hydrostatic pressure is exerted on the bubble.
The assumption of no interaction between adjacent tuyeres is obviously incorrect, as it
has been ascertained that there is tuyere interaction during converting,

4 but this
interaction appears to take place primarily during the copper blow and rarely involves
5 The effect of interaction on bubble growth and detachment are

more than two tuyeres.
not well known, however observations of interacting tuyeres in both physical models and
operating converters indicate that interaction has little effect on bubble frequency. The
tuyeres have a common gas feed, so the pressures in the bubbles will be the same
regardless of whether they are coalesced or not. With the only force working to alter the
bubble shape being the surface tension, which is very small in comparison to the other
forces involved, it is not unreasonable to assume that bubble coalescence during growth
66
5.2 Bubble Detachment Criterion
has no noticeable effect on the growth and detachment process.
The assumptions which will be replaced are:
1) the gas inside the bubble is backmixed;
2) the bubble detaches when its base reaches the top of the tuyere and
3) the drag coefficient has a constant value of 0.4.
The replacement for the first assumption will be discussed later. The original drag
coefficient will be replaced by a value calculated from
4tpgdz,
D
- PB Vj,
This correlation has been developed for spherical drops and bubbles in pure systems.
116 It
should be noted that surface active components within the bath will cause this to be an
underestimate particularly at high Reynold s numbers.

7 The bubble detachment
criterion will be discussed in the following section.
In previous models, the point at which the bubble detaches from the tuyere is
generally calculated as a simple relationship between the bubble radius and the distance
of the bubble centre from the tuyere. These simple equations can be used for vertical
injection, but not for horizontal injection. Ashman et at.

35 assumed that the bubble
detached when its base reached the top of the tuyere. This is similar in general form to
the vertical injection correlations. However, using the assumption that a volume of gas
equal to a hemisphere of diameter d, remains on the tuyere at detachment, a better
criterion can be determined. This assumption was introduced by Davidson and 5

SchUler
based on observations of vertical injection systems. The exact volume of gas remaining
on the tuyere is not known, so an assumption must be made.
67
Figure 5.4 shows the assumed process of detachment and Figure 5.5 shows the
geometry of the system at detachment. For this purpose it is assumed that the bubble
reverts to a spherical shape once necking has occurred, since gas momentum no longer
affects it. The geometry can be used to determine the position of the bubble when
detachment occurs as follows.
B.
C. D
Figure 5.4 Bubble detachment process.
The gas remaining on the tuyere at detachment forms part of a sphere as shown in
Figure 5.5. If it is assumed that the detaching bubble is touching the wall directely
above the tuyere, then at detachment
68
...[5.10]
h =(s2_r)2
Figure 5.5 Bubble detachment geometry.
Values of h and s for a range of bubble sizes at a tuyere diameter of 0.05 m are
plotted in Figure 5.6. It can be seen from the figure that, especially for larger bubble
sizes, detachment takes place considerably before the base of the bubble reaches the top
of the tuyere. This point can be seen more clearly from Figure 5.7. In this case it is
possible that the new bubble growing on the tuyere may punch through into the detached
bubble, causing further growth.
69
0.45
0.4
0.35
0.3
E
w 0.25
C)
z
0.2
0.15
0.1
0.05
0
0 0.1 0.2 0.3 0.4
BUBBLE RADIUS (m)
Figure 5.6 Variation of the height of the bubble centre above the tuyere centreline
(h) and the distance of the bubble centre from the tuyere centre (s) with bubble radius at
detachment.
70
5.3 Bubble Break-up During Growth
bath
10.1
Figure 5.7 Variation of bubble position at detachment with bubble diameter.
The growth and detachment equations outlined above are still not sufficient to
completely model the bubbling phenomenon. In particular, the predicted size of the
bubbles at detachment is much larger than can be considered reasonable. Therefore,
there must be some other mechanism which reduces bubble size at work. It has been
noted that large bubbles rising in a liquid are unstable and have a tendency to break up,
and this is likely to be the case for the bubbles growing on the tuyere. Thus it is proposed
71
that as a bubble grows on the tuyere it reaches a size where it becomes unstable and
breaks into two bubbles, one of which is still attached to the tuyere while the other is free
to rise.
To calculate the minimum bubble diameter at which breakup will occur a
combination of Kelvin-Helmolz and Rayleigh-Taylor instability theory is used.

8 This
theory has recently been applied to the bubbling/jetting transition in submerged
19 but is more applicable to the present application. It assumes that an initial

injection,
perturbation with amplitude q, produces a travelling wave with the equation
1 =q,exp[kc,t+ik(x Crt)] ...[5.1l]
Which can be rewritten as
11 Th exp[kctJ cos(k(x Crt)) ...[5. 12]
This equation indicates that c represents the disturbance propagation speed, and kc, is the
amplitude growth factor. The model of Kitscha and Kocamustafaogullari predicts the
8 For the
breakup of fluid particles using a relationship between these two quantities.
case of a bubble rising in a fluid (Figure 5.8) the propagation speed is given by
_( PBVBSifl8O ...[5.13]
cI
2pB+pbcoth(khb)
and the growth factor is given by

! ...[5.14]
k f PBPb 2
( l.
coth(khb)k VB Sfl
5
9)2
3
ak g I Ap I k
J

1.

(PB + Pb coth(khb))
2 PB + Pb coth(khb)
From Figure 5.8 it can be shown that for spherical bubbles
72
B.
VB
VB
Figure 5.8 Schematic illustration of flow around a bubble.

118
db ...[5.15]
hb 0
=--(cos8 cos8)
while for an ellipsoidal bubble
...[5.16]
hb 0
+
=(a

)
2
)cos9
(ba cosO
02 +
(a

) cose)
(ba cos9
where e0 is the point where the disturbance originates and e is the wake angle. Both of
these forms of the equation will be required since the cross-section perpendicular to the
tuyere axis will be circular.
From the above equations the breakup criterion may be derived as
...[5.17]
EpB+pbcoth(khb)ld 1 Eitan()i I2
(1.5vsinO)
ppcoth(khb)k g
3
ak IApIk l>
[ PBVB
3 Jb
Itan()I 1 (PB+PbCOthQthb))
2 PB+PbcothQthb)S
and for rising bubbles Cg is given by
73
...[5.18]
+ Pb coth(khb)J2
Cg =
To calculate the minimum bubble diameter at which breakup will occur values are
required for the wake angle and the wavenumber. The wake angle is given by the
empirical correlation

12
5it l9it ...[5.19]

e =+-jj-exp(O.62Re.)
04
To determine the wavenumber which will cause the most unstable wave growth,
equation 5.14 is differentiated with respect to k and set to zero. This results in the
equation
apbhb csch
3
k (khb)
2
jJ
0
[
2
(khb)coth(khb)
2
2hbpbcsch
+k2{3a[pB + p coth(kh)]
PBPJ1.51B h csch2(khb)]}
[5 20]
_k{2PBPb1.5vB sin[ coth(khb) +gpph csch2(khb)} gpB(pR + Pb coth(khb)) = 0
If the value of khb is large it can be assumed that coth(khb) is equal to one, and that terms
(khb) are negligible. Using these simplifications equation 5.20 can be

involving csch
2
reduced to
( ( 2 ...[5.21]
_2Pbl.5vBsinJJk_PB=0
2
3ak
This indicates that, for a given bath composition, the critical wavenumber is a function of
the velocity alone, and that it has a minimum value when the velocity is equal to zero. If
these assumptions are applied to equation 5.17 the maximum bubble diameter can be
calculated as
74
3vB ,..[5.22]
db
= c{*2252k2i23k}
where
...[5.23]
[Itan)I
[Itan)I
and
* Pb ...[5.241
P
PB
However, at low velocities, application of the above equations results in values of
the wavenumber which are considerably smaller than the minimum wavenumber which
could cause breakup:
2it ...[5.25]
kmill

C ,i
Also, at low velocities the simplifying assumptions are not valid. For this case, when the
calculated values of wavenumber which should give the most rapid breakup are less than
k., it follows that k should be used in equation 5.17. After considerable manipulation
this gives the equation
...[5.26]
I (1 + p) 2 ) J
*
PB 8W Ow) PB w
75
for the maximum bubble size. Equation 5.26 can be solved using the standard procedure
for quadratic equations. lii all of these calculations the bath velocity used must be the
velocity of the top surface of the bubble relative to the bath. It is important to note that
all of these derivations are for spherical bubbles. For the elliptical cross-section of the
bubble db must be replaced with 2b(l-e), where

! ...[5.27]
(b2 a2
2
8=1

i b2
is the eccentricity of the ellipse.
Figure 5.9 shows the variation of predicted maximum bubble sizes using
equations 5.22 and 5.26. This shows that equation 5.26 is only valid at very low
velocities (less than .33 ms), which are not likely to occur under injection conditions.
Using equation 5.22 for the conditions given in Table V-I gives a maximum bubble
diameter of approximately .2 m. This is considerably smaller than the diameter predicted
by the growth models. Figure 5.9 shows that there is a strong dependence on the bath
velocity, with a higher velocity allowing a larger bubble. This result is expected, as the
criterion by which the occurrence of breakup is determined, is based on a comparison of
the rate of disturbance growth with the rate the disturbance passes over the bubble
surface. If the disturbance reaches the side of the bubble before it is large enough to
cause breakup then it is swept off the bubble without any effect. Equation 5.13 indicates
that if the bath velocity is faster, the disturbance propagation speed (Cr) is also faster,
allowing a larger bubble to form.
76
5.4 Bubble Rise
1 350
0.9
300
0.8
0.7 250
E
LU 0.8
I- 200
LU LU
0.5
U D
LU z
-J LU
>
D
0.3 100
0.2
50
0.1
0 0
0 0.5 1 1.5 2
BATH VELOCITY (me)
Figure 5.9 Variation of maximum bubble diameter and wavenumber with bath
velocity.
5.4 Bubble Rise
After the bubbles detach, either from the tuyere or the growing bubble, they will
rise due to both the buoyancy force and the bath motion. For modelling, the assumption
that the bubbles rise at their terminal velocity should not introduce a significant error.
Thus the bubble rise velocity is given by

2
! ...[5.28]
(2(g lAp Idb
VT)L
P8
2
77
5.4 Bubble Rise
The assumption that the bubble rise velocity relative to the bath can be represented by the
rise velocity of a bubble in a stagnant bath has recently been shown to be valid under gas
injection conditions.
122
Further breakup of the bubbles may occur as they rise, and the same theory as
detailed in the previous section may be applied. In this case the velocity to be considered
is the bubble rise velocity with respect to the bath. From equation 5.28 it can be
determined that any bubble with a diameter less than 0.05 m will have a tenninal velocity
under 0.33 ms, and so will have a maximum bubble size as determined from
equation 5.26. For bubbles in this size range combining the bubble breakup criterion
with the terminal velocity expression gives
f a (2w3l ...[5.29]

2
d
b
sin2J_22}
2
{+)
For a bubble rising at its terminal velocity with a high Reynolds number
-. 5 ...[5.301
18
and for the large density difference in bubbling systems it can be assumed that
lAp ...[5.31]
PB
and that the term involving p is negligible. Using these assumptions the equilibrium
bubble size can be calculated as

...[5.32]
d,, = 3.258951--
i PB
78
5.5 Bubble Recombination
For larger bubbles the introduction of the terminal velocity equation does not result
in the same degree of simplification. Equation 5.21 becomes
0.l786gpdkgp=0
2
3ak ...[5.33]
The assumption that the term involving the bubble diameter is negligible introduces a
maximum error of under 0.1%, and leads to the simplified equation

1
[534]
k=1.8083J
Applying equations 5.28 and 5.34 to equation 5.22 results in
...[5.351
0.96868pbd+ 1.333d4PiJ 4a=0
The actual minimum bubble size will be determined by equation 5.35 if it is greater
than 0.05 m. Otherwise it will be calculated using equation 5.32. The bubbles will break
up progressively until the minimum diameter is reached. It is important to note that the
secondary and lower order bubbles formed by this procedure will also undergo breakup,
leading to the formation of a very large number of bubbles.
With the large number of bubbles formed within the relatively small plume area,
bubble coalescence is inevitable. Unfortunately, it is also very difficult to model
theoretically. Instead an semi-empirical measure is required to determine whether
recombination occurs. The work of Sano and Mon

23 regarding the size of bubbles in a
plume gives the following equation for bubble size.

0.5 ...[5.36]
dvs=6.903J v
0
1
79
This shows that the effect of the surface tension/density ratio, as discussed above, is
modified by the superficial gas velocity. The surface tension/density ratio represents the
equilibrium bubble size, while the effect of superficial gas velocity is due to bubble
coalescence. It is evident from equation 5.36, that at high superficial gas velocities
coalescence occurs more frequently, resulting in larger bubbles.
The effect of the superficial gas velocity appears to be important, but it has received
little attention, with only low values being used in physical modelling; ranging from
120
0.0065 ms
1 to 0.4 ms. The superficial gas velocity in the copper converter can be
over 3 ms, so it is probable that there will be considerably more coalescence than
observed in the physical models. In order for the gas volume flow through the bath to be
sufficient to give the required superficial velocity, the average bubble rise velocity must
be greater than the superficial velocity. Since the bubbles have been determined to be
rising at their terminal velocity relative to the bath, it follows that a high superficial gas
velocity will require larger bubble sizes to achieve the required volume throughput.
Therefore, in the model it is assumed that bubbles will coalesce until the average bubble
velocity is greater than the gas superficial velocity.
80
6.2.1 Bath Velocity and Gas Holdup
6 MODEL DEVELOPMENT
6.1 Introduction
In the past, models of copper and nickel converters have assumed that thermal and
thermodynamic equilibrium prevailed throughout the system. However, one study raised
some doubts as to whether the matte, slag and gas were at the same temperature.
97 This
would imply that interphase equilibrium was not attained, and this implication is
supported by gas temperature measurements carried out in a nickel converter.

25 A
further analysis of composition data obtained from a nickel converter
97 confirms that the
matte and slag are not in equilibrium. Therefore, to properly model the converter a
kinetic approach is required.
6.2 Preliminary Considerations
At least an approximate knowledge of the bath velocity is required, both for the gas
flow calculations, and for the calculation of mass and heat-transfer coefficients. The only
mathematical model of fluid flow in the copper converter determined that the maximum
bath velocity was 0.022 ms

126 However, this model did not consider the effect of the
.
1
slag layer, or calculate the velocity of the liquid in the plume. The calculated velocity
appears to be quite low, but it is explained by the large bath/refractory contact area and
low tuyere submergences, which are dictated by the form of the converter.
126 Physical
modelling of the Peirce-Smith converter has reported bath velocities of up to 0.168 ms
in a 1:4 scale water model.

113
An approximate estimate of the maximum bath velocity in the bubble column can
be obtained from the spout height. Applying an energy balance to the spout, considering
energy per unit volume, gives
81
Energy input = bath kinetic energy
PBV(1 P)
and
Energy output = bath potential energy .. . [6.2]
= pBgh
(
8 l
where is the gas fraction in the plume and , is the gas fraction in the spout. Equating
input to output gives
.[6.3]
PBVB(l
2 Pr) = pgh,(1
or
...[6.4]
(l_p)12
_(
2g hgp
VB
(1 ))

The gas holdup values can also be calculated from the spout height, by assuming
that the overall bath level is unaffected by gas injection. This implies that the volume of
gas in the plume is equal to the volume of liquid in the spout. With the assumption that
the basal radius of the spout is double the plume radius, based on time lapse photography
of the spout in a water model of a Peirce-Smith converter,
Ah4 =Ah(l )
or
3h
h
8(1 )
Substituting equation 6.6 into equation 6.4 gives
82
_____
2
[67]
yE 1
=h(
)J
This equation shows that the maximum bath velocity is independent of the value chosen
for the spout gas fraction, so only the spout height will be affected by.
An estimate of the gas holdup and liquid velocity in the plume can be obtained by
considering the volume of gas within the plume,
Vgp=Qtr
where tr is the average residence time of a bubble in the plume. The total plume volume,
is given by
V=Ah,
so
VgpQtr ...[6.10]
V Ah,
With
...[6.ll]
and

...[6.12]
= + VT
r
equation 6.10 becomes

...[6.13]
VB + VT
The average height reached by the liquid in the spout will be the centre of mass, so
...[6.14]

IB
( 4
2
cp))
83
6.2.2 Converter Geometry
Combining equations 6.13 and 6.14 and rearranging gives
...[6.15]
4Ijht
+,J 4=0

+2
vupv) + +2
vSUPvT)
If it is assumed that the average bubble is the equilibrium size calculated from
equation 5.33, then equation 6.15 may be solved numerically for q. It should be
emphasized that this is very approximate because the validity of some of the assumptions
is uncertain.
For mass and heat-transfer calculations within the converter, interfacial areas
between phases and solid/liquid contact areas are required. The horizontal cylinder form
of the converter adds some complication to this. Figures 6.1 and 6.2 show schematic
cross-sections of a converter, idle and blowing respectively.
The idle case is the easiest to deal with, so will be considered first. The matte/slag
interfacial area is given by
22
! ...[6.16]
1 2
AM/s = 2(r (r hM) )L
Similarly, the slag/gas interfacial area is given by
22
...[6.17]
1 2
As,G = 2(r
(r hM ) )L
5
h
Unfortunately, values for hM and h are not directly calculable. Given the mass of matte,
MM, and slag, M, present in the converter, hM can be determined from
...[6. 18]
MM (7r _j r JiM (r hM)
LL i
2 2

r sin rChM
2
(

=
hM)
2

and h is calculated from
84
2 2
_l(rchs(rchs)( 221
...[6.19]
r sin rh )
5
h
Ps 2

PM
Figure 6.1 Schematic cross-section of an idle converter.
The matte/refractory contact area is given by
_/rhM](rchM)
1
.[6.20]
2
sin I h)2]
.
AM,R (2rChM -
r 2
-
where the second term in the equation represents the end-wall contact area. Similarly, the
slag/refractory contact area is given by

2
(r h
)
5 ...[6.21]
Lr[1c 2siif 11+2 3 h)2]_AM/R
(2rh

ASIR =
),)

r rc
85
When air is being blown into the converter a spout is formed. The possible
variations in spout form are shown schematically in Figure 6.2. If the spout height is
greater than the slag thickness (Figure 6.2a), only the slag thickness and matte/slag
interfacial area are affected. The value of h must be modified to account for the spout
volume
r _iis] (r h
)
5 ...[6.221
L[rc2sin-{ 5 hJ ntabh
(2rh 8

Values of a and b can be determined from the bubble formation calculations outlined in
Section 5. If the modified slag thickness is greater than the spout height, then the
configuration conforms to Figure 6.2b. To calculate the slag/matte interfacial area the
extra area due to the spouts must be included. Unfortunately, the surface area of an
ellipsoid is calculable only for a few special cases, so an approximation must be used.
Therefore, it is assumed that the spout has a surface area equal to a regular ellipsoid, with
minor axes equal to the average of the maximum bubble width and the spout height, so
I N ...[6.23]
= 2(r (r ntab 2
a s sin EJ
where
b+h ...[6.24]
b=

If the matte spout height is less than the slag thickness (Figure 6.2b) the slag will
form part of the spout. The slag spout height can be calculated in a similar manner to the
matte spout height, using the value (hshspMhM) as the submergence. In this calculation
h will be given by equation 6.22 to account for the matte spout volume. The matte/slag
interfacial area is still given by equation 6.23, but the slag/gas interfacial area must be
86
sp
h,
Figure 6.2 Schematic cross-sections of an operating converter: a. no gas flow

through the slag, b. gas flow through matte and slag, c. gas flow through slag only.
87
modified to give
! ( ...[6.25]
= 2(r (r h + hM+ h,,j
L
)
2 n1t; ab a2__.sin_1 c
A third possibility is shown in Figure 6.2c. In this case the gas is blowing directly
into the slag, which may occur near the end of a blow when there is a relatively large slag
volume present. Under these conditions the matte/slag interfacial area will be given by
equation 6.20, and the slag/gas interfacial area will be given by equation 6.25. When
blister copper is present it is also possible that the gas will pass through it as well. In this
case the above equations must be modified.
The values of interfacial areas calculated in this fashion will be an underestimate in
most cases. Generally there will be a certain amount of wave formation, with the
extreme case being slopping, when the bath surface can be approximated by a standing
wave. In this case it is likely that the extent of inter-phase mixing will be increased
considerably. To obtain a better estimate of the matte/slag interfacial area during
blowing, a theoretical model of emulsion formation at the edge of the spout is used.
27
This model uses a force balance approach to determine the radius of the slag droplets
formed, and gives
1 ...[6.26]
r
2 !
rd_l6g(pM_ps)cos31l_[l__ 2
l28Gg(pMpS)Co5
sV.
2
P j
1 is the velocity at the matte/slag interface and
where v is the angle shown in Figure 6.3.
To calculate the interfacial velocity, the equation
11627
2 1 -2
N ( VMXS (VMXS V
..
(PM
K =0.13671 II II V I [(1 K)(0.11080.0693K)]
5
.-
Ps} V ) )

was derived, where
88
V. ...[6.281
K=
and x is the slag thickness.

127
Finally, an energy balance is carried out to determine the rate of droplet generation.
For the present case it is assumed that the combined spouts produce a linear interface for
droplet formation, stretching the length of the converter. This gives the number of
droplets formed per second as

27
...[6.291
= v
2
O.83O8L(pvx)
Ps)COS f
00
0 0
o 0
DROPLETS
000
0
0
QL
r0
0
0
0
MATTE
00
0
0
0
0
0
GAS
Figure 6.3 Schematic of emulsion formation during submerged injection.

27
89
6.3.1 Equilibrium Within Phases
6.3 Mass Balance
It is assumed for the calculations that each phase is in internal equilibrium. As
such, each must be considered separately.
6.3.1.1 Blister copper
The copper phase is the easiest to deal with, since it only contains components in
their elemental forms. Thus, there are no reactions and the composition will be governed
only by mass-transfer considerations.
6.3.1.2 Matte
The matte is considerably more complex, since it contains a mixture of sulphides,
oxides and elements. The equilibrium composition within the matte will be governed by
the sulphur potential. If it is assumed that all oxygen is present as magnetite, and all FeO
produced by reaction is carried directly to the slag by the rising bubbles, then no reactions
involve oxygen and an oxygen potential is not required. The reacting components of the
matte are given in Table VT-I, and the equations required to calculate the equilibrium
composition are given in Table VT-TI. All other components are considered non-reacting,
so are not subject to equilibrium calculations. The equilibrium calculations are combined
with mass balances for each element to give the final composition.
Elements Cu, Ni, Fe, Co, Pb, Zn, S

Compounds Cu
S
2 , NiS, Ni
S, FeS,
2
CoS, PbS, ZnS
Table VI-I. Reacting components of the matte.
90
Number Reaction
1 2Cu + 2
1/2S S
2
Cu
2 =NiS
2
Ni+112S
3 2Ni + 2 = Ni
1/2S S
2
4 =FeS
2
Fe+1/2S
5 Co + 2 = CoS
1/2S
6 =PbS
2
Pb+112S
7 =ZnS
2
Zn+112S
Table VT-il Reactions required to calculate the equilibrium composition of the
matte.
6.3.1.3 White metal
The white metal is a special case of the matte phase, in which Cu

S is the only
2
remaining sulphide component. As such its sulphur potential will be governed by
reaction 1 in Table VT-TI.
6.3.1.4 Slag
While the slag is a complex mixture of oxides, it can be assumed that iron is the
only component which has more than one oxide form present. As such, the oxygen
potential of the slag will be controlled by the reaction
3FeO + 1/202 = Fe
4
0
3 ...[6.30]
and the composition is determined by the iron and oxygen mass balances.
6.3.1.5 Gas
Like the slag, the equilibrium composition within the gas is dominated by a single
reaction
+
112S
=
2 S0
0 ...[6.31]
91
6.3.2 Gas-Liquid Mass-transfer
Combining this with sulphur and oxygen mass balances and setting the total pressure to
atmospheric, allows the composition to be cakulated.
6.3.1.6 Calculation Technique
For each of the phases, with the exception of the blister copper, there is a system of
simultaneous equations which must be solved. In some cases these will be solved
directly. In the case of the matte the system is more complex and requires the use of a
non-linear equation solving routine. As in a previous work, a Quasi-Newton technique is
28 Model flow charts are given in the Appendix.
97
used.
Over the majority of a cycle the gas within the bath will only be in contact with the
matte. However, reactions with the slag may also take place within the spout and on the
surface of the bath. Within the matte the rate of the gas-matte reaction is controlled by
gas-phase mass transfer. This suggests that the reaction will be
=FeO+S0
FeS+3/20
2 ...[6.32J
because the partial pressure of oxygen at the bubble surface will be very low, favouring
the least oxidized iron compound. Minor element removal may be controlled by
gas-phase, or liquid-phase mass-transfer, or by evaporation at the gas/liquid interface. To
calculate these rates a representation of the gas flow within the bath is required.
6.3.2.1 Gas flow
The basic theory regarding the gas flow within the bath has been developed in
Section 5. What remains is its implementation in a computer model. Two stages of the
model are required: bubble growth on the tuyeres and bubble rise. It is necessary that
these models also consider heat transfer to the bubble, so all aspects will be considered
92
together.
For the bubble growth calculations, the basic model of Ashman et al.
35 is followed,
with the modifications noted in Section 5. Assuming that the minor elements are present
in the gas in very small quantities, the mole balance within the bubble is given by
0
QP ...[6.33]
dn (x 1 2
where Ab is the bubble surface area given by
2 2tab ...[6.34]
ta +
2
Ab= sin e
. -
e is the bubble eccentricity, and x is the ratio of 02 reacted to SO

2 produced in the
reaction. It has a value of 1.5 for reaction with matte, 1 for reaction with white metal,
and will be infinite for reaction with slag and blister copper. In the latter case, to avoid
the numerical problems introduced by the us of infinity in the model, 10,000 is used so
that the term (x-1)/x in equation 6.33 is approximately equal to one.
The heat balance is given by
dTb QP dn ...[6.35]
nC---=CT +hbAb(TB -Tb)+Ab(cLT-61)-CPTl,---
3
This accounts for heating by convection and radiation. The heat of reaction is assumed to
report entirely to the bath. The bubble volume depends on the moles of gas and gas
temperature, according to
dVRTidn vT ...[6.36]
dtP dt+ dt
The upwards motion of the bubble is given by
93
dw dV ...[6.37]
V-j--=2V+CDitabw 2 -w-
where
WVbVB ...[6.38]
The change in oxygen content of the bubble can be calculated from
2
dC
J QP
0
k A b C02 C2
dV
...[6.39]
dt RTO) dt
and the sulphur dioxide content is given by
0
dC [6.40]
dV
dt
These equations determine the size and position of the growing bubble. In the
model the equation governing the bubble shape (equation 5.4) is solved by a fmite
difference technique, while the above equations are solved simultaneously using a
Runge-Kutta solution technique. At the end of each time step the bubble stability is
determined according to equation 5.31 or 5.35, depending on the interfacial velocity, If
the bubble is unstable then it is assumed to break up into two bubbles, one of which is
still attached to the tuyere. The size of the free (secondary) bubble will depend on the
size of the initial bubble at breakup, and must be used as a fitting parameter.
The equations relating to the motion and breakup of the bubble as it rises through
the bath have been developed in Section 5. What must be considered here is the heat and
mass balance within the rising bubble. The same basic equations can be used as in the
previous analysis, modified to account for the different conditions. Thus the mole
balance and heat balance become
94
p ...[6.41]
dri (x1,
dtl YQAbRT
and
dT,, dn ...[6.42]
respectively.
The equations governing the volume variation and sulphur dioxide concentration
(6.36 and 6.40) remain unchanged, while the change in oxygen concentration is given by
dC2_ [6.43]
dV
.
i A ,-b (-b ..
b-O
O
2
d
d
The modified equations can then be solved by the same technique. By calculating the
passage of a primary bubble and all its related secondary bubbles through the bath, a
number of different parameters may be determined. The gas composition and
temperature at the bath surface are calculated, along with the amount of oxygen reacted
and, therefore, the moles of FeO formed. From the amount of oxygen reacted, the heat
generated by the reaction can be calculated for use in the heat balance. Also, by
combining the gas flow model with a mass-transfer model for the minor elements, the
rate of minor element volatilization may be calculated. This will by dealt with in the
following section.
6.3.2.2 Mass transfer from liquid to gas bubbles
The mass transfer of the minor elements from any of the liquid phases to the gas
bubbles may be controlled by one of three transport steps, or by a combination of the
steps. These are the liquid phase transport from the bulk of the bath to the bubble
95
_________
surface, vapourization at the bubble surface, and gas phase transport from the bubble
surface to the bulk of the gas. The mass-transfer rate for each step may be detennined
separately, and the three combined to give an overall rate equation.
By assuming quasi steady state conditions, mass-transfer in the liquid phase can be
characterized by the equation
1 =
1i kA(Cf *)
1
C ...[6.44]
or, replacing concentrations with mole fractions to give compatibility with the
thermodynamic model
nI=kLAbp(Xr_X,*) ...[6.45]
The vapourization rate can be calculated using the Langmuir-Knudsen equation.
129
aAb *
...[6.46]
(PtP.)
2itRTM,
It is important to note that this equation was derived from the kinetic theory of gases for
vapourization of a solid into a vacuum,

and so some error may be introduced due to the
13
gas pressure within the bubble. This equation is also modified to allow for integration
with the equilibrium model using
p+po. ...[6.47]
which gives
...[6.48]
)
*
(Py.X. P.
-J2iR7M
Mass-transfer within the bubble can be characterized by the equation
kQAb * B
...[6.49]
n =--(P P
)
1
96
______
An overall equation for the mass transport rate to the gas bubbles can be obtained
by combining equations 6.45, 6.48, and 6.49. Rearranging equations 6.48 and 6.49 gives
...[6.50]
and
* (RT B
...[6.51]
1
P ni1jAJ+Pi
respectively. These equations can then be combined to give
= .(I2RTMI +z+PB ...[6.52]

Ac kGA)
Rearranging equation 6.45 gives
...[6.53]
X. =XB
*
, m
Lb PB
which, when combined with equation 6.52 and rearranged gives
,i. 1 1 pB ...[6.54]
-=I i 1 1 1x7
1 j:Oy
Ab kkkpm
where
...[6.55]
k=
-j2iuRTM,
and
y,
0
1
kP ...[6.561
kg
RT
97
6.3.3 Mass Transfer Between Liquid Phases
This equation is very similar to that derived for vacuum refining models, with differences
32 The one exception to this

being due to the gas pressure within the bubble.

131
formulation is the behaviour of the zinc in matte. Zinc oxide is thermodynamically more
stable than iron oxide, so the zinc reaching the gas/liquid interface will react. Thus, the
vapourizing zinc species will be zinc oxide, and any oxide which does not vapourize will
report to the slag.
Within any phase, I, the mass-transfer rate of component i to an interface is given
by
ri *
...[6.57]
= k[(C[ C[)
or, converting to mole fractions
...[6.58]
It is important to note that the interfacial concentration of a component will be different
on either side of the interface. At steady state, the rate of mass-transfer to the interface
will be equal to the rate of mass-transfer away from the interface in the other phase.
In general, at an interface between two liquid phases, I and J, there is a relationship
(assuming instantaneous chemical kinetics)
=
K(X*)n .. .[6.59]
where K is a constant determined by equilibrium considerations. In the second phase, J,
the mass transfer rate of i away from the interface is
ri *
...[6.601
j=kfp(Xi X!)
98
or, rearranging
ri1 ...[6.61]
Akp

Combining equations 6.58, 6.59 and 6.61, and rearranging, assuming n=1, gives
( 1 ...[6.62]
1
kp ?p
This is a general equation which can be used for mass-transfer between any two liquid
phases, including cases where there is a reaction. If n is not equal to one the equation
becomes more complex. However, this does not occur in the present case.
With no reaction, n=1 and
...[6.63]
K=L
Where there is a reaction at the interface, for example
1 1 ...[6.641
S) +
2
Cu = Cu
0
2 (s) + S
the equilibrium constant is calculated as
...[6.65]
oxcu
Ycu
o
2 P.
KR
SXCU
CU
S
2 P
so n=1 and
...[6.66]
oPs
ycu
2
99
6.4.1 Energy Loss
In these equations the partial pressures of sulphur and oxygen represent the sulphur and
oxygen potentials of the matte and slag respectively, and do not imply the presence of
gaseous species. The equilibrium constant is calculated at the average temperature of the
two phases.
6.4 Energy Balance
Without the assumption of thermal equilibrium each of the component phases
within the converter may be at different temperatures. While this adds to the complexity
of the model, the temperature variation may be significant. Heat transfer from the bath to
the gas is calculated as part of the overall gas flow model, so does not need to be
considered further. However, the cooling effect of the gas on the bath is important.
To calculate the temperature of each phase an energy balance must be carried out.
That is
energy accumulated = energy input + energy generated .. . [6.67]
- energy loss energy consumed

-
Each of the terms on the right hand side of equation 6.67 will be considered separately.
6.4.1 Energy Loss
Energy losses come from three sources, materials leaving the converter, conduction
through the walls, and radiation through the mouth. A thermodynamic model of the
nickel converter determined that, during blowing, energy leaving the converter as the
sensible heat of the gas accounted for almost 90% of the total energy losses, while
radiation accounted for the majority of the remaining losses.

5
100
6.4.1 Energy Loss
Energy lost with the gas leaving the converter is calculated as part of the energy
consumption term, so will be considered there. The sensible heat of skimmed or cast
liquids does not affect the temperature of the remaining materials, so is not required for
the model.
Radiation losses from the slag are assumed to be only to the mouth of the converter.
As such they will be dependent on either the hood temperature during blowing, or the
ambient temperature (no mouth cover) while the converter is idle. The rate of energy loss
will be given by
...[6.68]
The emissivity of the slag must be assumed.
Allowing the different phases to be at different temperatures adds complexity to the
calculation of energy loss through the walls. The losses are not uniform over the entire
converter, and the outer wall of the converter is not at a uniform temperature. This was
determined by radiation pyrometer measurements carried out on an operating nickel
converter, which indicated that there was a considerable temperature variation over the
converter shell.
33
However, since the wall losses are very small compared to the energy removed with
the gas and the radiation losses, a relatively simple calculation technique can be used.
Thus, for the end walls

97
k, ...[6.69]
4ew = 2ACf (TB
T)+--(T
T)]
and for the barrel section
L
1
2k r 1 .. .[6.70]
q cb = R I (TB
T) +
2
(T T)
ln(JL
101
6.4.2 Energy Consumption
where the constants k

1 and k
2 are due to the variation of refractory thermal conductivity
with temperature according to

134
kR =k
(1 +k
1 T)= 1.08(1 +4.5(10)T)
2 ...[6.71]
for chrome-magnesite refractory.
In the model the consumed energy is that which is required to bring all charged
materials up to the temperature of the phase to which it reports. This value is calculated
as
=
J
T
CP(T)dT+Ae12]
...[6.72]
The integral in equation 6.72 has been pre-calculated for use in the model, and gives a
final equation
I I d. i ...[6.73]
0 =
q Eai+biTB+ciT+_!JJ
TB
Values of the constants in this equation are given in Table VT-HI.

97
102
jCin J mor
i a b, 3
cx10 x10
1
d
5 Notes
Fe 7841.02 24.476 4.226
Ni -6529.9 25.104 3.766
Cu -141.3 31.38
Co -3940.3 13.807 12.259
FeS -8925.9 51.045 4.979 T<1468K
FeS 4664.09 71.128 T>1468K
S
2
Ni -25182.5 20.318
NiS -12784.5 38.911 13.389
S
2
Cu -6958.62 84.935
CoS -13682.7 44.35 5.251
4
0
3
Fe -52247.3 200.832
FeO -32218.8 68.199
NiO -9589.16 46.777 4.226
0
2
Cu -19636.7 62.342 11.924 T.<1509K
0
2
Cu -38545.1 96.274 .293 -1.925 T>1509K
CoO -14205.8 48.283 4.268 -1.674
2
S -12165.7 36.484 .355 3.766
02 -9507.5 29.957 2.092 1.674
2
SO -15407.7 43.43 5.314 5.941
2
N -8493.394 27.865 2.134
2
Si0 -29666.3 58.911 5.021
Table VT-HI Integrated values of C for use in equation 6.73.135
103
6.4.3 Energy Generation
6.4.3 Energy Generation
The only sources of generated energy in the converter are the reactions. Since the
rates of the main reactions are controlled by oxygen mass-transfer within the gas, the
total energy generated within a time step is approximated by
qgen = A1RAt
2
flO ...[6.741
The value of AHR will depend on the phase in which the reaction occurs. The reactions
which may occur are: in blister copper
2Cu + 1/202 = Cu
0
2 ...[6.751
in white metal
S
2
Cu + 02= 2Cu + SO
2 ...[6.76]
in matte
FeS + 3/202 = FeO + SO

2 .. .[6.77]
and in slag
3FeO + 1/202 4
0
3
Fe ...[6.78]
Values of the enthalpies of reaction for each of these are given in Table VI-TV. The
actual reaction heat is also dependent on the temperature, so the values in Table VT-TV
are modified accordingly. Some energy generation or consumption may also result from
enthalpies of solution, but this will be small in comparison to the main reaction enthalpy.
Reaction AHR
(klmor
)
1
6.75 -166.7
6.76 -190.4
6.77 -463.4
6.78 -317.6
136
Table VI-IV Enthalpies of reaction required for energy generation calculation.
104
6.5.1 Physical and Thermal Properties
6.4.4 Interphase Heat-transfer
Energy will be transferred between phases by convection and mass-transfer. The
convective heat-transfer will be given by
1
4
(
A!,
11
=h

1 T
1
T) ...[6.79]
and the heat transferred with materials passing between phases is given by
= ...[6.80]
It should be noted that in cases where there is a reaction at the interface the heat
generated by the reaction is assumed to be contained in the metal-containing product, and
will report to its corresponding phase.
6.5 Data
In a model of this sort a wide range of data is required. Unfortunately, much of this
data is unavailable in the literature, or only present for a narrow range of temperatures
and/or compositions. Therefore, it is necessary to assume that whatever data is available
is valid over the entire range of conditions present in the model and, if nothing is
available, required values must be assumed or fitted.
Data concerning the physical and thermal properties is required for the gas and the
three condensed phases. Most of these properties vary considerably with composition
and temperature, but it is unusual to find a study which considers both together. The
required properties and the equations used to calculate them are given in Table VT-V.
The equation for the slag viscosity given in Table VT-V is derived directly from
measured viscosities,
40 while the equations for matte and blister copper viscosities are
estimated from measured diffusivities. The constants used in the gas viscosity equation
in Table VT-V are given in Table VT-VT.
105
Phase Property Ref.

Density_(kg m
)
3
Slag 8 0.1 1454T[SiO
3297 + 128.45[FeO] 1
2 137
Matte 3880 + 403.6[Cu]M + 4589[Cu] 3750[Cu] 138
Blister Copper 7800 139

Gas G
3.469(103)_J
-
Viscosity_(kg_rn_i s
)
1
Slag [Fej V 140
2.063(10 0.7l43[s.QJ
,JJ
Matte 139
J
5000
3.36(loiexp(
TM
Blister Copper 4866 141

7.688(10
)
5 exPL\ TB
Gas 2
Co+ClTG+C
T
3
7
4 +C 142
Surface Tension (N m
)
1
Slag 0.71483.17(10)(T273) 138
Matte ( 4
X (2.2711.673x ( X, (1.149+1.188Xg 143
XF+XCJL 53X JXF+XcuJ1 XN
2
+
3 J
Blister Copper 1.136 )TB
5
1.6(10 144
Thermal_Conductivity_(W rn_i K
)
1
Slag 2.09 77
Matte 13.399 17.875[Cu]M+25.551[CU1 13.74[Cu] 138
Blister Copper 133.9 139

Table VT-V Physical and thermal properties of the gas and condensed phases.
106
6.5.2 Thermodynamic Data
Co C, 2
C 3
C 4
C
(x10
)
5 (x10
)
7 (x10
)
9 (xlO
)
2 (xlO
)
6
7.164 -5.083 1.578 -1.785 6.667
Table VT-VT Coefficients for gas viscosity equation (air).
42
6.5.2.1 Free energy
To calculate the equilibrium composition of the matte the free energies of the
reactions given in Table VT-il must be known. Values of these are given in Table VI-Vil.
Reaction AG
)
1
(Jmo1
2Cu + 2 = Cu
1/2S S
2 -147 100+42.05T
Ni + 2 = NiS
112S -l29300+54.06T
2Ni + 2 = Ni
112S S
2 -152500+46.06T
Fe+ 1/2S
=FeS
2 -115300+30.63T
Co + 2 = CoS
1/2S -125000+48.12T
Pb+ 112S
= PbS
2 -138400+64.14T
Zn + 1/2S
2 = ZnS -264800+98.20T
Table VT-Vil Free energy of formation of matte compounds.
42
In addition, free energy data is required to calculate the equilibrium constants used
to determine rates of interphase mass-transfer. The reactions and their corresponding free
energies are given in Table VI-VITI.
Finally, to calculate the compositions of the slag and gas phases, free energies of
two further reactions are required. These are given in Table VT-TX.
107
Reaction AG
(J_mor)
S
2
Cu + 1/202 = Cu
0
2 + 2
1/2S 28360-2.59T
NiS + 1/20 = NiO + 2
112S -122800+41.67T
FeS + 1/202 = FeO + 2
112S -128200+21.13T
CoS + 1/202 = CoO + 2
1/2S -107800+22.6 iT
PbS + 1/202 = PbO + 2
1/2S -57950+21.38T
ZnS + 1/202 = ZnO + 1/2S
2 -80330-3.35T
Table VT-Vu Free energy of reaction for matte-slag reactions.
35
Reaction AG
(Jmol)
3FeO + 1/202 = Fe
4
0
3 -402000+169.77T
2 + 02 = SO
1/2S 2 -363000+72.42T
Table VI-IX Free energy of reaction for slag and gas reactions.
35
The data available regarding the free energies the minor elements presents some
problems. While the agreement for reactions involving single elements in the gas phase
is not bad (Figure 6.4), the free energy of formation of the oxides and suiphides of arsenic
and antimony do not appear to be consistent. Figure 6.5 shows the variation of AG with
temperature for the formation of SbO and SbS, and Figure 6.6 shows the values for AsO
and AsS. It is obvious that a problem exists, particularly in the case of SbO, where two
papers, published in the same year and having one author in common,
3 use vastly

30
different equations for the free energy of the reaction
1 1 ...[6.811
(g) + 2
2
Sb 0
( g) = SbO (g)
108
50
40
30
20
C)
10
-10
-20
1000 1200 1400 1600 1800 2000
TEMPERATURE (K)
Figure 6.4 Comparison of reported values of free energy of reaction.
109
5
SbS
Chaubal et al. [291

Seo and Sohn [30]
-10
Nagamori and Chaubal [26]
-
Hino et al. [144]

Kim and Sohn [31]
.----
-20 -
-25 I I
1000 1200 1400 1600 1800 2000

TEMPERATURE (K)
20
SbO
10
-10
-20 I
1000 1200 1400 1600 1800 2000

TEMPERATURE (K)
Figure 6.5 Comparison of reported values of free energy of formation of SbS and
SbO.
110
5
AsS
0
Chaubal et al. [29]

-5 Sea and Sohn [30]
Nagamori and Chaubal [261
-10
0
-15
-20
-25
1400 1600 1800 2000
TEMPERATURE (K)
-5
AsO
-20
-25
-30
1000 1200 1400 1600 1800 2000

TEMPERATURE (K)
Figure 6.6 Comparison of reported values of free energy of formation of AsS and
AsO.
6.5.2.2 Enthalpy of Reaction
Values required to calculate the heat produced by the reactions are given in
Table VI-IV.
111
6.5.2.3 Activity coefficients
The equilibrium calculations within each phase and the mass-transfer calculations
between phases, require values for activity coefficients. Equations for calculating these
for most of the major constituents can be found from the literature, and those used are
given in Table VI-X.
Phase i Ref.
Slag FeO exp()log(l.42Xpo .2)) 20
4
0
3
Fe 0.69 + 56
XFeO
8
. + 5.45X
0 17
NiO exp(() 1.62) 146
0
2
Cu 9 147
CoO 0.66 148
Matte Fe 40 149
Ni 15 97
Cu 14 17
Co 25 149
FeS exp((8)ln(.54 + + .52XFeS)) 20
(1 1840 I
I I j I.6
S
2
Ni 10 M)
150
NiS 1 97
S
2
Cu 1 17
CoS .4 151
4
0
3
Fe (1573\ 20
expq
TM J
(4.96 + 9.9 logX + 7.43(logX)
2
))
3
)
2
+2.55(logX
Table VI-X Activity coefficients of the major constituents of the matte and slag.
112
Lead is a common contaminant in copper mattes, and is often present in relatively
large concentrations. Copper is also an important contaminant in lead, so there is
considerable information available.

15261 Azuma et al. have determined that the activity
coefficient of lead in copper mattes is equal to one at 1473 K.

52 However, the data of
Eric and Timuin suggest that there is a considerable negative deviation from ideality,
particularly at high matte grades.

58 The same study indicates that the activity coefficient
of PbS at infinite dilution in white metal is 0.035,158 and in dilute solutions
lny = 6.970Xpbs 3.344 ...[6.82]

at 1473 K. Rome and Jailcanen calculated a value of 0.155 for the same parameter, and
suggest that it is relatively constant down to X

2 = 0.7.160 Their results also indicate that
the activity coefficient of lead in white metal is approximately 4, but is quite sensitive to
the sulphur activity.
The activity coefficient of lead in copper metal has been calculated by a number of
162468 and there is fairly good agreement between the various studies. A value
researchers,
of 5.7 is used in the model. The activity coefficient of PbO in slag in zinc slag-fuming is
given by
169
(3926 ...[6.83]
T J
and this agrees well with measurements in copper smelting slags.
This value appears
7
to be unaffected by the oxygen partial pressure.
There is considerably less information available regarding zinc. However, there is
sufficient data to give values for activity coefficients in the three phases. In copper, zinc
is reported to be a regular solution with

63
113
r64O0X1 ...[6.84]
Yzn=exP[
RT j
For dilute solutions of ZnS in matte, the activity coefficient has been calculated as
25
= 6.8 O.02(T 1523) [Cu]M ...[6.85]

while at 1523 K it is reported to be represented by the polynomial
33
= 14.21 136.6X + 437.3X 405X ...[6.861

In slag the ZnO activity coefficient can be calculated from
26
E9201 ...[6.87]
Unlike lead and zinc, antimony is generally thought to dissolve in atomic form in all
three condensed phases present in copper converting. The activity coefficient of
antimony in copper is very low, with reported values ranging from 3.7x10
3 to
1
.
2

60
1 2 The higher of these values are considered to be the more accurate.
.4x10
6 71
72

The activity coefficient of antimony in matte and white metal is considerably higher
than for copper, with the value for white metal being 0.44 and the value in matte
calculated from
173
=exp[4.8584 l.936X] ...[6.88]
at 1473 K. However, both of these values are very sensitive to the sulphur activity when
the matte is sulphur deficient. The activity coefficient of antimony in matte is also
sensitive to the oxygen potential of the system, indicating that some oxide may be formed
at high oxygen partial pressures.

93
There is relatively little data concerning antimony dissolution in slags.

174 What is

170
available is given in the form of distribution ratios, which must be converted to activity
coefficients. An analysis of the data of Nagamori et al. indicates that there is a
114
considerable scatter in the experimental results.
The distribution ratio (Lsb) was given
7
as 30, with the oxygen potential having no apparent effect. This results in an activity
coefficient of 0.4 for antimony in slag.
The behavior of arsenic in copper converting systems is similar to antimony. As in
the case of antimony there is a wide variety of information available concerning arsenic
dissolution in
160
matte,
1 61 and 1
73
75 27
copper,
1
75181
62 with much less available
63
regarding the slag.

182 There is a very wide range of reported values of ; from

70
167
7
5x10 to
18 Some variation with temperature is seen, but it is not consistent
.
2
1x10
between experimenters. It is probable that the lower values of arsenic activity coefficient
are incorrect due to the values of free energy and gas vapour pressures used in their
181
calculation.
The activity coefficient of arsenic in white metal is reported to be in the range 0.2 to
0.12, dropping to 2
l.2x10 as sulphur is removed.
176 Variation of the iron content of the
matte has been found to cause a considerable change in the arsenic activity
160
coefficient.
1
61 At 1473 K
73
log = 1.35 0.848X

2 ...[6.89]
but sulphur deficiency in the matte causes a considerable reduction in the value
calculated from this equation.

73
There is significant scatter in measured data regarding arsenic in slags, although
there is agreement that the dissolved form is monatomic As. Lynch and Schwartze
measured values of varying from 1 to 10 depending on slag composition.

82 Nagamori
et al. reported an average value of LAS of 300, indicating that dissolution of arsenic in
slag equilibrated with molten copper is very small.

7
115
Like antimony and arsenic, it is generally accepted that bismuth dissolves in
monatomic form in all phases concerned in copper converting, although there is some
evidence of sulphide formation at high sulphur activities.

60 However, its behaviour does
not follow the same trends. The activity of bismuth in copper shows a positive deviation
from ideality,
83 with an activity coefficient given by

63
7
c 43751 ...[6.91]
exp[ 2.04
j
=
+ T
51001 ...[6.92]
YB=exp 2.45+
T
Both of these equations give values which agree well with the results of other
Information on bismuth in white metal and matte is limited, and the studies
available show very poor However, the difference can be explained
by the value of bismuth vapour pressure used.

85 Oxygen has no noticeable effect on the
activity of bismuth in matte, and BiS vapour is formed in preference to BiO, which is
closer to the behavior of lead than arsenic and antimony.

6
A number of studies have been carried out concerning the distribution of bismuth
between slag and copper or

7
161
matte.
8 192
0 Most of these calculate distribution
coefficients, and there is considerable disagreement regarding the form of bismuth in the
92 report that oxygen partial pressure has an

slag. However, the most recent studies

6
effect on the amount of bismuth reporting to slag, and one gives activity coefficients in
slag of 1500 and 1.1(108) for Bi and BiO respectively at 1458K and 92
). At
4
PBI=7.5(10
116
higher temperatures the activity coefficient of Bi is increased and that of BiO is reduced.
However, the magnitude of these numbers indicates that very little bismuth will report to
the slag.
Table VI-XI summarizes the activity coefficients of the minor elements used in the
model.
Matte
Pb 23
PbS exp(.2008 2.3245X)
Zn 25
ZnS 6.8 (TM
02
O. 1523) [CuJM
As (1.35_ o.848x)
1
Sb exp(4.8584 l.936X
)
5
Bi 13.6
White Metal
Pb 4
PbS exp(6.97XPbS 3.344)
Zn 3
ZnS 6.8 O.02(TM lS
)[CuJM
23
As 0.12
Sb 0.44
Bi 6.1
Table VI-XI Minor element activity coefficients used in the model.
117
Slag
PbO (3926
expi
ZnO (920
expiT
8

As 5
Sb .4
Bi 1500
Blister Copper
Pb 5.7
Zn
expi
( 6400X
RTB
As 1(102)
Sb 1.4(102)
Bi exp_2.04+4?5J
Table VI-XI Minor element activity coefficients used in the model (continued).
6.5.2.4 Equilibrium vapour pressures
Equilibrium vapour pressures of the minor elements are required to calculate
liquid-gas mass-transfer rates. The values used are given in Table V-Xll.
118
6.5.3 Kinetic Data
Specie Vapour Pressure Ref.
As exp((_)+ 10.62) 31
Bi exp((_22)+ 11.75) 31
Sb exp((_)+12.336) 29
( 23325
Pb exp_)+l9.O65_0.985lnT) 29
PbO exp(()+13.843) 29
PbS exp((_6)+12.977) 29
I( 15243
Zn exp(_--)+21.782_1.255lnT) 26
ZnO exp((_2)+4.651) 26
Table VI-Xll Equilibrium vapour pressures of the minor elements.
6.5.3 Kinetic Data
6.5.3.1 Diffusivities
The diffusivity of each species in each phase is required for the mass-transfer
calculations. Unfortunately, very little data is available for the system under
consideration. Therefore, a theoretical approach must be used. Assuming spherical
particles following Stokes law in a viscous liquid, the Nernst-Einstein relation for the
diffusivity is
193
kT ...[6.92]
6iitr
where r is the atomic/molecular radius of the particle and k is the B oltzman constant.
119
6.5.3 Kinetic Data
This equation requires atomic or molecular radii of the diffusing species, which
poses another problem: while the minor elements and blister copper constituents are
present in elemental form, the other species are present as compounds. The radius values
used to calculate the diffusivity in the matte and slag will depend on the nature of the
solution, If the solution is ionic then the ionic radii of the diffusing elements must be
used, whereas, if the solution is covalent then the molecular radius of the diffusing
species should be used. To determine which case should be used the approximate degree
of ionic bonding can be found using the Pauling electronegativity scale. This suggests
that the bonding in mattes is less than 12% ionic, while that in slags is closer to 50%.136
It is important to note that these numbers are for solid compound, and there may be some
differences for liquids. In fact, it has been suggested that the molten matte is completely
94 but there is no direct evidence of this. The relatively low amount of ionic
ionic,
bonding in mattes suggests that the diffusing species will be covalent molecules, while in
slags diffusion of ions is likely to predominate. Based on this assumption the required
radii are given in Table VI-XllI. Values of diffusivity caluculated using equation 6.92
for Fe
2 diffusion in slag and matte can be compared with measured values. A diffusivity
of 1 .4( 10h1) m
c is calculated for Fe
2 2 diffusion in a slag with an iron to silica ratio of
0.25 at 1400 K, while a value of 1.13(1 O) m

s is obtained for Pe
2 2 diffusion in matte at
the same temperature. These are lower than reported values, which range between
5(10h1) s and 5(108) m
2
m 98 and between 2.9(10) m
s in slag
2
95 s and 1.4(10) m
2 s
2
in
In the gas phase oxygen is the primary diffusing species and its diffusivity is given
4
by
120
6.5.3 Kinetic Data
Specie/ion radius Specie/ion radius

(nm) (nm)
As 0.125
4
Cu 0.096
Bi 0.17 24
Pb 0.12
Sb 0.145
24
Zn 0.074
Cu 0.128 24
Fe 0.076
Pb 0.175 3
Fe 0.064
Zn 0.133 2
Ni 0.072
FeS 0.241
24
Co 0.074
S
2
Cu 0.35 1 NiS 0.237
CoS 0.239 S
2
Ni 0.303
PbS 0.285 2
5i0 0.299
ZnS 0.239
Table VI-XllI Atomic/ionic/molecular radii of matte, slag and bullion
constituents.
36
= 3.754(10
)T2.31(10j
7 ...[6.93]
This equation is actually for oxygen diffusivity in argon, but calculations based on an
equation derived from the kinetic theory of gases indicate that the error involved in using
this equation is less than five percent.

20
6.5.3.2 Mass-Transfer Coefficients
The mass-transfer coefficient between the liquid and gas for rising bubbles is
calculated from
42
...[6.941
d,.
1
k ( dbw
= 1+1 l+
q3i
121
6.5.3 Kinetic Data
Unfortunately, there are no correlations available for mass-transfer on the gas side during
bubble rise, so it is assumed that equation 6.94 holds for both sides of the gas-liquid
interface. However, an equation for mass-transfer during drop formation has been
20
derived,
15
...[6.95]
D )rb
0
(v
2
kg =2.31
Ub
which can be applied to the bubble formation section of the model.
The liquid-liquid mass-transfer coefficient can be given as
...[6.961
k, =
where 8 is the boundary layer thickness. While values of boundary layer thickness are
not known, they can be approximately calculated if it is assumed that they are
comparable to the velocity boundary layer.
6.5.3.3 Heat-Transfer Coefficients
The gas-liquid heat-transfer coefficient is calculated from

143
Nu =2+ O.6Rep) . [6.97]

and the liquid-liquid heat-transfer coefficient between phases I and J is calculated from
h
1 ...[6.98]
h
= 6
1+ 6
h h
1
122
7.1.1 Bubble Growth
7 MODEL VALIDATION
7.1 Bubble Model Validation
7.1.1 Bubble Growth
There is a limited amount of data available concerning bubble growth during
horizontal injection for comparing with the model predictions, however some validation
can be carried out. Oryall and Brimacombe have reported the gas fraction distribution in
horizontal injection of air into mercury.

From this an approximate maximum bubble
1
penetration can be determined for comparison with the model. Table Vu-I compares the
model predicted maximum bubble penetration for four different injection conditions with
the 1% gas fraction line reported by Oryall and Brimacombe.

1 The maximum
difference is 6 mm, indicating a relatively good fit.
Gas Flow Tuyere Predicted Measured Predicted Measured

Rate diameter Penetration Penetration Width Width
)
1
s
3
(Nm (m) (m) (m) (m) (m)
0.002676 .00325 .076 .07 .047 .046
0.001615 .00325 .058 .064 .039 -
0.001844 .00476 .054 .055 .042 -
0.000710 .00325 .037 .043 .029 -
Table Vll-I Comparison of measured

and predicted gas penetration in mercury.
1
Further validation can be obtained from the bubble frequency. Hoefele and
Brimacombe have reported a bubble formation frequency of between 10 and 12 s_i in a
nickel converter.
202 The model predicts a variation in bubble formation frequency, with a
range of 9.5 - 10.5 s. Other studies have determined that the bubble frequency in copper
converters is affected by the extent of refractory wear.

203 The bubble frequency in a

5
newly relined converter was found to be between 8 and 14 s_I, but this value dropped
rapidly to a steady value close to 4 The rapid decrease in bubble frequency is
123
7.1.2 Bubble Rise
explained by the accelerated refractory wear around the tuyereline, which usually results
in the formation of a notch. There are two main mechanisms by which the notch reduces
bubble frequency; by reducing the bath flow rate at the tuyere tip, and by preventing the
section of the bubble close to the tuyere from rising. The notch may also increase tuyere
interaction, but this does not appear to affect the bubble frequency.
15 The model
assumes that there is no notch, so the agreement is good when compared to the newly
relined converter.
7.1.2 Bubble Rise
Verification of the bubble rise portion of the model is even more difficult. Only a
small amount of information relating to horizontal injection is available. The physical
modelling carried out by Adjei gives some data which can be used, but it can only give a
rough validation due to its imprecise nature.

37
The formula derived for calculating the bath velocity within the plume, gas holdup,
and spout height can be tested by comparing measured and predicted spout heights and
gas fractions. Figure 7.1 shows a comparison of calculated spout heights with those
. It can be seen that the model predicts a shorter spout height than
measured by Adjei
37
was measured. However, this is to be expected, as the spout heights were measured from
time lapse photographs, which tend to include the liquid ejected from the spout in the
spout itself, thus increasing the apparent size. This suggests that the predicted values are
at least approximately correct.
Physical modelling in bottom injection systems also provides some data which may
be used for verification. Table Vil-il shows a comparison of measured values of gas
fraction, bath velocity in the plume, and spout height with those predicted by the model.
It can be seen that the predicted spout heights are slightly higher than those measured,
124
7.1.2 Bubble Rise
018 -
V
0.17- TUYERE SUBMERGENCE (m)
0.16 -
086 A MEASURED
0.15 PREDICTED
v MEASURED
-
.117
0.14 -
PREDICTED
0.13 -
I
I 0.12 -
0
0.11 -
0 V
A
----------------
V
V
0.08 -
0.07
0.06 -
0.05
0.04- I I
0.001 0.003 0.005 0.007 0.009
GAS FLOW RATE m

1s
Figure 7.1. Comparison of measured

37 and predicted spout height.
while the predicted gas fractions are high at the low flow rate and low at the high flow
rate. However, the values of superficial gas velocity are not precise, due to uncertainties
in the cross-sectional area of the plume. Also, the data of Castillejos and
205 indicate that the average gas fraction varies with height above the
204
Brimacombe
tuyere in bottom injection, while Oryall and Brimacombe report that the gas fraction is
relatively constant in the plume region for horizontal injection.

11
The predicted bubble surface area and gas-phase mass-transfer can be tested by a
comparison of predicted and measured gas utilization. However, there is a problem with
the measured data, since Adjei

37 did not consider the effect of a surface reaction. In this
case the model calculates a considerably lower gas utilization than was measured.
Unfortunately there is not sufficient information available to calculate the extent of the
surface reaction. In particular, the diffusion boundary layer thickness on the bath surface
125
7.1.2 Bubble Rise
Gas Approximate Approximate Predicted Approximate Predicted Approximate Predicted Ref.

flow superficial gas fraction gas bath velocity bath spout height spout
rate gas velocity fraction )
1
(ms velocity (cm) height
s)
3
(cm (ms) )
1
(ms (cm)
371 .11 .12 .16 - - - - 204

1257 .18 .25 .22 - - - - 204
371 .11 - .16 4 4.7 206
876 .17 - .21 - - 6 6.9 206
1257 .18 - .22 - - 7 7.4 206
1630 .21 - .25 - - 8 9 206
167(1) .11 .26 .2 207
500(1) .32 .54 .39 207
1000(1) .66 .61 .57 207
167(2) .059 .15 .13 V 207
500(2) .17 .26 .27
V
207
1000(2) .45 .42 .41 207
100 .03 .05-.3 .08 .2-.3 .235 - - 122
(1) nozzle diameter = .28 cm
(2) nozzle diameter = .5 cm
Table VU-TI Comparison of measured and predicted gas fraction, bath velocity,
and spout height in vertical injection systems.
and the total bath surface area are required, but are not calculable. The diffusion
boundary layer thickness wifi be inversly proportional to the square root of the gas
velocity over the bath surface

, so will be reduced by increasing both the gas flow rate
208
and the tuyere submergence. Both of these factors will also increase the bath surface
area, and so have a large effect on the surface mass-transfer. If it is assumed that the bath
surface is flat and that the surface boundary layer thickness is a function of the gas flow
rate and tuyere submergence, then the predicted overall gas utilization can be fitted to the
measured values using
o = (.2374 20.06Q
+ .00256
J (1.621 (l0)
+ 4.023(10-5)]
126
7.1.2 Bubble Rise
and Figures 7.2 and 7.3 show the fit obtained. While these curves are fitted, they show
that the model is at least able to predict the general trends in gas utilization. It should
also be noted that some of the errors in gas utilization may be caused by the uncertainty
in the gas-phase masstransfer coefficient.
099 -
o
+
LU
0.95 -
.&. __
+ -
a: ---p
LU
Q o. ---.
o -
a:
D -
TUYERE SUBMERGENCE (m)

X MEASURED
0.85 - .057 PREDICTED
0.001 0.003 0.005 0.007 0.009
GAS FLOW RATE (ms)

Figure 7.2 Variation of fraction sulphur dioxide reacted with gas flow rate
including the fitted effect of surface reaction.
127
___________
7.2.1 Bath Temperature
0.95
C
uJ
0.9
w
a: 0.85
(ii
C
0.8
+
C
a: 0.75
D
j 0.7
D
Cl) MEASURED
0.65 PREDICTED
F
0
a:
LI
0.55
0.5 I I I I I I
0.01 0.03 0.05 0.07 0.09 0.11 0.13
BATH DEPTH (m)
Figure 7.3 Variation of fraction sulphur dioxide reacted with tuyere submergence
including the fitted effect of surface reaction.
7.2 Copper Converter Validation
The charges followed in the plant trials were simulated using the model. The
validity of the model can be tested by comparing predicted temperatures and
compositions.
The temperature variation for the three charges are given in Figures 7.4-7.6.
Although there are only a small number of measured temperatures, it can be seen that the
model predictions are reasonable in the slag blows. The matte and slag temperatures
predicted in the copper blows are generally low, but the blister copper temperature fits
the measured temperatures well.
128
1700
1600
1500
LU
a: 1400
D
I
a:
LU 1300
0
LU
I-
1200
1100
1000
0 100 200 300 400 500
TIME (mm)
Figure 7.4 Comparison of measured and predicted copper converter temperatures
charge 586, February, 1994.
1600
1500
LU 1400
D
UJ
a 1300
LU
I-
1200
1100
0 100 200 300 400 500
TIME (mm)
129
7.2.2 Slag Composition
1600
1550
1500
Ui
a:
D
1450
a:
Ui
a
LU
IU 1400
1350
1300
0 100 200 300 400 500
TIME (mm)
A comparison of the measured and predicted slag compositions are given in
Tables Vil-ifi VII-V, and Figure 7.7 shows a comparison of the measured and predicted
-
slag iron and silica contents. The iron contents of the slags are predicted well for charges
586 and 595, but not as well for charge 588. Tn most cases, the amount of silica in the
slag is overpredicted. There are two factors which contribute to this overprediction: the
model includes all inert materials with the silica and a large, but unknown, quantity of
flux is lost as the converter begins blowing after a flux addition. This latter reason will
also explain some of the discrepancies in the iron assays.
The amount of copper in the slags is underpredicted in almost every case. The
exceptions being in charge 595, following the addition of copper slag to the converter. In
130
one of these slags the copper content is overpredicted, while in the other it is very close to
the measured value. Zinc in slags is generally overpredicted, while lead is usually
overpredicted for the slags early in the charge, and underpredicted for later slags. The
arsenic content of the slags is underpredicted for charges 586 and 588, but is quite close
for charge 595, for which more accurate assays were available.
Slag Fe Cu Zn Pb 2
Si0 As
1 Model 45.4 2.81 4.62 .55 27.9 .02
Assay 41.6 7.13 3.97 0.7 17.6 .04
2 Model 40.0 0.85 4.55 0.18 38.0 .010
Assay 39.2 6.46 3.89 .73 22.0 .04
3 Model 38.7 0.78 4.29 0.16 39.5 .01
Assay 37.4 6.13 4.00 1.28 22.8 .04
Table Vil-ifi Comparison of model predicted slag compositions with assays,
(weight percent), #1 converter charge 586, Feb., 1994.
Slag Fe Cu Zn Pb 2
Si0 As
[ 1 Model 40.9 3.41 6.18 1.54 29.8 .0252
L_________ Assay 45.1 5.35 4.51 .67 21.8 .05
2 Model 49.7 2.19 5.38 .372 21.2 .021
Assay 36.5 7.04 3.82 .95 23.2 .05
Table Vll-IV Comparison of model predicted slag compositions with assays,
131
Slag Fe Cu Zn Pb 2
Si0 As Sb Bi
1 Model 36.9 13.9 4.19 1.41 26.3 .0241
Assay 39.8 8.1 3.93 0.8 18.8 .015
2 Model 39.5 12.6 4.61 1.27 23.8 .0218 .0019 .0002
Assay 38.3 12.4 3.80 0.7 17.8 .022 .0058 .0007
3 Model 44.1 6.44 3.72 0.645 26.2 .0113
Assay 38.2 4.16 4.38 1.45 25.5 .012
4 Model 48.7 2.43 3.68 0.239 24.9 .0044 .0014 .0003
Assay 40.6 3.52_- 4.44 2.06 24.3 .016 .0057 .0002
Table Vll-V Comparison of model predicted slag compositions with assays,
60
I
Z 40
uJ
-
C.)
Lu
0
I
z
(!3
ij 30- A
A
A
Lu
IR0N
A A SILICA
20 -
10 I
10 20 30 40 50
MEASURED (WEIGHT PERCENT)
copper converter slags, charges 586, 588, and 595, Feb. 1994.
132
7.2.3 Matte Composition
Matte and blister copper compositions are compared in Tables Vil-VI Vil-VIll,
-
and Figure 7.8 shows a comparison of the measured and predicted iron and copper
contents of all sampled mattes. The tables and the figure show that the predicted iron,
copper and sulphur in the matte are close to the measured values, up until the formation
of white metal. The one sample of metal taken during the copper blow of charge 586
(sample 4, Table Vil-VI) has a much higher copper content and correspondingly lower
sulphur content than is predicted by the model, this sample is not included in Figure 7.8.
This is most likely explained by entrainment of blister copper in the matte. The predicted
compositions of three mattes reported in the tables, one in Table Vil-Vil and two in
Table Vil-Vifi, are actually a combination of matte and slag in the correct proportions to
give the assayed silica content of the mattes. Even with this correction, however, the
model predictions are not good. Some later mattes in charge 595 also had a relatively
high silica content, (see Table IV-TV), but the model predicted silica contents close to the
assayed values so no correction was made.
Zinc is predicted reasonably well for charges 586 and 588, but is consistently
underpredicted for charge 595. The lead content of the mattes is overpredicted for almost
every sample. This, combined with the underprediction of lead content in the slags,
indicates that there is more oxidation of lead from the matte, particularly at higher matte
grades. Matte arsenic contents are predicted well for all charges, and the antimony and
bismuth predictions for charge 595 are also reasonable, with the exception of the bismuth
in sample 9 which is too high.
133
Matte Fe Cu Zn Pb S As
1 Model 6.24 68.6 1.1 2.21 19.3 .032
Assay 4.1 70.9 .83 2.89 20.2 .03
2 Model 4.18 71.4 .69 2.38 19.0 .031
Assay 3.09 71.0 .59 2.63 21.6 .02
3 Model 1.13 74.9 .093 3.24 18.1 .033
Assay 1.1 74.7 .3 .65 19.8 .01
4 Model .62 73.9 .125 4.38 17.7 .045
Assay .49 90.1 .13 .23 5.55 .04
Blister Model - 99.707 .1449 .145 1 - .0020
Assay - 99.04 .002 1 .0072 - .0073
Table Vil-VI Comparison of model predicted matte and blister copper
compositions with assays, (weight percent), #1 converter charge 586, Feb., 1994.
__Matte Fe Cu Zn Pb S As
1 Model* 22.7 40.2 1.41 3.0 12.3 .0351
Assay 38.6 23.2 4.82 .47 7.7 .03
2 Model 4.03 71.5 .42 1.21 18.9 .0365
Assay 2.87 70.3 .66 .51 20.8 .03
3 Model 1.11 73.9 .19 1.11 18.3 .0346
Assay 1.43 74.0 .28 .4 19.7 .02
Blister Model - 99.68 .1729 .1731 - .0006
Assay - 97.89 .0044 .0072 - .0096
Table Vu-Vu Comparison of model predicted matte and blister copper
compositions with assays, (weight percent), #1 converter charge 588, Feb., 1994.
Asterisk indicates combined matte and slag to bring the matte silica content up to assayed
value.
134
Matte Fe Cu Zn Pb S As Sb Bi
1 Model* 17.1 52.2 1.81 1.38 16.8 .0248
Assay 23.3 37.3 2.75 1.00 15.1 .022
2 Model* 18.4 49.3 1.9 1.43 14.8 .0221
Assay 25.6 31.2 2.95 .8 11.1 .019
3 Model 9.29 62.0 .973 1.5 18.2 .0202 .0026 .0016
Assay 11.8 57.1 1.6 1.17 17.9 .014 .0028 .0013
4 Model 10.9 60.8 .747 1.56 18.4 .0188
Assay 14.5 49.8 1.83 1.01 17.1 .02
5 Model 10.3 62.0 .451 1.62 18.4 .0147
Assay 9.01 58.4 1.31 1.13 18.4 .014
6 Model 10.6 62.1 .292 1.7 18.9 .0156 .0021 .0014
Assay 7.43 63.2 1.33 1.21 20.1 .018 .0022 .0014
7 Model 12.0 60.9 .395 1.7 19.5 .0172
Assay 8.89 58.5 1.48 1.18 20.0 .016
8 Model 10.7 62.6 .22 1.69 19.4 .0171
Assay 8.45 59.0 1.45 1.32 21.2 .015
9 Model 8.2 65.6 .0658 1.79 19.2 .0167 .0022 .0015
Assay 7.87 62.7 1.3 1.15 20.3 .015 .0019 .0002
10 Model 6.28 68.1 .172 1.84 19.3 .0182
Assay 4.15 65.7 .75 .89 19.9 .012
11 Model 2.59 72.5 .0315 1.98 18.7 .0175
Assay 4.39 62.8 .82 .73 17.3 .01
Table Vil-Vill Comparison of model predicted matte compositions with assays,
(weight percent), #1 converter charge 595, Feb., 1994. Asterisk indicates combined
matte and slag to bring the matte silica content up to assayed value.
135
7.3 Nickel Converter Validation
a. 15
I
z
w
5 10 15
b.
70
2
uJ
II 65
uJ
I
I
0
ij 60
45
45 50 55 60 65 70 75
Figure 7.8 Comparison of measured and predicted a. iron and b. copper contents in
copper converter mattes, charges 586, 588, and 595, Feb. 1994.
7.3 Nickel Converter Validation
As with the copper converter, there is phase composition and temperature data
available for the nickel converter which may be compared to the model predictions. In
this case, however, there is considerably more temperature data available, but the
136
compositions are less accurate.
A comparison of the measured and predicted bath temperatures are given in
Figures 7.9-7.12. The measured temperatures were obtained using a two colour
pyrometer mounted in the hood and aimed at the bath surface, so in most cases should
give the slag temperature. However, the figures contain both the predicted matte and slag
temperatures, because, at the beginning of a blow, there is usually only a thin layer of
slag present so, depending on where the pyrometer is aimed, the measured temperature
may be matte rather than slag.
It can be seen from the figures that the temperature fit is quite good, especially
considering the lack of accurate weights of the materials charged to and skimmed from
the converter. In most cases, the largest disparity between the measured and predicted
temperatures are at the beginning of the charge. This is most likely caused by the
unknown quantity of mush remaining in the converter from the previous charge.
Generally, the mush is a very high silica slag with a large amount of entrained
Bessemer matte. It usually provides all the silica for the first blow of the following
charge, but its composition, weight, and temperature are all unknown. It is interesting to
note that in a number of cases the matte temperature is close at the beginning of the blow,
and the slag temperature is close at the end of the blow. This suggests that at some point
during the blow, the slag thickness becomes sufficient to completely cover the bath
surface, including the spout. There is often an abrupt change in the slope of the measured
temperatures, and this coincides with the change from matte temperature to slag
temperature. This is particularly evident at the beginning of charge 106 and in the second
blow of charge 108.
137
1600
1550
Ui
1500
D
I
ct
Ui
0.
LU 1450
I-
1400
1350
0 100 200 300 400 500 600 700 800
TIME (miii)
Figure 7.9 Comparison of model predicted matte and slag temperatures with plant
data, #3 converter charge 105, May 1988.
1550
1600
Ui
a
1450
LU
I-
1400
1350
100 200 300 400
TIME (mm)
138
1550
1500
w
D
1450
w
0
w
I-
1400
1350
0 100 200 300 400 500 600 700
TIME (mm)
1550
1500
Lii
D
I
1450
Lii
a
w
I
1400
1350
0 100 200 300 400 500
TIME (mm)
139
A comparison of measured and predicted slag compositions are given in
Tables Vil-IX VII-XII, and Figure 7.13 shows a comparison of the measured and
-
predicted iron and silica contents of the slags. Of the minor elements, only lead and zinc
are included in the tables, because the measured concentrations of arsenic, antimony, and
bismuth were below the lower threshold of the assay technique. Also, the Si0
includes
2
the other inert materials, such as alumina and lime. In all charges the Si0
values
2
predicted are close to the measured, as are the iron contents up until the miss blow; the
penultimate blow, before which furnace matte is not added. After this point the predicted
iron content is considerably lower than the measured value and the nickel and cobalt
contents are considerably higher. There are a number of possible reasons for this,
including insufficient iron being added to the model, the model predicting more reaction
than is actually occurring, and the value of liquid-phase diffusivity of iron being too low.
The model generally underpredicts the amount of copper, nickel, and cobalt in the
early slags. This discrepancy, for the most part, can be explained by the entrainment of
matte in the slag, which is not accounted for in the model. Tables IV-Vffl IV-XI-
indicate that there is a relatively large amount of sulphur in the early slags, which
indicates a correspondingly large amount of entrainment. The amounts of lead and zinc
in the slag are predicted fairly well, but the zinc predictions are high for the last slags.
The reason for this is most likely for the same as for the increased nickel and cobalt.
140
Slag Fe Ni Cu Co 0 Pb Zn
2
Si0
1 Model 54.5 .58 .37 .35 21.0 .052 .061 22.7
Assay 51.1 .97 .57 .59 22.2 .042 .055 24.4
2 Model 52.4 .24 .09 .05 19.8 .021 .061 26.9
Assay 51.7 .77 .48 .53 17.6 .035 .057 28.6
3 Model 49.3 .3 .08 .04 18.7 .021 .05 31.1
Assay 50.6 1.02 .49 .6 16.3 .041 .055 31.0
4 Model 47.5 .29 .09 .04 16.3 .025 .15 35.0
Assay 49.7 .9 .44 .67 14.7 .05 .052 33.6
5 Model 33.6 10.7 .08 5.23 17.0 .022 .54 32.3
Assay 48.6 3.39 1.43 1.14 15.3 .059 .047 30.1
6 Model 21.0 17.4 .11 3.12 13.6 .032 .26 43.8
Assay 44.6 3.35 1.07 1.55 15.5 .078 .04 34.0
Table Vil-IX Comparison of model predicted slag compositions with assays taken
at the end of the blow, (weight percent), #3 converter charge 105, May 1988.
2
Si0
1 Model 49.0 .82 .64 .51 18.7 .071 .052 29.9
Assay 49.8 2.28 1.1 .79 17.6 .049 .054 28.4
2 Model 51.1 .78 .59 .46 19.7 .064 .052 26.9
Assay 51.1 2.6 .86 1.37 13.6 .061 .044 30.5
3 Model 47.2 1.76 1.62 2.69 19.3 .017 .286 26.2
Assay 55.6 1.17 .71 .51 17.4 .036 .079 24.6
4 Model 25.9 21.1 2.33 2.13 16.4 .014 .153 30.7
Assay 46.0 3.95 1.23 1.56 16.7 .0833 .0418 30.56
Table Vll-X Comparison of model predicted slag compositions with assays taken
141
2
Si0
1 Model 55.5 .84 .32 .22 20.8 .041 .044 21.9
Assay 55.2 1.39 .75 .54 16.2 .033 .061 25.9
2 Model 51.9 .83 .42 .06 19.5 .014 .04 25.8
Assay 52.6 .99 .54 .60 16.3 .035 .051 29.0
3 Model 49.5 .88 .45 .038 18.7 .01 .036 28.7
Assay 48.6 4.37 1.72 .75 15.0 .038 .044 29.6
4 Model 46.4 .61 .29 3.45 18.7 .011 .29 29.2
Assay 48.0 3.46 1.32 .78 15.3 .042 .047 31.1
5 Model 30.5 12.1 .47 3.93 16.0 .014 .15 35.1
Assay 42.7 4.79 1.85 1.09 14.3 .064 .036 35.3
6 Model 22.6 21.9 .33 2.35 15.1 .015 .096 36.2
Assay 39.3 6.0 2.22 1.36 13.9 .067 .033 37.2
Table VII-XI Comparison of model predicted slag compositions with assays taken
2
Si0
1 Model 56.4 1.56 .47 .46 21.8 .033 .057 18.5
Assay 50.4 2.27 .95 .66 15.9 .046 .05 26.5
2 Model 51.4 .73 .33 .654 19.4 .011 .046 27.4
Assay 49.2 1.54 .63 .78 15.2 .054 .047 32.6
3 Model 37.5 7.85 .16 2.87 17.1 .013 .095 33.9
Assay 46.8 2.82 .86 1.31 14.8 .064 .043 33.4
Table Vll-XII Comparison of model predicted slag compositions with assays
taken at the end of the blow, (weight percent), #3 converter charge 108, May 1988.
142
60
I
Z 50
w
C-)
cc
w
0
I
C3
i:i 40
w
I
0
0
w
cc
0
20
20 30 40 50 60

nickel converter slags, #3 converter, charges 105, 106, 107, and 108, May 1988.
A comparison of predicted and assayed matte compositions are given in
Tables VII-XIll Vll-XVI, and a comparison of measured and predicted iron, nickel, and
-
copper contents of all matte samples is given in Figure 7.14. The tables and the figure
indicate that the model predictions are relatively close for the major elements, although
the relative amounts of nickel and copper do not always correspond. This will be due to
uncertainties in the feed compositions. Of the minor elements, zinc is generally predicted
well, but lead and arsenic are consistently overpredicted. This could be the result of
uncertainties in the diffusion coefficients, or an underprediction of the matte/slag
interfacial area.
143
Matte Fe Ni Cu Co 0 S Pb Zn As
1 Model 16.2 38.2 14.6 1.61 1.52 27.3 .1 .016 .02
Assay 16.9 38.8 13.8 1.60 3.54 25.2 .08 .012 .02
2 Model 9.76 43.9 15.9 1.82 .88 26.9 .52 .005 .049
Assay 11.4 42.5 15.4 1.45 3.97 24.9 .071 .004 .022
F Model .82 50.8 22.4 .15 .29 24.1 .7 .001 .137
Assay .792 48.3 23.5 .949 3.34 22.4 .0625 .003 .025
Table VII-XIII Comparison of model predicted matte compositions with assays,
(weight percent), #3 converter charge 105, May 1988.
_Matte Fe Ni Cu Co 0 S Pb Zn As
1 Model 9.89 41.9 20.9 1.37 .715 24.35 .082 .011 .044
Assay 9.83 42.5 18.4 1.27 3.64 24.1 .069 - .017
2 Model 2.42 48.1 24.1 .919 .834 22.3 1.1 .001 .044
Assay 5.79 46.8 21.7 1.03 1.91 22.5 .085 - .017
F Model .8 50.7 27.6 .28 .28 21.1 .686 .0002 .133
Assay .96 51.4 24.1 .79 .83 21.8 .058 - .023
Table VII-XIV Comparison of model predicted matte compositions with assays,
1 Model 16.4 37.7 14.6 1.33 1.72 27.5 .39 .007 .02
Assay 14.6 42.8 14.7 1.53 .66 25.5 .085 .004 .02
F Model .78 50.2 22.8 .134 .293 24.1 .4 .0004 .33
Assay 1.17 51.7 21.9 1.10 .8 23.0 .063 - .035
Table VII-XV Comparison of model predicted matte compositions with assays,
144
1 Model 12.0 41.9 13.7 1.58 1.02 27.1 .19 .01 .041
Assay 12.5 45.5 14.8 1.53 .09 25.5 .0916 .005 .0263
2 Model 8.02 45.3 14.4 1.78 .796 27.0 .89 .003 .061
Assay 12.4 44.9 14.9 1.39 .71 24.5 .0813 .0074 .0243
F Model 1.15 50.7 18.7 .366 .431 25.1 1.38 .0001 .105
Assay 1.10 55.6 19.5 1.05 - 23.0 .061 - .033
Table VII-XVI Comparison of model predicted matte compositions with assays,
60
60- A A
I
z
w A
C) A
40-
w
a A
I-.
(5
w 30
x
-
0
w -
20 -
x-
0
w _
IRON
a:
a. 4__ A NICKEL
10 X COPPER
-
0 w_______ I I
0 10 20 30 40 50 60
Figure 7.14 Comparison of measured and predicted iron, nickel and copper
contents in nickel converter mattes, #3 converter, charges 105, 106, 107, and 108, May
1988.
145
7.4.1 Phase Compositions
7.4 Discussion
The overall compositions of the condensed phases are generally predicted well for
both the copper and nickel converters, with some errors in the minor element
compositions. There are a number of possible sources for these errors, including
problems with the activity coefficients, diffusivities, interfacial areas, and assayed
compositions. Certain assumptions made in the modelling may also add to the errors.
7.4.1.1 Error in assays
Errors in assayed compositions are a particular problem in the nickel converter
analysis, because of the assay technique used. This point is best illustrated by comparing
two sets of assays for the same material. These are available for slag samples obtained
from charge 110 during the plant trials at Copper Cliff. Table VII-XVII shows a
comparison of assay results for the major components obtained using the standard ICP
technique, by which all other assays of the nickel converter samples were obtained, with
wet assay techniques. It is evident that there are some large differences between the
values, so the model predicted values are, for the most part, within the accuracy of the
assays.
146
Slag Assay technique Cu Ni Co Fe 2

Si0
1 ICP 1.34 3.10 0.718 54.2 21.9
wet 0.9 2.3 0.74 52.1 22.7
2 ICP 0.54 1.1 0.586 55.4 23.8
wet 0.53 1.32 0.62 50.9 24.4
3 ICP 0.673 1.58 0.712 53.4 25.6
wet 0.59 1.58 0.75 50.1 25.9
4 ICP 0.784 2.12 0.839 51.6 27.8
wet 1.41 4.33 0.95 45.5 29.0
5 ICP 0.911 2.99 1.37 48.7 29.6
wet 0.92 3.23 1.6 45.8 28.7
Table VII-XVII Comparison of slag assays obtained using ICP and wet assay
techniques.
7.4.1.2 Sulphur in slag
Neglecting the presence of sulphur in the slag will have some effect on the
predicted slag compositions. The sulphur content of the slags will be mainly due to matte
entrainment, because the slags were skimmed while in contact with a high grade matte
and so should have a dissolved sulphur content under 0.9%.89 There are two main
mechanisms by which matte entrainment may occur; emulsification of matte in slag and
splashing from the spout. The former mechanism is not usually reported in physical
modelling studies, but has been reported in one experimental system,

209 and is found in
top blowing and combined blowing systems.

21 This suggests that the majority of

210
entrained matte is produced by splashing from the spout, that is, matte which is either
carried out of the spout by its own momentum, or ejected from the spout by collapsing
bubb1es. The extent of this will vary considerably with the injection conditions, and the
residence time of the matte in the slag will also depend on the slag viscosity. Thus, a
147
single value of a suspension index as used by Nagamori and Mackey for the Noranda
reactor will not be valid for this system. While it may be possible to produce a formula
for suspension indices to give a better fit between the predicted and assayed slag
compositions, it would not be particularly meaningful considering the other inaccuracies
involved in the plant trials.
7.4.1.3 Oxygen in matte
For the modelling it was assumed that all of the oxygen in the matte was in the form
of Fe
, however, it is probable that there is also some FeO present. The equilibrium
4
0
3
mole fraction of FeO in matte may be obtained from the reaction
1 ...[7.3]
3FeO+O = Fe
2 4
0
3
The oxygen potential of the matte may be obtained from the magnetite formation
reaction, and the activity coefficient of FeO in matte is given by

2
YFeO = exp{
J (5.1 + 6.2 logX + 6.41 (1ogX )
2
+ 2.8(logXcus)3)}
The resulting variation of Fe

4 and FeO with time, calculated by the model for charge
0
3
586, are given in Figure 7.15. While the mole fraction of FeO is as high as 50% of the
magnetite mole fraction, the relative proportions of iron and oxygen present as FeO will
be considerably less. The effect of including FeO will be to increase the iron content in
the matte slightly.
148
0.035
0.03
0.025
z
0
0.02
0.015
0
0.01
0.005
0 100 200 300 400 500

TIME (mm)
Figure 7.15 Calculated variation of mole fractions of Fe

4 and FeO in matte.
0
3
7.4.1.4 Minor element distribution
The magnitude of the errors in the assays, along with the uncertainties inherent in
industrial scale tests raises some questions regarding the validity of any analysis of minor
element behaviour. However, for the purpose of the analysis of the copper converter,
precise values are not as important as overall distributions. If the model predicts the
measured distributions correctly, then the transport mechanisms assumed are likely to be
correct. If this is the case, then the model should still predict the effects of changes in
operation on the minor element distribution correctly.
Figure 7.16 shows a comparison of the measured and model predicted distributions
of lead, zinc and arsenic in the copper converter. From the figure it can be seen that the
model predicts the distribution of zinc and arsenic quite well. The amount of lead
reporting to the matte/blister copper is also predicted well, but the lead distribution
between the slag and gas is not close. The most likely cause of this is the behaviour of
lead at the gas/liquid interface. The model assumes that it vapourizes, in a manner
149
similar to arsenic, while it appears from the distributions that at least part of the lead
reaching the interface is oxidized and reports to the slag. The comparisons of predicted
and assayed slag compositions suggest that the majority of this oxidation takes place
towards the end of a charge. The free energies of formation of lead and copper oxides are
very close over the temperature range seen in converters, so it is likely that some of the
lead will oxidize towards the end of the slag blows and during the copper blow.
A comparison of the measured and predicted antimony and bismuth distributions
for charge 595 is given in Figure 7.17. This shows that the model can predict these
distributions well, particularly the proportion reporting to the matte. The difference
between the predicted and actual antimony in the slag indicates that some oxidation may
be occurring.
The predicted minor element distributions in the nickel converter are not as close as
for the copper converter. Figure 7.18 shows that, while the arsenic distribution is
predicted reasonably, the amount of lead and zinc reporting to the slag is underpredicted.
The most likely explanation for this is that the activity coefficients of the minor elements
used in the model are for copper mattes, and may be considerably different for nickel
mattes.
150
_____ ______________
100
Pb Zn As
e x
80
MEASURED +
586
588
A595
w
C/) +
< 60
PREDICTED
0 x586
+588
i595
40
0
0
w
+
o
- A
20
0 -I
SLAG MATTE GAS SLAG MATTE GAS SLAG MATTE GAS
with measured values, copper converter charges 586, 588, and 595, Fun Flon, February
1994. Solid lines indicate commercially observed range.
31
151
100
MEASURED +
Sb Bi
80
PREDICTED
w XSb Bi
(I)
I
60
0

I
(D
z
I
o 40
x
x
20 -
+
0 I
SLAG MATTE GAS
Figure 7.17 Comparison of model predicted antimony and bismuth distributions

with measured values, copper converter charge 595, Fun Flon, February 1994.
152
7.4.2 Copper Blow
100
Pb MEASURED As
0 105
107
108
80
PREDICTED
x 105
Iii + 107
(I)
.. 108
:i: +
0 60
0
I
z x
I
a::
0
a 40
w
cr
+ x
A *

20
x
+
+
-I. -I.
0
SLAG MATTE GAS SLAG MATTE GAS SLAG MATTE GAS
with measured values, nickel converter charges 105, 107, and 108, Copper Cliff, May
1988.
7.4.2 Copper Blow
Overall, the model is able to predict the bath temperature reasonably well for both
the copper and nickel converters, although the measured matte and slag temperatures
during the copper blow are suspect. Towards the end of the copper blow it is probable
that the small amounts of matte and slag remaining are well mixed, increasing the extent
of matte-slag reaction. Since the slag at this stage is highly oxidized, the increased
reaction will reduce the sulphur content of the matte significantly.
153
7.4.2 Copper Blow
To determine the reaction products of the matte-slag reaction, the most stable
species can be found from a predominance area diagram. Figure 7.19 shows
predominance area diagrams for the iron-copper-sulphur-oxygen system at 1300 K and
1500 K. These are equilibrium diagrams which assume an ideal solution, but should give
a good idea of which species will be produced by the reaction. It is interesting to note
that Cu
0 is not stable at either temperature, with the oxidized copper being in a copper
2
ferrite form. In fact, the formation of the ferrite considerably reduces the range of
stability of copper metal at lower temperatures. The composition of the copper slags
indicates that their oxygen potential is higher than 0.05, so the product of the matte-slag
reaction is most likely to be 2

0.Fe
Cu
.
3
0
This suggests that the main reaction between the matte and the slag at this stage is
likely to be
S
2
Cu + 4=2
O
3
4Fe 0.Fe
Cu
3
0 + lOFeO + SO
2
This reaction will reduce both the oxygen and sulphur potentials of the mixture, and will
continue until one of these values drops below a level at which the copper ferrite is no
longer stable. Whether or not any reaction occurs beyond this point will depend on the
sulphur potential of the system. The presence of the ferromagnetic copper ferrite also
explains the high values measured for magnetite content in the copper slags, since there is
insufficient iron present to form the amount of magnetite measured. Its presence has also
been found in accretions formed during the copper blow of a test converter.
211
The formation of a matte-slag emulsion will also have a stabilizing effect on the
temperature of the two phases. During the majority of the copper blow, the predicted
slag temperature is very low due to a combination of the radiation losses and absence of a
reaction with the gas. In the actual converter it is probable that the radiation losses would
154
7.4.2 Copper Blow
-2
-4
a:
D
-6 (1)
U)
Lii
a:
-8 0
-J
-10
a-
-12
:i:
a-
-14
U)
(!3
- 0
-j
-18
-20
-20 -18 -16 -14 -12 -10 -8 -6 -4 -2 0
LOG(OXYGEN PARTIAL PRESSURE)
0
-2
-4 ii;
a:
-6 U)
(I)
w
a:
-8 a-
-J
-10
a-
-12
a-
-14
U)
-IQ
0
-j
-18
-20
-20 -18 -16 -14 -12 -10 -8 -6 -4 -2 0
LOG(OXYGEN PARTIAL PRESSURE)
Figure 7.19 Predominance area diagrams for the iron-copper-sulphur-oxygen

system; a. 1300 K, b. 1500 K. Dashed lines indicate partial pressure of sulphur dioxide.
155
7.4.2 Copper Blow
be from the emulsion rather than just the slag. Also, the presence of the slag within the
matte would allow some gas-slag contact and, hence, reaction. The increased matte-slag
reaction will also produce extra heat which is not included in the model.
156
8.1 Gas Flow Model
8 MODEL PREDICTIONS AND DISCUSSION

8.1 Gas Flow Model
The predictions of the gas flow section of the model are of interest by themselves,
and so are considered separately here. The following discussion will consider a single
bubbling event, and only follow the gas phase. However, the results of this portion of the
model will be useful in discussing the predictions of the complete model.
The model predicted gas temperature is shown in Figure 8.1, for the standard
conditions shown in Table V-I. All reaction heat is assumed to report to the liquid phase,
so before detachment the gas temperature is controlled by a balance between the heat
input from the bath and the cooling effect of the injected gas. Initially, the heat input
predominates, but as the bubble grows the two factors become more equal. This causes
the gas temperature to level out below the bath temperature. In some cases, as the bubble
grows the gas temperature starts to decrease until breakup occurs and the temperature
starts to rise again. This effect is small, and does not show on Figure 8.1. After
detachment at 0.107 s, the gas temperature rises quickly to the bath temperature, and the
primary bubble exits the bath 0.113 s after detachment.
A comparison of the temperatures predicted by the present model with those
35 shows that the changes made in the initial assumptions

predicted by Ashman et al.
cause considerable differences. The present model predicts a much faster temperature
increase, due both to the bubble shape and the heat-transfer coefficient. An elliptical
bubble has more surface area than a spherical one of equal volume (Figure 8.2) giving an
increased area available for heat transfer. Also, Ashman et al.

35 used a constant
1 which is considerably lower than that predicted

heat-transfer coefficient of 290 Wm
K
2
by equation 6.97, and does not account for variations with bubble size. Bubble breakup
157
8.1 Gas Flow Model
1400
w
1200
Lu
E:
1000
400
0 0.05 0.1 0.15 0.2
TIME (s)
Figure 8.1 Variation of primary bubble temperature with time for injection
conditions given in Table V-I.
during growth will also affect the gas temperature, because larger bubbles heat up more
slowly than small bubbles. Figure 8.3 shows that four bubbles break off from the
primary bubble before detachment, and that the primary bubble breaks up one more time
before leaving the bath. At the bath surface the primary bubble has a volume of 0.05 m
3
and represents approximately 34% of the gas input during a single bubbling event.
Figure 8.4 shows that there is an initial rapid decrease in the total bubble oxygen
content during bubble growth, but the rate of decrease drops off before detachment. This
is caused by the reduced mass-transfer rate due to increased bubble size. After
detachment the oxygen content of the gas decreases more rapidly, but does not reach the
initial rate, since there is no longer enhancement of the mass-transfer rate due to the gas
injection. After 0.22 s the oxygen partial pressure becomes essentially constant. This is
because only small bubbles are remaining in the bath. These bubbles contain a relatively
158
8.1 Gas Flow Model
small proportion of the total gas and, due to their size, already have a low oxygen partial
pressure. Therefore, the amount of oxygen removed from these bubbles is insignificant
when compared to the oxygen which has already exited the bath in the larger bubbles. It
is evident that a relatively large proportion of the oxygen is not reacted (11.5%), which
appears to contradict the high oxygen efficiencies reported for converters. If the tuyere
submergence is increased to 0.7 m the partial pressure of oxygen remaining decreases
slightly to 0.015 atm. This value is approximately half of that reported by Rodoiff and
98 for a copper converter with a tuyere submergence of 0.76 m and a Froude number
Rana
of 10.92. This difference may be related to the amount of slag present in the actual
converter, or could indicate that the gas-phase mass-transfer coefficient used in the model
is too high.
The effect of changing the tuyere diameter on the primary bubble temperature is
small, with the main difference being caused by slightly different detachment times.
However, decreasing the tuyere diameter causes a significant increase in oxygen use, as
shown in Figure 8.5. This is caused by the increased gas velocity which increases the
rate of mass transfer during bubble formation. A similar trend was reported by Rodolff
and Rana
98 and is also predicted for changes in flow rate. The effect of tuyere diameter
on the extent of bubble break up during growth is large. Figure 8.6 shows that increasing
the tuyere diameter significantly increases the number of times the bubble breaks up.
This is caused by the reduced gas velocity which reduces the equilibrium bubble size as
explained in Section 5.3. The reduced slope of the oxygen in gas curves after
detachment at lower tuyere diameters (Figure 8.5) is a result of the reduced break up as
well as the lower oxygen concentration. Mass-transfer of oxygen from the bubbles is
reduced both by the larger bubble size and the lower driving force.
159
8.1 Gas Flow Model
2.5
1.5
0 0.2 0.4 0.6 0.8

ECCENTRICITY
Figure 8.2 Effect of ellipse eccentricity on surface area at constant volume, shaded
area indicates range of eccentricity predicted by the model.
0.07
0.06
0.05
0.04
D
0.03
-
0.02
0.01
0
0 0.05 0.1 0.15 0.2
TIME (s)
Figure 8.3 Variation of primary bubble volume with time for injection conditions
given in Table V-I.
160
8.1 Gas Flow Model
0.2
z
UI
>-
><
0 0.15
0
UI
D
Cl)
C)
UI
a: 0.1
a-
-J
I-
a:
0.
Ui 0.05
a:
UI
0
0 0.1 0.2 0.3 0.4
TIME (s)
Figure 8.4 Variation of average oxygen partial pressure with tuyere submergence
for injection conditions given in Table V-I.
0.2
z
UI
(
>-
x
0 0.15
U
0
UI
a:
D
Cl)
Cl)
UI
a: 0.1
a-
-J
I
a:
a-
UI
(3 0.05
a:
UI
>
0
0 0.1 0.2 0.3
TIME (s)
Figure 8.5 Variation of average oxygen partial pressure with tuyere diameter, all
other conditions given in Table V-I.
161
8.1 Gas Flow Model
0.08
0.07
0.06
w
D
_i 0.05
0
>
w
0.04
D
>. 0.03
0.02
a-
0.01
0
0 0.05 0.1 0.15 0.2
TIME (s)
Figure 8.6 Variation of primary bubble volume with tuyere diameter, all other
Increasing the oxygen content of the gas results in an increase in the oxygen partial
pressure of the off gas. However, Figure 8.7 shows that the actual amount of oxygen
reacted is also increased. There is also a corresponding increase in the partial pressure of
sulphur dioxide in the off gas. These are the result of a higher oxygen mass-transfer rate
caused by the higher partial pressure of oxygen in the bulk of the gas.
The model predicts a slightly higher oxygen utilization in the copper blow than in
the slag blow, which was also found by Rodoiff and Rana.
98 However, the lowest value
of oxygen remaining was attained for the case of blowing directly into slag. The primary
reasons for this can be seen from Figures 8.8 and 8.9. When blowing into slag the gas
temperature rises slowly, due to the low slag thermal conductivity, Also, the higher
162
8.1 Gas Flow Model
viscosity of the slag reduces the bubble velocity, allowing increased bubble breakup.
These result in the formation of a larger number of smaller bubbles, which increases the
amount of mass-transfer, as well as the total bubble residence time.
The effect of tuyere interaction can be approximated by artificially doubling the gas
input to the bubble, while keeping the gas flow rate through the tuyere constant. The
model predicts that tuyere interaction will have a small effect on the primary bubble
temperature. The initial heating rate is lower than with no interaction, due to the larger
bubble size, but the bath temperature is still attained shortly after detachment. The
oxygen utilization, however, is reduced considerably, as shown in Figure 8.10. This
effect is also caused by the increased bubble size during the formation stage,
(Figure 8.11) which reduces the mass-transfer rate. This indicates that heat and mass
transfer effects are not exactly analogous. Figure 8.11 also shows that even with the
increased bubble size, the primary bubble still breaks up only four times before
detachment. This effect is again caused by the increased growth velocity which allows a
larger bubble to form.
163
8.1 Gas Flow Model
0.25
Cl)
w 0.2
-J
0
0
Ui
I 0.15
0
a:
z
Ui
0 0.1
>-
><
0
0.05
0
0 0.05 0.1 0.15 0.2 0.25 0.3
TIME (s)
Figure 8.7 Variation of total oxygen reacted with inlet gas oxygen content, all other
1600
1400
1200
Ui
1000
Ui
0
Ui
F-
600
400
200
0 0.05 0.1 0.15 0.2 0.25 0.3 0.35
TIME (s)
Figure 8.8 Variation of primary bubble temperature with bath material, all other
164
8.1 Gas Flow Model
25
20
15
Ui
-J
LU
LU
D
LU
10
0
0 0.05 0.1 0.15 0.2 0.25 0.3 0.35
TIME (s)
Figure 8.9 Variation of number of bubbles formed with bath material, all other
0.2
z
Ui
ci,
0 0.15
U
0
Ui
cc
D
CO
CO
Ui
cc 0.1
0
-J
I-
cc
Ui
0.05
Ui
>
0
0 0.05 0.1 0.15 0.2 0.25 0.3
TIME (s)
Figure 8.10 Effect of tuyere interaction on average oxygen partial pressure all ,
other conditions given in Table V-I.
165
8.2.1 Introduction
0.15
COS
w
D
0
>
w
-J
XI
D
m
>_
0.05
ci
0
0 0.05 0.1 0.15 0.2
TIME (s)
Figure 8.11 Effect of tuyere interaction on primary bubble volume, all other
8.2 Converter Model
8.2.1 Introduction
For the purposes of this discussion, a single copper converter charge is used to test
the effects of variations of model and operating parameters. While none of the industrial
charges followed were normal, charge 586 can be considered as representing the final
two slag blows and the copper blow of a normal charge, because the transferred matte
was an initial charge to the converter. As in a previous work, the discussion will focus on
the matte temperature and iron content,

98 but other properties will be discussed as
required.
166
8.2.2 Copper Converter Charge
The predicted matte temperature from charge 586 is shown in Figure 8.12.
Although there are some similarities between the temperature variations of copper and
nickel converter charges, the temperature of the copper charge does not follow the regular
pattern exhibited by the nickel converter temperature (Figure 4.1). While the figure does
show the same rapid temperature increase during blowing, there is not the initial
temperature decrease that is seen in the nickel converter. This difference is caused by the
fluxing methods used. At Copper Cliff, the flux is added through the mouth of the
converter while it is blowing, usually over the first ten to fifteen minutes of each blow.
At Flin Ron, flux is added from ladles as it is needed throughout the charge. Thus,
instead of one initial, large temperature drop, there are a few small drops throughout the
blow (marked F on Figure 8.12). The weight of flux required is also much lower at Flin
Flon, due to the smaller converter size and the higher initial matte grade.
The matte temperature falls only slightly during idle periods. This is caused by the
insulating effect of the slag, which prevents radiation losses. The only heat losses from
the matte are through the walls and to the slag, both of which are small. Some probable
causes of the low predicted temperatures during the slag blow have been discussed in
Section 7.4, but a further examination is required. A temperature decrease, as predicted
during the copper blow, can be caused by material additions or reduced heat inputs to the
bath. Since extra material is only added at the times indicated in Figure 8.12, it follows
that the heat input has been reduced. There are two further reasons for this decline in
heat production. In the copper blow, copper suiphide is being oxidized rather than iron
sulphide, so the principle reaction is
167
1600
1500
1400
D
1300
1200
1100
0 100 200 300 400 500
TIME (mm)
Figure 8.12 Predicted matte temperature, charge 586. F-flux addition, M-matte
addition, I-idle period start, I*idle period end, S-slag skimmed, Sc-scrap added,
C-copper blow start.
S + O = 2Cu + SO
2
Cu 2 AHR = 190.4kJ moF
whereas, in the slag blows, the reaction is
=FeO+SO
FeS+O
2 AIIR =308.9kJmoF
1
Thus the heat produced per mole of oxygen reacting is reduced by 38 percent.
The second reason can be seen in Figure 8.13. This shows that the oxygen use is
considerably lower in the copper blow than in the slag blows. It is important to note that
the graph shows oxygen use, not oxygen efficiency. For the purpose of this discussion,
oxygen use is defined as
168
oxygen use =
(I 1 ----s
,
x 100% =
(I 1
pp
2 2
x 100%
...[8.3]
L 2 i
The nitrogen partial pressure terms in equation 8.3 are to account for the change in total
moles of gas present due to reaction, the total moles of nitrogen being unchanged. There
are two main reasons for the reduction in oxygen use during the copper blow; low slag
volume and reduced tuyere submergence. The rapid heating rate of the slag during slag
blows (Figures 7.7-7.9) indicates that there is a considerable amount of slag oxidation
occurring, and this accounts for a large proportion of the total heat input to the converter.
However, slag is routinely skimmed just prior to the copper blow, to reduce copper
losses. This leaves approximately five tonnes of slag, which is barely sufficient to cover
the surface of the bath. If the slag remains as a separate phase when a spout is formed
there will be very little contact between the gas and the slag, but it is likely that the slag is
completely emulsified in the matte. Under either of these conditions there will be little
reaction of the slag with the gas, causing a reduction in the total heat generated.
Also, as copper is produced, the total volume of material in the converter is
reduced. The resulting reduction in tuyere submergence is shown in Figure 8.14. For
example, if 120 tomies of white metal is reacted to produce blister copper, there is a 45
percent reduction in volume, which results in a 0.5 m decrease in tuyere submergence.
At Flin Ron the tuyere submergence can not be increased during the copper blow due to
the requirement for almost continuous tuyere punching, which can only be carried out at
a specific converter position. Figure 8.4 shows that decreasing the tuyere submergence
reduces oxygen use, leading to the considerably lower heat generation. This point is
emphasized in Figure 8.15, which shows that there is a definite relationship between
tuyere submergence and oxygen use. However, the scatter in Figure 8.15 indicates that
169
100
90
80
w
Cl)
D
z
w
(3
70
0
60
50
0 100 200 300 400 500
TIME (mm)
Figure 8.13 Predicted variation of oxygen use with time.
other variables also contribute to determining the total oxygen use.
0.9
0.8
E 0.7
w
0
z
w
(3 0.6
Iii
m
D 0.5
Cl)
w
w
>- 0.4
D
I
0.3
0.2
0 100 200 300 400 500
TIME (mm)
Figure 8.14 Predicted variation of tuyere submergence (including spout) with time.
170
8.2.3 Sensitivity Analysis
100
H NH
90

N N
H N
Lii H
U,
z
Lii
0
70
0
60
IlN
I I
50
0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
TUVERE SUBMERGENCE (m)
Figure 8.15 Predicted variation of oxygen use with tuyere submergence (including
spout), charge 586, Feb. 1994.
In the development and operation of the model there are a number of parameters for
which accurate values or equations are not available. It is important to determine the
effects of these parameters on the model predictions. This process can identify areas
where further work is required to obtain better values, and may also aid in understanding
what is happening in the converter. Table V1ll-I gives the parameters analyzed and the
range of values used.
A shorter time step should increase the accuracy of the model predictions, but
increases the total running time. Figure 8.16 shows that reducing the time step to one
minute only has a small effect on the matte temperature and iron content. While running
time is not a serious problem for the model, the inaccuracies involved in the plant trials
171
Parameter low base high

Time step (mm) 1 2 -
Gas flow calculation frequency (time steps) 1 5 -
Initial bath temperature (K) 1350 1400 1450

Hood temperature (K) 623 823 1023
Slag emissivity .5 .7
Liquid-phase diffusivity base/lO eq. 6.92 basexl0
Gas-phase diffusivity base-l0% eq. 6.93 base+10%
Gas-phase mass-transfer coefficient base-10% eq. 6.94 base+l0%
Matte ladle size (tonnes) 14.4 16 17.6
Water in flux (%) 2.5 5 7.5
Spout gas fraction multiplier

-J 1.1 1.5
. . .
Table Vu-I Parameters tested in the sensitivity analysis.
and other parameters are sufficiently large to make the difference essentially
insignificant. The most time consuming section of the model is the gas flow calculation.
To avoid long running times this calculation was only carried out every five time steps
(10 minutes), or immediately following an idle period. This could represent a significant
source of error for the model, particularly when the temperature is changing rapidly.
However, Figure 8.17 shows that the difference between carrying out the gas flow
calculation every time step and every five time steps is small.
172
1600
1500
w
a:
D
a: 1400
w
0
1300
1200
0
0 100 200 300 400 500
TIME (ml,,)
Figure 8.16 Effect of model time step on the predicted variation of matte
temperature and iron content (weight percent) with time.
The initial bath temperature is not known, but can be estimated based on measured
matte temperatures at the end of a slag blow. This basis is used because the initial matte
for charge 586 was transferred from another converter, rather than from the reverberatory
furnace. Figure 8.18 shows that an increase in the initial temperature only has an effect
on the first blow temperature and iron content, with the difference at later stages of the
173
1600
1500
w
D 1400
1300
w
I
w 1200
I
1100
1000
6
I
5
4
z
0 3
0
0 100 200 300 400 500
TIME (mm)
Figure 8.17 Effect of gas flow calculation frequency on the predicted variation of
matte temperature and iron content (weight percent) with time.
charge being negligible. The temperature difference is reduced throughout the first blow,
with the difference in the higher initial temperature case being reduced faster due to
higher heat losses. The difference in iron content is primarily due to the temperature
dependance of the magnetite activity coefficient. A lower temperature increases the
activity coefficient and so reduces the iron content. This can be seen from the variation
of matte oxygen content given in Figure 8.19.
174
1600
1500
LU 1400
D
LU
0 1300
LU
I
LU
I
1200
1100
0.08
0.07
0.06
LU
I
0.05
0.04
z
0
0.03
0.02
0.01
0
0 100 200 300 400 500
TIME (mm)
Figure 8.18 Effect of initial bath temperature on the predicted variation of matte
Variations in the hood temperature and slag emissivity have only a small effect on
the matte temperature, and even less on the matte iron content. The slag emissivity,
175
1.5
0.5
0
0 100 200 300 400 500
TIME (mm)
Figure 8.19 Effect of initial bath temperature on the predicted variation of matte
oxygen content (weight percent) with time.
however, has a relatively large effect on the slag temperature (Figure 8.20). An increase
in the hood temperature has a larger effect on slag temperature than a decrease, but it is
small compared to the effect of emissivity. Neither of these parameters has a significant
effect on the slag composition.
The liquid-phase diffusivities are calculated from a theoretical equation and, as
shown in Section 6.5.3.1, may be too low. However, if the system is under gas-phase
diffusion mass-transfer control, diffusivities in the liquid should not have a significant
effect on the model predictions. Figure 8.21, however, indicates that there is an effect,
both to the matte temperature and iron content. The effect of an increase in diffusivity is
caused by an increased amount of zinc reacting. Figure 8.22 shows that with the higher
diffusivity the zinc removal from the matte is very rapid. This is because the zinc
concentration is low enough to be under liquid-phase diffusion control, so an increase in
176
1700
1600
1500
UI
0 1400
D
1300
UI
F-
1200
1100
1000
0 100 200 300 400 500
TIME (mm)
Figure 8.20 Effect of slag emissivity on the predicted variation of slag temperature
with time.
the diffusivity allows more zinc to reach the gas/liquid interface. All of the zinc arriving
at the interface should react, because ZnO is thermodynamically more stable than FeO.
This reduces the amount of iron oxidized and, to a lesser extent, the heat generated.
The increased iron content of the matte during the slag blows caused by a decrease
in liquid-phase diffusivity indicates that the reaction of iron has also become controlled
by diffusion in the liquid. That is, there is insufficient iron reaching the gas/liquid
interface to react with all the oxygen. This should not affect the amount of oxygen
reacting, so there is an increase in the amount of copper reacting. This causes the copper
phase to be formed at an early stage of the process. This reduced iron removal and
increased copper removal combine to produce the large increase in matte iron content
seen in Figure 8.21, particularly at the end of the first blow. After this point the effect of
an increase in diffusivity is reduced, due to the lower levels of zinc in the matte. The
177
1800
1700
1600
1500
1400
I
w
1300
1200
1100
0 100 200 300 400 500

TIME (mm)
Figure 8.21 Effect of liquid-phase diffusivity on the predicted variation of matte

rapid increase in matte temperature seen at the end of the low diffusivity case in
Figure 8.21 corresponds to an increase in the matte magnetite content. The heat
generated to produce the magnetite combined with the small amount of matte remaining
cause the very rapid temperature increase. The effect of changing the liquid-phase
178
diffusivity on the oxygen content of the slag (Figure 8.23) reveals another interesting
point. Reducing the diffusivity has a considerable effect on the slag oxygen content,
again indicating that the oxidation reaction in the slag is under liquid-phase diffusion
control. However, there is no other component in the slag to react, so there is a reduction
in the overall oxygen use (Figure 8.24). Increasing the liquid-phase diffusivity had no
effect on the oxygen content of the slag over the first ten minutes of the first blow.
However, after this time there is an increase in the slag oxygen content, indicating that in
the base case there is a change in the reaction controlling mechanism from gas-phase
diffusion to liquid-phase diffusion. This same pattern is repeated in the second blow, and
the decreased oxygen use is evident in Figure 8.24. This figure also shows that
increasing the liquid-phase diffusivity has a slight effect on the oxygen use, suggesting
that the gas/slag reaction is under mixed control throughout the charge.
1.5
0.5
0
0 100 200 300 400 500
TIME (mm)
Figure 8.22 Effect of liquid-phase diffusivity on the predicted variation of matte
zinc content (weight percent) with time.
179
20
19
18
17
(3
a) 16
z
z
w
(3 15
>-
><
0
14
13
12
0 100 200 300 400 500
TIME (mm)
Figure 8.23 Effect of liquid-phase diffusivity on the predicted variation of slag
oxygen content (weight percent) with time.
100
90
80
w
C,)
D
z 70
LLI
(3
>-
x
60
50
40
0 100 200 300 400 500
TIME (mm)
Figure 8.24 Effect of liquid-phase diffusivity on the predicted variation of oxygen

use with time.
180
The effects of changing the gas-phase diffusivity and the gas-phase mass-transfer
coefficient are essentially the same. Figure 8.25 shows that increasing the gas-phase
mass-transfer coefficient increases the matte temperature and reduces its iron content.
These results are what would be expected for a system controlled by gas-phase diffusion.
The increased mass-transfer coefficient results in more oxygen reaching the gas/liquid
interface, allowing more reaction to occur which produces more heat and removes more
iron from the matte. The magnitude of the effect on iron content increases with time
during the slag blows. In the initial stages of the first blow, the difference between the
cases is too small to show in Figure 8.25, but becomes evident 46 minutes into the blow.
At the beginning of the copper blow the case with the higher gas-phase mass-transfer
coefficient has a higher matte iron content than the other cases. This is caused by the
reaction between the gas and iron suiphide coming under liquid-phase control at a higher
iron content in the matte, which is caused by the increased amount of oxygen reaching
the reaction site. It is important to note that the model is very sensitive to the gas-phase
diffusivity, with a very high value causing extreme temperatures. This is indicative of a
process under gas phase mass transfer control. However, since the model appears to
predict the converter temperatures reasonably well, it can be argued that either the value
used is close to the actual, or the gas surface area is under or over predicted and
compensates for an error in the mass transfer coefficient.
The effect of increasing the gas-phase mass-transfer coefficient on the slag,
however, is very small. Figure 8.26 shows that the oxygen content of the slag is changed
very little by the increase, again indicating that the reaction in the slag is controlled by
liquid-phase diffusion. The fact that a reduction in the gas-phase mass-transfer
coefficient does reduce the slag oxygen content again suggests that the gas/slag reaction
181
1600
w
Ix
D 1500
w
1400
w
I
1300
1200
1100
0 100 200 300 400 500

TIME (mm)
Figure 8.25 Effect of gas-phase mass-transfer coefficient on the predicted variation
of matte temperature and iron content (weight percent) with time.
in the base case is under mixed gas-phase and liquid-phase mass-transfer control.
182
19
18
17
C!,
16
-J
Cl)
z
z 15
w
>-
x
0 14
13
12
0 100 200 300 400 500
TIME (mm)
Figure 8.26 Effect of gas-phase mass-transfer coefficient on the predicted variation

of slag oxygen content (weight percent) with time.
The amount of weight added in a ladle can be calculated approximately based on
the ladle volume. However, the shape of the ladle is such that a large proportion of the
weight is in the top section. This means that a small difference in the height to which it is
filled will have a large effect on the actual amount of matte added. Generally, the weight
of matte added will average out to calculated amount. Figure 8.27 shows that an increase
in the amount of matte added results in an increase in matte temperature and iron content,
although the iron content is not increased by as much as may be expected. The increase
in matte temperature is caused by the increased tuyere submergence due to the greater
total volume of matte in the converter. The increased amount of reaction occurring
because of the extra tuyere submergence is the reason for the lower than expected iron
content; more iron is being added, but more is also being removed.
183
The flux used at Fun Hon is sand taken from a local sand pit and brought to the
smelter by truck. The water content of the flux is quite variable, and will often depend on
the weather conditions. A variation of the water content of the flux, however, has no
noticeable effect on the matte, and only a slight effect on the slag temperature and silica
content. The effect of the assumed spout gas fraction-plume gas fraction ratio is also
small. This value only affects the calculated spout height, and so represents a small
portion of the total tuyere submergence. As such, an increase in the ratio does increase
the matte temperature slightly due to the slightly increased extent of reaction. This also
reduces the iron content of the matte by a small amount. The size of these variations is
insignificant when compared to the other uncertainties in the system.
184
1600
1500
w
1400
cc
Lii
1300
1200
1100
0
0 100 200 300 400 500
TIME (mm)
Figure 8.27 Effect of weight of matte in a ladle on the predicted variation of matte
185
There are very few operating parameters which can be changed on a copper
converter. This is probably one of the reasons it has continued, relatively unchanged, for
so long: a copper converter will run by itself with very little control and only intermittent
operator intervention required. In the past, there have been suggestions made of ways to
improve operation, and these almost always relate to gas injection. Unfortunately,
changes to the gas injection can seriously affect the overall heat balance. To determine
the effect of changes on the length of a charge, the time taken to produce 72 tonnes of
blister copper will be compared. This approach is required because the actual end point
of a charge depends on the extent of the matte/slag reaction during the copper blow,
which can not be predicted by the model. The particular weight chosen is the amount
predicted to have been produced after 400 minutes of the base charge.
8.2.4.1 Gas flow rate
Perhaps the most direct method to improve converter operation is to increase the
gas flow rate. This should shorten the total charge time without altering the heat balance,
but is limited by the onset of slopping and causes increased splash from the spout. The
model predicts that increasing the gas flow rate does increase the rate of iron removal
from the bath, but Figure 8.28 also shows that it will reduce the matte temperature. This
effect is caused by a decrease in the total oxygen use. The amount of heat obtained from
the reaction per unit volume of gas is decreased, while the heat lost per unit volume of
gas is unchanged. Since the overall heat balance of the converter is essentially controlled
by these two factors, decreasing the heat input without changing the heat removed will
result in a reduction in the heat accumulated in the matte. Thus, even though there is
more oxygen reacting, the matte temperature is reduced by the increased heat lost to the
186
gas.
1600
1500
w 1400
a:
D
1300
0
1200
1100
1000
0
0 100 200 300 400 500
TIME (mm)
Figure 8.28 Effect of gas flow rate on the predicted variation of matte temperature
and iron content (weight percent) with time.
187
8.2.4.2 Oxygen enrichment
Oxygen enrichment of the injected gas is used in some installations to reduce
charge times and allow an increased amount of cold charge addition. The extra scrap
burning capability is available because the use of oxygen enrichment affects the heat
balance. The effects of oxygen enrichment can be analyzed in two different ways;
keeping the total moles of oxygen added constant by reducing the number of tuyeres
used, or increasing the total amount of oxygen added. The latter is what is carried out in
industry, but the former may prove interesting.
Figure 8.29 shows the results of using oxygen enrichment while keeping the total
oxygen input constant using a reduced number of tuyeres. The matte temperature is
considerably higher than without oxygen enrichment, but the iron content of the matte is
also increased. However, the oxygen content of the matte is higher, indicating that the
increased iron content is mainly caused by the reduction of the magnetite activity
coefficient in the matte at the higher temperatures. If the weight percent of iron as
magnetite is subtracted from the total iron content, (Figure 8.30) it can be seen that there
is a small improvement in iron removal with increasing oxygen enrichment, which results
in a two minute reduction in charge time at 30% oxygen in the gas. This is the result of
an increase in mass-transfer rate within the bubble, which is just sufficient to overcome
the reduction in the number of tuyeres used.
If the total oxygen input to the converter is increased the temperature rise is even
larger than in the previous case. The increased mass-transfer rate through the regular
number of tuyeres increases the iron removal, and, hence, the temperature. Figure 8.31
shows that, even with the large increase in temperature, which will increase the matte
magnetite content, the total iron in the matte is reduced. This figure also shows that the
188
case with 30% oxygen in the gas took about 80 minutes less to complete the charge. The
improvement was only 10 minutes for oxygen enrichment to 25%, and in both cases is
due to the increased rate of mass-transfer to the gas/liquid interface. This effect is
enhanced by higher temperatures, which is the explanation for the large differences in
charge times. The higher temperatures are also the cause of the high iron content in the
matte during the copper blow, as explained in Section 8.2.2.
189
1800
- 1700
w
1600
1500
Lii 1400
1300
1200
1100
0
0 100 200 300 400 500
TIME (mm)
Figure 8.29 Effect of gas oxygen content, with total oxygen input constant, on the
predicted variation of matte temperature and iron content (weight percent) with time.
190
0
0 100 200 300 400 500
TIME (mm)
Figure 8.30 Effect of gas oxygen content, with total oxygen input constant, on the
predicted variation of matte iron content with iron as magnetite removed (weight percent)
with time.
To further analyze the effects of oxygen enrichment, the model can be modified to
keep the temperatures of each phase constant. This allows higher gas oxygen contents to
be studied, while removing the complications introduced by the high temperatures
normally produced. For this analysis the total oxygen input to the converter was also
kept constant, with the number of tuyeres used being reduced in proportion to the
increases in oxygen content. This technique significantly reduces the total gas/liquid
interfacial area, but the liquid-phase kinetics around a single tuyere are not altered.
Figure 8.32 shows the predicted effect of increasing the oxygen enrichment on the
matte iron content. It is evident that there is an initial increase in iron removal rate with
increasing oxygen enrichment, but at some point between oxygen contents of 35% and
42% the rate of iron removal begins to decrease, and at high oxygen enrichments the
191
2200
2000
1800
w
ft
D
1600
ft
w
0
1400
I
1200
1000
0
0 100 200 300 400 500
TIME (mm)
Figure 8.31 Effect of gas oxygen content, with increased oxygen input, on the
predicted variation of matte temperature and iron content (weight percent) with time.
192
matte iron content remains higher than the base case (21% oxygen). A possible
explanation for this is that the reduced interfacial area may be reducing the total amount
of reaction occurring. However, Figure 8.33 shows that, while the total oxygen use is
reduced during the slag blows at higher oxygen enrichments, the magnitude of the
reduction is not large, indicating that the overall amount of reaction occurring in the
matte has increased. This suggests that at some point during the charge the reaction of
iron is coming under liquid-phase mass-transfer control, and copper suiphide is also
reacting.
Figure 8.34 shows that there is some reaction with copper sulphide occurring during
the slag blows. The amount of copper suiphide reacting, however, is not sufficient to
account for all of the increase in iron content. The effect of the oxygen enrichment on the
weight of blister copper produced is shown in Figure 8.35. This figure shows that there is
copper production throughout the charge, even when there is no direct reaction of the gas
with copper sulphide. The prediction that there is copper produced early in the charge,
even for the base case, is unexpected, and can be explained by the sulphur potential of the
matte. Figure 8.36 shows that the sulphur potential of the matte varies between iO
7 and
10.6.8, but is not significantly affected by increasing the oxygen enrichment. It can be
seen from a potential area diagram of the system (Figure 7.13) that these values are close
to the boundary between copper and copper sulphide, which is why some copper is being
produced. This effect will be greater at higher temperatures, where the copper phase is
stable at higher sulphur potentials.
The reduction in charge time achieved with oxygen enrichment to 84% at 1400 K is
28 minutes. However, the total amount of copper produced after the full 450 minutes is
193
increased by 20 tonnes, while the weight and copper content of the matte remaining is
significantly reduced. This is not likely to occur in the actual process due to the
matte/slag reaction, which forms the copper slag.
This analysis indicates that, in general, increasing the oxygen content of the gas will
reduce the overall charge time by a combination of mechanisms. Increasing the total
amount of oxygen supplied to the bath allows more reaction to take place, and increases
the rate of mass-transfer to the gas-liquid interface, however, the percent of the oxygen
used is reduced. At very high oxygen enrichments, or with the use of tonnage oxygen,
rates of liquid-phase mass-transport begin to become important, and some reaction with
copper sulphide is possible at lower matte grades. However, at the oxygen enrichment
levels usable under the temperature constraints of the converter, the reduction in charge
time achieved is relatively small, but could be improved if the temperature is controlled
using high grade scrap. It should be noted that, while this increased copper oxidation
would be advantageous in copper converting, it represents a limit to oxygen enrichment
in the nickel converter. In nickel converting, this form of liquid-phase mass-transport
control would cause increased cobalt and nickel oxidation, and result in higher slag
losses.
194
10
0
0 100 200 300 400 500
TIME (mm)
Figure 8.32 Effect of gas oxygen content on the predicted variation of matte iron
content (weight percent) with time at 1400 K.
100
90
w 80
U)
D
z
w
0 70
0
60
50
40
0 100 200 300 400 500
TIME (mm)
Figure 8.33 Effect of gas oxygen content on the predicted variation of oxygen use
with time at 1400 K.
195
100
z 80
0
I
0
w
a: 60
-J
I
0
I.
LL
0 40
I
z
w
0
a:
w
0
20
0
0 100 200 300 400 500
TIME (mm)
Figure 8.34 Variation of the predicted amount of iron and copper suiphides
reacting, as a percentage of the total reaction in the matte, with time at 1400 K and 84%
oxygen in the injected gas.
120
100
80
Lii
z
z
0
b 60
F
w
40
20
0
0 100 200 300 400 500
TIME (mm)
Figure 8.35 Effect of gas oxygen content on the predicted variation of copper
produced with time at 1400 K.
196
-6.6
-6.7
-6.8
-6.9
-J
I.-_.-. -7
ZE
-7.1
-7.2
j_J 7.3
D
Cl)
-7.4
-7.5
-7.6
-7.7
0 100 200 300 400 500
TIME (ml,,)
Figure 8.36 Effect of gas oxygen content on the predicted variation of sulphur
potential with time at 1400 K.
8.2.4.3 Tuyere submergence and diameter
The tuyere submergence in a Peirce-Smith converter is usually limited both by the
design of the converter and by the requirement for tuyere punching. However, in a
system which is controlled by gas-phase mass-transfer, increasing the total contact area
between the gas and liquid-phases, by increasing the tuyere submergence, should
improve the overall process efficiency. Figure 8.37 shows that it does increase the
amount of reaction and, since there is no additional cooling, the matte temperature.
Increasing the tuyere submergence by 0.1 m reduces the time required to produce
72 tonnes of blister copper by 20 minutes, while a similar decrease in tuyere
submergence increases the time by 12 minutes. It should be noted that the tuyere
submergence varies throughout the charge (Figure 8.14), based on the volume of material
197
in the bath, so the base submergence can not be given as a number.
The use of a reduced tuyere diameter, to increase the velocity of the gas leaving the
tuyere, has been tested. This removes the need to punch the tuyeres, and reduce
tuyereline refractory wear. Figure 8.38 indicates that there is another advantage to using
smaller diameter tuyeres. The increased tuyere velocity produces a more elongated
bubble, and enhances mixing in the bubble during growth. Both of these lead to more
efficient mass-transfer during bubble growth, and an overall increase in the iron removal,
such that charge time is reduced by 18 minutes.
Both reducing the tuyere diameter and increasing the tuyere submergence improve
the kinetics of converting, so combining the two offers the possibility of making a
considerable improvement to the operation. There is, however, one possible drawback.
Figure 8.39 shows that, while the rapid decrease in iron is as desired, the increase in
matte temperature is considerable. If a reliable source of high grade scrap material is
available, then this may be an asset rather than a drawback, but if the scrap is not
available the increased temperatures may seriously degrade the refractory.
198
1700
1600
w 1500
1400
w
0
w
I 1300
LU
I
1200
1100
6
LU
I
5
z
z
0
3
0
0 100 200 300 400 500
TIME (mm)
Figure 8.37 Effect of tuyere submergence on the predicted variation of matte
199
1900
1800
1700
W 1600
cc
D
1500
cc
1400
w
I 1300
1200
1100
1000
0
0 100 200 300 400 500
TIME (mm)
Figure 8.38 Effect of tuyere diameter on the predicted variation of matte
200
1900
1800
g
w 1700
D
I 1600
Ui
0 1500
UI
I
1400
1300
1200
1100
0
0 100 200 300 400 500
TIME (mm)
Figure 8.39 Effect of a combined reduction in tuyere diameter and increase in
tuyere submergence on the predicted variation of matte temperature and iron content
(weight percent) with time.
201
8.2.4.4 Slag skimming procedure
Slag skimming is usually carried out at the end of each blow, before the addition of
matte. This results in a low initial slag cover, which increases throughout the blow. The
effect of altering this practice to provide either an increase or decrease in the slag
thickness during blowing is shown in Figure 8.40. In the low slag cover case, after the
initial skim at 38 minutes, slag is skimmed as soon as 12.5 toimes (one ladle) is present,
while in the high slag cover case, the base amount of slag skimmed is reduced by one
half. In all cases the slag cover in the copper blow is the same.
It is evident from Figure 8.40 that a low slag cover reduces the matte temperature.
This is primarily caused by a large reduction in the slag temperature due to the absence of
a gas/slag reaction, and the low thermal mass of the slag. The absence of the gas/slag
reaction can be clearly seen from the reduction in oxygen use shown in Figure 8.41. A
small part of this reduction is also caused by the lower temperatures, which reduce the
oxygen mass-transfer rate and, hence, the extent of the gas/matte reaction. This results in
a 12 minute increase in the charge time, and is the cause of the higher amount of iron in
matte during the slag blows.
202
.-. 1600
w
1500
I
1400
0
1300
1200
1100
1000
0
0 100 200 300 400 500
TUYERE SUBMERGENCE (m)
Figure 8.40 Effect of skimming procedure on the predicted variation of matte
203
8.2.5 Minor Element Removal
100
90
80
C,)
D
z
w
C!3
70
0
60
50
0 100 200 300 400 500
TIME (mm)
Figure 8.41 Effect of skimming procedure on the predicted variation of oxygen use
with time.
8.2.5.1 Introduction
The removal of minor elements from the matte is an important factor which must be
considered when operating variables are to be changed. The effects of changing the same
operating variables as in the previous section will be considered. For this purpose the
distribution of the minor elements between the phases will be considered, although there
are occasions when the actual predicted concentrations are required. In particular, if
changing a variable results in the formation of a greater amount of any particular phase
the percentage of the total input reporting to that phase may increase, even though the
actual concentrations within the phase are reduced.
204
For the purposes of calculating distributions, the copper slag is considered as being
a mixture of the remaining matte and slag at the end of the charge. In an actual converter
the two phases will be well mixed, and there will be a considerable reaction between
them, removing the majority of the sulphur from the matte. This reaction has not been
included in the model due to insufficient data concerning the mixing and reaction. This is
particularly important for lead and, to a lesser extent, zinc, as a relatively large proportion
of these are removed in the copper slag. For this analysis, distributions will be calculated
at a constant weight of blister produced. This provides a constant basis for the
comparisons.
8.2.5.2 Minor element behaviour in the base charge
While the minor element distributions give an overall indication of the minor
element behaviour, the variation of the minor element content of each phase with time
can give a better idea of what is actually happening. The discussion of distributions will
focus on the proportions of the minor elements reporting to the blister copper and the
dust. The base distributions to these phases are given in Table VIlI-Il
Element Distribution (%)

Blister Dust
Pb 3.93 36.7
Zn 3.61 9.90
As 2.28 61.5
Sb 0.568 40.1
Bi 1.20 37.7
Table VIlI-Il Predicted distribution of minor elements to the blister copper and
dust after 400 minutes of charge 586 (72 tonnes of blister copper produced).
205
Figures 8.42, 8.44, and 8.45 show the variation with time of the concentration of
minor elements in the blister copper, matte and slag respectively, while Figure 8.46
shows the variation of their partial pressures in the off gas. The concentrations of all of
the minor elements in the blister copper follow the same pattern. There is an initial rapid
increase in minor element content, caused by the large surface area to volume ratio of the
blister copper (Figure 8.43). The rate of change of minor element concentration in the
blister copper is directly proportional to this ratio, so it can be seen that at deeper depths
of blister copper the rate of change will be reduced. At higher volumes of copper the rate
of minor element transfer does not keep pace with the rate of copper production, causing
the levelling off of the curve in Figure 8.42. When the copper blow begins, the minor
element content in the blister copper begins to drop, because the rate of copper
production is considerably higher than the minor element mass-transfer rate. The sudden
increases in minor element content during the copper blow correspond to the addition of
scrap, which has a higher minor element content than the blister copper. Otherwise, the
minor element content decreases during the copper blow. However, this does not imply
that the minor elements are being transferred from the blister to the matte. In fact, the
total weight of the minor elements in the copper is increasing slightly, but not as quickly
as the total weight of copper. The magnitude of the effect of the cold charge addition is
related to the concentration of the particular minor element in the cold charge.
Concentrations of lead, zinc, and arsenic are relatively large, so the cold charge addition
has a larger effect on their concentrations. However, for antimony and bismuth, the
concentrations in the cold charge are not much higher than their concentrations in the
blister copper, so the effect is smaller.
206
a. 200 200
ci
ci
Ct
w 150 .4n
I.Jv
0 0
0 0
0 0
C) C)
100 100 Ct
F-
w
I
Cl) C/)
-J -J
50 50
U C)
w z
-j N
0 0
0 100 200 300 400 500
TIME (mm)
ci
h ci 30
It
w
0
0
0
C)
Ct 20
w
I
C/)
:i 15
z
z 10
0
a:
I
z
w
o 0
z 0 100 200 300 400 500
0
O TIME (mm)
Figure 8.42 Predicted variation of minor element concentrations in blister copper
with time, a. lead and zinc, b. arsenic, antimony, and bismuth.
207
2.3
2.2
2.1
1.9
1.8
1.7
1.6
0 0.1 0.2 0.3 0.4
DEPTH (m)
Figure 8.43 Variation of surface area-to-volume ratio of blister copper with depth.
The variation of the minor element content of the matte (Figure 8.44) shows that
arsenic, antimony, and bismuth follow the same basic pattern, while the lead and zinc
behave differently. Figure 8.44a shows that the zinc content in matte decreases during
blowing, with sudden increases when matte is added. The rate of the decrease of zinc
content becomes much smaller during the copper blow. The behaviour of the lead in
matte is the opposite of this. The lead content increases continuously throughout the
charge, except for the abrupt decreases caused by matte addition. The increase continues
throughout the copper blow, as lead is concentrated in the matte. The concentrations of
the other minor elements in the matte are relatively constant throughout the slag blows
(Figure 8.44b), but increase slightly during the copper blow. This concentrating effect in
the matte occurs because the rate of copper removal from the matte is considerably faster
than the rate of minor element removal.
208
The behaviour of the minor elements in the slag is shown in Figure 8.45. This
shows that all of the minor elements except for zinc behave in a similar manner;
decreasing during the slag blows and remaining relatively constant during the copper
blow. The zinc behaviour is quite different. During the slag blows the zinc content tends
to increase, but is subject to rapid drops when flux is added. The increasing zinc content
is caused by the reaction of ZnS in the matte with oxygen to form ZnO. The extent of
this reaction becomes very small during the copper blow, when the high concentration of
zinc oxide in the slag causes a fairly rapid rate of mass-transfer to the matte/slag
interface. The oxide reacts with sulphur at the interface, and the zinc is returned to the
matte. This causes the reduction of the zinc content during the copper blow.
The variations of the minor element partial pressures in the gas, shown in
Figure 8.46, all follow the same basic pattern; increasing during the slag blows and
decreasing during the copper blow. The extent of the decrease at the beginning of the
copper blow is related to the difference in activity coefficients between matte and white
metal. Thus, arsenic and antimony partial pressures drop significantly, while the partial
pressures of lead, zinc, and bismuth are only slightly decreased. The increase in partial
pressure during the slag blows is caused by the increasing bath temperatures, and
likewise, the decrease during the copper blow is caused by the decreasing temperatures.
209
__
4 1.4
a.
.3.5 1.2
UI
2.5 0.8
0.6
z z
0.4
UI
-J N
1 0.2
0.5 0
0 100 200 300 400 500
TIME (mm)
900
b.
800
F-
F
600
Z 500
400
300
1t 200
I
Z 100
Lu
00
Z 0 100 200 300 400 500
0
0 TIME (mm)
Figure 8.44 Predicted variation of minor element concentrations in matte with
time, a. lead and zinc, b. arsenic, antimony, and bismuth.
210
2 5
a.
A
+.c: o
1.5 0
CD 4
-J 1 -J
C,) Cl)
z 3.5z
0 0
LU 0.5 z
-J 3Ri
0
0 100 200 300 400
TIME (mm)
-5OO
b.
CD 400
-J
Cl)
300
z
0
200
F
z
LU 100
0
z
0
00
0 100 200 300 400 500
TIME (mm)
Figure 8.45 Predicted variation of minor element concentrations in slag with time,
a. lead and zinc, b. arsenic, antimony, and bismuth.
211
(/ -2
<
-
-10
0 100 200 300 400 500
TIME (mm)
-3
-4
-5 -f
C),
-6
z
Ui -7
-8
-9
_1
-10 I
-J
11
0
-J
-12
0 100 200 300 400 500
TIME (mm)
Figure 8.46 Predicted variation of minor element partial pressures in gas with
time, a. lead and zinc, b. arsenic, antimony, and bismuth.
212
8.2.5.3 Model predictions
8.2.5.3.1 Gas flow rate
Increasing the gas flow rate should increase the total gas/liquid interfacial area, as
well as the total gas throughput. Both of these factors should improve the removal
kinetics of the minor elements to the gas, and this is predicted by the model. Figure 8.47
shows that there is an increase in the distribution of all of the minor elements to the dust.
This is particularly evident for lead, the proportion of which reporting to the dust is
increased by 33%. The increase in arsenic, antimony, and bismuth in the low gas flow
rate case is unexpected, but can be explained by the increased time required to reach the
end point and the increased tuyere submergences due to the reduced iron removal rate.
These combine to increase the overall surface area available for mass-transfer. The
distribution of minor elements to the blister is not significantly affected by the gas flow
rate.
213
::-
a.
b.
61.55
::
61.45
d.
-10% BASE +10%
GAS FLOW RATE
Figure 8.47 Predicted variation of minor element distribution to the dust with gas
flow rate, a. lead b. zinc, c. arsenic, d. antimony, and e. bismuth.
8.2.5.3.2 Oxygen enrichment
Using oxygen enrichment, while keeping the total volume of oxygen constant, will
reduce the total gas flow rate, and so may be expected to reduce removal to the dust.
This effect is predicted by the model, as shown in Figure 8.48. There is also an increase
in the distribution to the slag by all materials except zinc. The reduction of zinc reporting
to the slag is caused by the reduced gas/liquid interfacial area. The increases in the other
minor elements in the slag are caused by the higher concentrations in the matte, which
214
increase the driving force for mass-transfer between the liquid phases. This effect is also
seen in the increased concentration of minor elements in the blister copper. In particular,
increasing the oxygen content to 30% causes the concentration of antimony in blister
copper to increase by 27%, while arsenic and bismuth are increased by 10%
(Figure 8.49). The differences in the magnitude of these increases is related to the
activity coefficients in the matte and copper.
If the total gas flow rate is not changed while oxygen enrichment is used there are
some significant differences. Figure 8.50 shows that there is an increase in the proportion
of minor elements reporting to the dust. The primary explanation for these differences is
the bath temperature. At higher gas oxygen contents the bath temperature is dramatically
increased, which increases the rate of mass-transfer to the gas/liquid interface. The
resulting increase in vapourization (Figure 8.51) more than makes up for the slight
decrease in off-gas volume caused by the increased oxygen content.
While there is a slight increase in the proportion of minor elements reporting to the
blister copper at 24% oxygen, Figure 8.52 shows that only the antimony concentration is
increased at 30% oxygen in the gas. The explanation of this is more complicated. At
24% oxygen enrichment the increase is caused by the higher mass-transfer rates at
increased temperatures and this is also the case for the antimony at 30% oxygen.
However, for the other minor elements the composition of the cold charge becomes
important.
215
a.
C.
61.2-
d.
::
40.1 -Sb
e. - Bi
37.65 -
37.55
21 25 30
GAS OXYGEN CONTENT (%)

oxygen content with constant total oxygen input, a. lead b. zinc, c. arsenic, d. antimony,
and e. bismuth.
216
a. Pb
3.96
3.92
b. Zn
3.64
3.62 -
3.6 -
2.5 As
2 2.4
2.3
d.
Sb
0.7
0.6-
1.32 Bi
e.
.
1.28 -
1.24 -
1.2 -
2530

Figure 8.49 Predicted variation of minor element distribution to the blister copper
with gas oxygen content with constant total oxygen input, a. lead b. zinc, c. arsenic,
d. antimony, and e. bismuth.
217
E
C.
. 61.4
d. 41.2
Sb
e.
37.5
21 25 30
oxygen content with increased total oxygen input, a. lead b. zinc, c. arsenic, d. antimony,
and e. bismuth.
218
-3
-4
/.-
LU
II
-5
D
U) L
r /
U)
w
U: -6
0
-J
I-
-7
U:
0
-8 GAS OXYGEN CONTENT (%)
0 21 (BASE)
0
-J
-9 24
30
-10
11
0 100 200 300 400 500
TIME (mm)
Figure 8.51 Effect of gas oxygen content with increased total oxygen input, on
predicted variation of arsenic partial pressure in the off gas with time.
At an oxygen enrichment of 30%, there are some significant differences in the
minor element behaviour in the blister copper, as shown in Figure 8.53. The increased
temperatures cause the arsenic content in the copper to rise more quickly, but there is a
rapid drop close to the end of the first blow. This is because essentially all of the iron
suiphide has been removed from the matte, causing the production of copper, as well as a
considerable drop in the arsenic activity coefficient. In this case the direction of
mass-transfer is reversed and, when combined with the initial small volume of copper
present and the production of additional copper, the effect is quite large. Following the
addition of matte, the arsenic content begins to increase again, until copper begins to be
produced. After this point the curve follows the same pattern as the base curve.
However, copper is produced faster at the higher oxygen content, so when the scrap is
added it has a smaller effect on the minor element concentrations, due to the larger total
219
C. 2.4 As
d.
0.56
2 25 30

with gas oxygen content with increased total oxygen input, a. lead b. zinc, c. arsenic,
d. antimony, and e. bismuth.
mass of copper present. Thus the arsenic concentration in the blister copper remains
lower at the higher oxygen enrichment. If the effect of the scrap is overestimated,
however, the final arsenic content of the blister copper in the oxygen enriched case may
actually be higher than the base case.
220
This is actually seen for the antimony, as shown in Figure 8.54. While the same
pattern is followed for the behaviour of the antimony concentration in the base charge,
there is considerably less antimony in the scrap. In this case, the increased initial
antimony content caused by the higher temperatures is not reduced to the level of the
base charge, and the scrap additions to the base charge do not bring its antimony content
above the oxygen enriched case. This emphasizes the importance of obtaining good
expressions for transport properties.
25
20
15
10
0
0 100 200 300 400 500
TIME (mm)
Figure 8.53 Effect of gas oxygen content, with increased total oxygen input, on the
predicted variation of arsenic content in blister copper with time.
If the model is run using oxygen enrichment, but assuming that the temperature is
constant, some interesting results are obtained. Increasing the oxygen content under
these conditions reduces the distribution of minor elements to the blister copper, as
shown in Figure 8.55. The lower concentrations are primarily caused by the increased
rate of copper production early in the charge (Figure 8.56). The increased amount of
221
20
15
IQ
S
1:
0
0 100 200 300 400 500
TIME (mm)
Figure 8.54 Effect of gas oxygen content, with increased total oxygen input, on the
predicted variation of antimony content in blister copper with time.
copper reduces the interfacial area to volume ratio, so while the mass-transfer rate is
essentially unchanged, the actual concentrations in the copper remain lower. The
increased weight of copper also reduces the effect of the cold charge addition as
explained above.
While increasing the oxygen enrichment to 42% causes a small decrease in the
proportions of arsenic, antimony, and bismuth reporting to the dust, Figure 8.57 shows
that increasing the oxygen content to 84% increases the proportions of all of the minor
elements reporting to the dust. This result is not expected, and requires some
explanation. The off gas volume, at 84% oxygen in the injected gas, will be reduced by
considerably more than a factor of four, so to increase the distribution to the dust, the
partial pressures of these minor elements must increase by even more. Figure 8.58 shows
that the arsenic partial pressure is increased at high oxygen contents, and remains
222
relatively high, even through the copper blow. Most of the increase in arsenic partial
pressure will be directly related to the reduced off-gas volume. It is important to note,
however, that the volume of gas injected through a single tuyere is unchanged by the
oxygen enrichment. This means that, for the bubble growth and early in the bubble rise,
the surface area available for mass-transfer per tuyere is only slightly reduced.
Therefore, there is little change in the initial mass-transfer of arsenic to the gas around a
single tuyere. As the oxygen is removed from the gas by reaction there is a concentrating
effect which causes the higher partial pressure.
This effect alone will not increase the total amount of minor elements removed to
the dust, so some other mechanism must be involved. The explanation of this can be seen
in Figure 8.59. This figure shows that, for the slag blows, there is a very slight increase
in the arsenic content of the matte at 84% oxygen in the gas. During the slag blows the
arsenic content of the matte drops quite quickly, but during the copper blow the removal
rate is very low. This is because the activity coefficients of the minor elements are much
lower in white metal, reducing the driving force for mass transfer. The composition
dependence of the activity coefficients in the matte is also the reason the matte arsenic
content in the case with a high gas oxygen content remains close to the base case during
the slag blows. The difference between the two cases occurs at the end of the second slag
blow. Throughout the charge, the mole fraction of copper suiphide is lower at the high
gas oxygen content, and this effectively prolongs the slag blow, allowing the increased
removal rate to continue for a longer time. This results in the lower final arsenic content
in the matte seen in Figure 8.59. The reason the effect is not seen for lead is that its
activity coefficient is not as sensitive to matte grade, so its mass-transfer rate is not
increased significantly over the base charge. It should be noted that the formation of
223
white metal is determined by the iron suiphide content of the matte. Theoretically, white
S, but it is actually a matte with a very low iron sulphide content. The
metal is Cu
2
presence of lead and zinc suiphides cause the white metal to have a Cu
S mole fraction
2
between 0.8 and 0.9.
224
a.
::
2.1
z
0
-
1.9 -
I
D
m 1.7-
1.5-
0
d. Sb
::
214284

with gas oxygen content with constant total oxygen input and temperature, a. lead b. zinc,
c. arsenic, d. antimony, and e. bismuth.
225
25
20
z Is
0
I
z
uJ 10
()
z
0
C-)
0
0 100 200 300 400 500
TIME (mm)
Figure 8.56 Effect of gas oxygen content, with constant total oxygen input, on the
predicted variation of arsenic content in blister copper with time at 1400 K.
226
a. 33-Pb
32.8 -
32.6-
32.4 -
32.2 -
32 -
b. Zn
16
14 -
12-
10 -
As
65
Q63-
D
61-
C)
d. Sb
41-
39-
Bi
e. 41
39
37
21 42 84

oxygen content with constant total oxygen input and temperature, a. lead b. zinc,
c. arsenic, d. antimony, and e. bismuth.
227
.4 GAS OXYGEN CONTENT (%)

_________ 21
84
2 -5
(U
2
(U
-6
.7
I I I I
-8
0 100 200 300 400 500
TIME (mm)
predicted variation of arsenic partial pressure in the off gas with time at 1400 K.
550 0.9
i
C
0
0.8
(a
500
w
a)
0
E
w
0.7
450 z
w
0
0.6
0.
-J
D
C)
400 Ui
0
0.5
C)
350 0.4
100 200 300 400 500
TIME (mm)
predicted variation of moles of arsenic and mole fraction of copper sulphide in matte with
time at 1400 K.
228
8.2.5.3.3 Tuyere submergence and diameter
The predicted distributions of the minor elements to the dust and copper for changes
in tuyere submergence are shown in Figures 8.60 and 8.61 respectively. Increasing the
tuyere submergence is predicted to increase the amount of minor elements reporting to
the dusts and reduce the amount of minor elements (with the exception of zinc) reporting
to the slag. The increased concentration in the dust is caused by an increase in the
gas/liquid interfacial area, which allows more vapourization to occur. The increased
interfacial area also increases the amount of zinc oxidized and, hence, the zinc content of
the slag.
During the copper blow the rate of removal of the minor elements from the matte is
considerably slower than the rate of copper fonnation. This causes them to be
concentrated in the matte remaining at the end of the charge, which forms the copper
slag. Figure 8.61 shows that the use of tuyere submergences less than the base value
has little effect on the lead and zinc reporting to the blister copper. However, the
distributions of all of the minor elements to the copper is reduced by an increase in the
tuyere submergence. Reducing the tuyere submergence also decreases the proportions of
arsenic, antimony, and bismuth in the blister. Figure 8.62 shows the variation of arsenic
concentration in the blister copper up to the point where 72 tonnes of copper have been
produced. Although the higher bath temperature causes a more rapid increase in the
arsenic content of the copper, the reduction in total concentration begins earlier, and the
rate of copper production is greater. The larger weight of copper present at scrap
additions reduces the effect of the added arsenic, so the arsenic content at deeper tuyere
submergences is lower throughout the copper blow. The reduced distribution to the
copper seen for arsenic, antimony, and bismuth is caused by the length of time between
229
the last scrap addition and the end point. Figure 8.62 shows that the increased time
between the addition of the scrap and the end point at the reduced tuyere submergence
allows the arsenic content of the blister copper to drop below the final arsenic content of
the base case, causing the reduced distribution. This indicates that scrap should not be
added close to the end of a charge.
The effect of reducing the tuyere diameter follows the same basic pattern as
increasing the tuyere submergence. The increased temperatures and gas/liquid interfacial
area tend to increase the removal of zinc to the slag and the other minor elements to the
dust. As might be expected, combining a high tuyere submergence with a low tuyere
diameter has the same effect as each of the separate changes. The overall effect,
however, is slightly larger, with a lower final concentration of minor elements in the
blister copper, and a higher percentage reporting to the dust.
230
a. Pb
b Zn
3.5 -
3-
2.5 -
c. - As
2.2-
z 2-
D
m 1.8 -
1 1.6 -
- Sb
0.56 -
0.54 -
0:::
- Bi
1.2 -
0.9
.BSE+.m
with tuyere submergence, a. lead b. zinc, c. arsenic, d. antimony, and e. bismuth.
231
a.
z 2-
F =
1.8-
ci:
1.6-
d.
-.lm BASE +.1m
tuyere submergence, a. lead b. zinc, c. arsenic, d. antimony, and e. bismuth.
232
30
25
E
cc
w 20
0
0
0
0
cc
w 15
I
Cl)
-J
z
0 10
z
w
C,)
cc
5
0
0 100 200 300 400 500
TIME (mm)
Figure 8.62 Effect of tuyere submergence on the predicted variation of arsenic
content in blister copper with time.
8.2.5.4 Summary
In general, factors which increase the extent of oxygen use or the total gas flow
through the bath will increase the minor element removal to the dust and reduce the
distribution to the blister copper. The same factors which have the greatest effect on
oxygen use, gas/liquid interfacial area, temperature, and, to a lesser extent, gas injection
velocity, also affect the rate of minor element transport to the gas. Low levels of oxygen
enrichment are detrimental to minor element removal, due to the lower gas volume
produced, but this may be overcome by the effect of temperature. Very high levels of
oxygen enrichment have a large effect on the distributions to the dust and blister copper,
increasing the former and decreasing the latter. These effects are directly related to the
process kinetics. The timing of scrap additions is also predicted to have a large effect on
233
8.2.6 Comparison with Previous Work
the amount of minor elements reporting to the blister copper. The scrap provides a large
proportion of the total amount of minor elements in the blister copper, but its effect can
be reduced by increasing the time between the final scrap addition and the end of the
charge.
8.2.6.1 Overall model
While the publications regarding most previous models do not contain sufficient
data to allow a reasonable comparison, a comparison may be made with the results of an
equilibrium model of the nickel 97

converter. In fact, the data obtained from the previous
study has been used in the verification of the present model, so there is a good basis for
comparison. The equilibrium model assumed that the two condensed phases were at the
same temperature, and that they were in equilibrium with the gas exiting the bath. An
overall oxygen efficiency of 95% was used.
A direct comparison of the temperatures and compositions predicted by both
models for the Copper Cliff nickel charges, shows that the predictive ability of the two
models is similar. The temperatures in the equilibrium model, however, did require some
fitting at the beginning of each charge to account for the shape of the temperature curve.
This fitting was carried out by assuming that the mush dissolved slowly and removed
heat continuously throughout the first part of the first blow. Fitting of this nature is not
required in the kinetic model, because the abrupt change in the slope of the measured
temperatures matched the crossover between matte and slag temperatures in most cases
(see Section 7.3.1). This also occurred in later blows, where the equilibrium model again
failed to match the lower initial temperatures.
234
The compositions predicted by both models are also comparable, and generally
within the error of the measurements. The equilibrium model is closer for slags at the
ends of the charges, but the kinetic model is better for most slags at other times. The
kinetic model is also better able to predict the Bessemer matte composition. In general,
however, both models are able to predict the measured temperatures and compositions to
within the accuracy of the measurements, although minor elements were not included in
the equilibrium model, so no comparison of them may be made.
It is in the predictions regarding operating parameters that the models differ. Both
models do predict the same trends for increases in oxygen enrichment and gas flow rate,
but such variables as tuyere submergence and tuyere diameter have no effect on the
equilibrium model. These are parameters which affect the process kinetics, so have no
bearing on the system if equilibrium is assumed. Perhaps the most important difference
between the two models is that, using the equilibrium model, it was determined that there
was little which could be done to improve the chemistry of the converter.
97 However, the
kinetic model indicates that there are some variables which may be altered to improve
converter kinetics.
8.2.6.2 Minor element distribution
Previous modelling work on minor element distribution has been limited to a
number of versions of a single model. These concentrate on determining the effects of
oxygen use and initial matte

2
6 6 In all cases it has also been assumed that
grade.
3
2 13
1
the three condensed phases were in equilibrium with each other and the gas. The
distribution of minor elements between phases was calculated using distribution
coefficients and the volatilization of minor elements was also based on equilibrium
235
considerations. It was assumed that the oxygen efficiency was 100%, with all of the
oxygen reacting with FeS until white metal was formed, at which point reaction with
S began. The models also assumed isothermal conditions.

2
Cu
The results of these models, for converting conditions, indicate that the amount of
minor element removal is almost entirely determined by the total volume of off gas
produced during smelting and/or converting. As such, increasing oxygen enrichment and
initial matte grade both reduce the amount of minor element removal to the dust. The
oxygen dependence of the distribution coefficients does suggest that there will be
increased slagging of minor elements at higher oxygen enrichments, but the extent of this
is much smaller than the reduction in volatilization. One of the papers did note that the
increase in temperature accompanying oxygen enrichment would counteract the reduced
gas volume.
213
The large differences in the basic assumptions between the previous models and the
present case make a comparison difficult. While some of the same trends are predicted in
both cases, in particular, the basic effect of total off gas volume and the effect of
increasing temperature, the effects caused by general kinetic considerations and
especially variations in matte composition due to kinetic effects, are completely
overlooked by the equilibrium models. With respect to the comparative validity of the
two models, the present case appears to able to calculate the minor element distributions
in a copper converter charge quite well, whereas Table VIll-ilI shows that the
volatilization models have some difficulties. While the present model does appear to
have difficulty predicting the bismuth distribution, this arises only during the copper
blow. Predictions up to the end of the slag blows are close to measured values. The
equilibrium model predictions of lead and arsenic are outside of the observed range, and
236
the distributions of antimony and bismuth to the gas are very close to the top of the range.
The fact that all of the predicted distributions to the gas, with the exception of zinc,
appear to be high is an indication that the removal kinetics are controlling the
volatilization rates, rather than the thermodynamics.
Phase I Pb I Zn As I Sb Bi
Commercially Observed
16
slag 40-80 70-90 10-50 30-70 5-20
gas 20-55 10-30 20-70 5-50 70-90
Equilibrium Model
6
slag 29 82 8 33 6
gas 64 18 80 48 85
Kinetic Model
slag 59 86 36 59 45
gas 37 10 62 40 54
Table Vu-Ill Comparison of equilibrium and kinetic model predicted minor
element distributions with commercially observed ranges.
237
9.1 Introduction
9 MODEL APPLICATION
9.1 Introduction
The kinetic model developed here can be applied to determine improved operating
conditions for the Peirce-Smith converter in its present form, or to indicate a direction for
the development of a new process.
9.2 Converter Optimization
There are three primary factors to be considered when trying to optimize the
performance of the Peirce-Smith converter: process time, oxygen efficiency, and minor
element deportment. Any optimization must also be carried out within the constraints set
by bath temperature and bath motion considerations. The variables which may be used
are tuyere submergence and diameter, gas flow rate, gas oxygen content, slag skimming
practice, and number of tuyeres used. Each of these will affect the primary factors in
different ways, both beneficial and detrimental. It is important to note that if only oxygen
efficiency and the process time are considered, equilibrium operation should be optimal.
However, under equilibrium conditions the amount of minor elements reporting to the
blister copper will be high, so the kinetics become important.
Oxygen enrichment is not available in many installations, and its effect on the bath
temperature generally limits its use to situations where extra scrap is available. At low
levels, it has a detrimental effect on minor element removal, and the extent of oxygen
enrichment usable is limited by its effect on the tuyere-line refractory. All of these
factors suggest that oxygen enrichment contributes little to the process, and so should not
be considered further.
238
Of the remaining variables, a reduced tuyere diameter and an increased tuyere
submergence both increase the oxygen use and reduce the total charge time, as well as
having a beneficial effect on the minor element removal to the dust. Increasing the tuyere
submergence also allows a higher gas flow rate to be used without initiating bath
9 Reducing the tuyere diameter increases the gas exit velocity, which has been
slopping.
shown to remove the need for tuyere punching due to the formation of stable,
8 The increased gas velocity also reduces the

non-blocking accretions on the tuyeres.
115 and does not affect the bath motion, which is related to the
extent of tuyere interaction,
buoyant power per unit mass of the bath.

9 All of these factors suggest that a small tuyere
diameter in a deep bath will provide the optimum operation. However, both of these
variables also cause an increase in the bath temperature, so there is a limit to their use.
Increasing the gas flow rate was also found to reduce the total charge time and the
distribution of the minor elements to the blister copper. Unlike the changes in tuyere
submergence and diameter, an increased gas flow reduces the oxygen use and the bath
temperature. Increasing the gas flow rate may also cause bath slopping, but this may be
9 Reducing the slag cover increases the
controlled by an increased tuyere submergence.
total charge time slightly and reduces both the oxygen use and the matte temperature.
These factors indicate that present converter operations can be improved
considerably by using a smaller tuyere diameter at a deeper tuyere submergence and a
higher gas flow rate. The increased gas flow rate will aid in controlling the temperature
increase, and may be aided by altering the skimming practice. The reduced tuyere size
should remove the need for tuyere punching, and so extend refractory life. The increased
tuyere submergence will reduce the likelihood of bath slopping, even at the higher gas
flow rate. In addition to this a reduced number of tuyeres could be used to further
239
increase the gas exit velocity and reduce the amount of tuyere interaction.
To illustrate this, Figure 9.1 shows the results of an improved version of the base
charge used in Section 8. The conditions used for this prediction are given in Table IX-I.
the lengths of the slag blows are reduced, but all idle times are unchanged. Figure 9.1
shows that the total charge time is reduced by 70 minutes, while the bath temperature is
kept within the range of the base charge. Figure 9.2 shows that the oxygen use in the
improved charge is lower than the base charge during the slag blows, but is higher
during the copper blow. This suggests that there is still room for improvements, but they
may be limited by the bath temperature. In fact, it is quite possible that 100% oxygen use
is not attainable because of the temperature constraints.
Variable Value
Tuyere submergence base+0.05 m
Tuyere diameter 0.03 8 m
Gas flow rate base+10%
Slag cover low
Table IX-I Conditions used in the improved charge.
240
1700
1600
w
1500
1400
1300
1200
1100
1000
Lii 6
I
5
4
z
0 3
Cl
2
0
0 100 200 300 400 500
TIME (miri)
Figure 9.1 Effect of modifications given in Table IX-I on the predicted variation of
matte temperature and iron content (weight percent) with time.
241
9.3 New Process Development
100
90
80
C/)
D
z
w
(3
70
0
60
50
0 100 200 300 400 500
TIME (mm)
Figure 9.2 Effect of modifications given in Table IX-I on the predicted variation of
oxygen use with time.
The results of the model runs using a very high oxygen content in the gas at a
constant temperature indicate a possible direction for process development. In the
standard converter, equilibrium represents the limit to operating efficiency, which can be
approached by altering variables to improve the kinetics. At high levels of oxygen
enrichment the kinetics of the system can be used to give considerable improvements in
operation. Unfortunately, high levels of oxygen in the gas also cause a large increase in
the bath temperature.
242
The Peirce-Smith converter, like most other pyrometallurgical reactors, is designed
to keep heat in. This is the opposite of what is required to allow process improvement. If
the reactor walls are designed to remove heat, rather than retain it, then higher levels of
oxygen could be used. For example, the use of water cooled panels would increase the
heat lost through the walls considerably, and give a certain degree of control over the
bath temperature. The bath temperature can also be controlled by the addition of cold
materials such as flux, concentrate, or solidified matte.
The primary improvement available using a high gas oxygen content is the direct
production of copper from matte. This is possible if the extent of the reaction of iron
sulphide becomes controlled by liquid-phase mass-transfer. Under these circumstances
the excess oxygen at the gas/liquid interface will react with copper suiphide to form
copper. A process designed to utilize this would have the added advantages of low gas
2 content.
volumes and an off gas with a high SO
To provide an example of such a process, the model has been modified to increase
the heat flux through the walls. The initial conditions of the base charge are used subject
to the modifications given in Table DC-il. The composition of the matte added is given in
Table TX-ill. Both solidified matte and flux are added continuously throughout the run
and 15 tonnes of slag is skimmed every 10 minutes. Figure 9.3 shows the predicted
variation of matte temperature and iron content for this process. Following an initial
decrease, the bath temperature increases up to the end of the run. This could be
controlled by increasing the heat removal through the walls, to provide an essentially
isothermal system. The weight percent of iron in the matte drops initially, but begins to
level out towards the end of the run. This could also be controlled by altering the iron
content of the added matte, the rate of matte addition, the gas flow rate, or the gas oxygen
243
content, to provide a constant value.
Figure 9.4 shows that the oxygen use in this system is very high. Even with the
high oxygen content in the gas, the oxygen use is higher than the model preducts for any
of the regular converter charges. Finally, Figure 9.5 indicates that the rate of blister
copper production is almost one tonne per minute. This is considerably higher than the
Peirce-Smith converter, which can produce about 10 tonnes per hour.

98
Variable Value
Tuyere submergence base+0.3 m
Tuyere diameter 0.03 m
Gas flow rate/tuyere 0.2325 Nm
s
3
Gas oxygen content 95%
Number of tuyeres 20
Flux addition rate 0.5 tonnes min
1
Matte addition rate 2.75 tonnes min
1
Table TX-il Conditions used in the new process.
Element Fe Cu 0 S Pb Zn
Content (wt.%) 24.7 43.8 3.4 24.1 1.16 2.66
Table TX-ill Composition of matte added in the new process.
244
1650
w
1600
w
1550
w
I
1500
1450
TIME (mm)
Figure 9.3 Predicted variation of matte temperature and iron content (weight
percent) with time for the new process.
245
100
99
98
UI
(I,
D
z
UI
0
97
0
96
95
0 10 20 30 40 60
TIME (mm)
Figure 9.4 Predicted variation of oxygen use with time for the new process.
50
(I)
a>
C
C
.2
40
Ui
0
D
0
0 30
UI
0
0
0
0
cx 20
UI
10
0
0 10 20 30 40 50
TIME (mm)
Figure 9,3 Predicted variation of weight of blister copper produced with time for
the new process
246
10 CONCLUSIONS AND FURTHER WORK
The kinetic model of the Peirce-Smith converter developed here, has been shown to
be able to predict both temperatures and compositions of the condensed phases to within
the accuracy of the measurements. A number of conclusions may be drawn based on the
predictions of both the gas flow model and the overall model, but it must be recognized
that there are still considerable inaccuracies involved with some of the data used.
The apparent success of the gas flow model indicates that it is possible to
theoretically model the formation and rise of gas bubbles through a liquid bath. While
the fluid flow portion of the model is far from rigorous, it is effective, and able to predict
gas fractions within the plume and spout heights with reasonable accuracy. Perhaps more
important is that gas/liquid interfacial areas are predicted well enough to use for kinetic
modelling purposes, however the almost complete lack of information regarding
gas-phase mass-transfer in bubbles does add some doubt to the accuracies of the
predictions.
Using the gas flow model, it can be concluded that increases in the tuyere
submergence and the gas exit velocity would increase the amount of oxygen available for
reaction. While increasing the oxygen content of the gas produces more reaction, it also
leaves a larger amount of unreacted oxygen because the increase in the mass-transfer rate
is not sufficient to react all of the extra oxygen. The material properties of the liquid
phase also have an effect on the rate of bubble growth, and tuyere interaction
significantly reduces the amount of oxygen available for reaction due to the larger
bubbles produced.
The increased oxygen use with increased tuyere submergence and gas exit velocity
98 can only be explained if the converter is kinetically
reported in an operating converter
247
controlled. These phenomena were predicted by the gas flow model, and are directly
transferred to the overall model. Thus, to properly model the converting process, the
kinetics of the system must be considered.
The effects of many of the process variables on the major components in the
converter follow directly from the results of the gas flow model. Any variable which
increases the oxygen use will increase the rates of iron removal and temperature increase
in the matte. What cannot be predicted by the gas flow model are the relative amounts of
reaction in the matte and slag, and the behaviour of the minor elements. The separation
of the reactions with the matte and slag are an important part of the kinetic model, which
is not possible with the assumption that all of the phases are in equilibrium.
A number of important conclusions may be drawn from the overall model. The
effects of tuyere submergence and gas exit velocity (controlled by the tuyere diameter
and the gas flow rate) have already been mentioned. As well, it has been determined that
the reaction between the gas and slag is at least partially controlled by liquid-phase
mass-transfer. As such it may be possible to alter the amount of reaction occurring by
changing the physical properties of the slag. In particular, the slag viscosity will have a
direct effect on the liquid-phase diffusivities, and can be altered by changing the iron to
silica ratio. It has also been determined that small amounts of copper are produced
throughout the converting cycle.
Oxygen enrichment does not necessarily cause an increase in the amount of minor
elements reporting to the blister copper. The higher temperatures associated with oxygen
enrichment increase the mass-transfer rates within the liquid phases as well as the
equilibrium vapour pressures, so more of the minor elements are vapourized. At very
high oxygen enrichments it is predicted that white metal is formed later in the converting
248
cycle, with copper being produced directly from a high grade matte. This could have a
bearing on future process design, as it also increases the amount of minor element
vapourization.
There is still insufficient data regarding these, particularly with respect to
mass-transport, so the predictions regarding them must be considered to be tentative. The
inaccuracies involved in the overall model may also fairly large. Measurements made on
operating equipment are far from precise, and make any validation uncertain. To
improve on this carefully controlled cold modelling could be used, or, ideally a small
scale test converter could be used. Some tests have been carried out, but insufficient data
has been reported to allow their use in the present case.
Some other physical modelling studies could provide information which would be
useful in improving the kinetic model. These would primarily involve injection into two
and three phase systems, to obtain a better understanding of the behaviour of the
interfaces involved. Ideally these would also involve mass-transfer measurements.
Perhaps most important is the development of an expression relating to gas-phase
mass-transfer coefficient in rising bubbles. Such an expression is essential to improving
our understanding of all gas injection processes.
249
11 NOMENCLATURE
11 NOMENCLATURE
A Area (m
)
2
a Minor axis of ellipse (m)
b Maj or axis of effipse (m)
C Concentration (mol m
)
3
CD Drag coefficient
Heat capacity (J kg Kj
Disturbance propagation speed (eq. 4.22)
Diffusivity (m
2 s)
d Diameter (m)
F Force (N)
Fr Modified Froude number
f Fraction 02 in gas
2)
g Acceleration due to gravity (9.81 m
h Height (m)
h Heat-transfer coefficient (W m
2K)
1
hB Height shown in Figure. 4.7
K Constant
k Mass-transfer coefficient (m sj
k Wave number (ma) (2t
kc
1 Growth factor (eq. 4.23)
L Converter length (m)
1
L Distribution coefficient between copper and slag
1 Length (m)
M Molecular weight (g mor)
M Mass (kg)
[M] Weight percent of element M
Nu Nusselt number
n Number, Moles
ii Molar flux (mol sj
250
11 NOMENCLATURE
P Pressure (Pa)
P Equilibrium vapor pressure of pure substance (Pa)
Pr Prandtl number
p Partial pressure (Pa)
Q Volume flow rate (m
3s )
1
4 Heat flux (J s)
R Gas Constant
Re Reynolds number
r Radius (m)
s Distance from tuyere centre to bubble centre (m)
T Temperature (K)
t Time (s)
V Volume (m)
3
v Velocity (m s)
w Relative velocity of bubble with respect to the bath (m 1
)
X Mole fraction
x Thickness (m)
x Reaction constant (equation 6.34)
Greek letters
Accommodation coefficient in Langmuir-Knudsen equation

Thermal diffusivity 2
(m s)
Absorptivity of gas
Angle (Figure 5.4 or Figure 6.3)
Activity coefficient
boundary layer thickness (m)
8 Eccentricity of ellipse
8 Emissivity
ln[(
[Itan(I
Perterbation amplitude (m)
251
11 NOMENCLATURE
00 Disturbance initiation angle
Wake angle
Wavelength (m)
Dynamic viscosity (kg m
11 s
)
v Kinematic viscosity (m
2 s)
p Density (kg m
)
3
,rn Molar density (mol m
)
3
Dimensionless density
a Surface tension (N m
)
1
a Stefan-Boltzman constant, 5.67(108) W m
2K4
Gas holdup
252
11 NOMENCLATURE
Subscripts
amb Ambient
B Bath
Bu Buoyancy
b Bubble
c converter
cb converter barrel
con Consumed
D Drag
d droplet
e Evaporation
ew End wall
ext External
G Gas-phase
g Gas
gp Gas in plume
gen Generated
H Hood
i Specie, Initial, Interfacial
mt Internal
L Liquid-phase
M Matte-phase
m Mouth
mm Minimum
mt Mass-transfer
o Oriface
p Plume
R Reaction, Refractory
r Remaining, Residence
rad Radiation
S Slag-phase, Sphere
s Surface tension
sp Spout
253
11 NOMENCLATURE
sup superficial
T Temina1
t Tuyere
w Wall
x Cross-section
Superscripts
B Bulk
C Copper
I Interfacial
I,J Phase
M Matte
S Slag
W White metal
* Interfacial (actual)
+ Interfacial (equilibrium)
254
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13 APPENDIX
13 APPENDIX
Model Calculation Technique
A simplified flow chart of the overall model calculation technique is given in
Figure 13.1, and more detailed flow charts of the bubble, mass balance, and heat balance
calculations are shown in Figures 13.2-13.4. Figure 13.1 shows that if the change in the
temperature of any phase is greater than a preset tolerence (10 K), then the mass balance
calculation is carried out again using the average temperatures. The heat balance is then
recalculated based on the modified compositions. With this exception, it is assumed that
all interphase heat and mass-transfer can be calculated based on the temperatures and
compositions at the end of the previous time step.
266
13 APPENDIX
INPUT OPERATING PARAMETERS
CALCULATE PHASE DEPTHS
GAS FLOW CALCULATION
MASS BALANCE CALCULATION
*
HEAT BALANCE CALCULATION
I MODIFY
I_TEMPERATURE
YES
AT>r)
NO
NO
t=t+At t>t
YES
END
Figure 13.1 Simplified flow chart of the overall model.
267
13 APPENDIX
INPUT BLOWING PARAMETERS
BUBBLE GROWTH CALCUlATION
STABILITY CALCULATION
NO
DETACHMENT?
YBS
t=t+At
4
PLUMB CHARACTERISTICS
BUBBLE RISE CALCULATION
STABILITY Cl LCULATION
OUThUT
Figure 13.2 Flow chart of the gas flow calculation.
268
13 APPENDIX
LUT
MAJOR COMPONENTS REACTION CALCULATION
MINOR COMPONENTS MASS-TRANSFER CALCULATION
LIQUID/LIQUID MASS-TRANSFER
EQUILIBRIUM CALCULATIONS
OUTPUT
Figure 13.3 Flow chart of the mass balance calculation.
269
13 APPENDIX
INPUT
MATTE HEAT BALANCE CALCULATION
SLAG HEAT BALANCE CALCULATION
BLISTER
YES
BLISTER HEAT BALANCE CALCULATION
Figure 13.4 Flow chart of the heat balance calculation.
270

A Kinetic Model of The Peirce-Smith Converter

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A KINETIC MODEL OF THE

ANDREW KEVIN KYLLO

A THESIS SUBMITTED IN PARTIAL FULFILLMENT OF THE

We accept this thesis as conforming

THE UMVERSITY OF BRITISH COLUMBIA

In presenting this thesis in partial fulfilment of the requirements for an advanced

The University of British Columbia

techniques have been developed, including considerable improvements to non-ferrous

operated at thermodynamic equilibrium.

each phase is assumed to be in internal equilibrium. As well as calculating the behaviour

minor elements is considered. The model is validated using published physical

modelling results, as well as measurements made on operating converters.

size are predicted to provide a substantial improvement in operation efficiency, without

chemistry, with the amount of iron reacting being controlled by liquid-phase

8 MODEL PREDICTIONS AND DISCUSSION 157

9 MODEL APPLICATION 238

10 CONCLUSIONS AND FURTHER WORK 247

Table IV-I Details of copper charges followed 22

Table IV-Vll Details of nickel converter charges 29

Table IV-Xll Overall oxygen efficiencies for copper converter charges

Table IV-XllI Oxygen efficiencies calculated from matte samples 34

Table IV-XTV Calculated nickel converter oxygen efficiencies 35

Table TV-XV Distribution of major components between output streams of the

Table IV-XVT Distribution of major components in nickel converting 38

Table IV-XVTI Compositions of converter dust samples 44

Table V-TI Bubble size at detachment calculated from different models 61

Table VT-I. Reacting components of the matte 90

Table VT-fl Reactions required to calculate the equilibrium composition of the

Table VT-HI Integrated values of C. for use in equation 6.73. 103

Table VT-TV Enthalpies of reaction required for energy generation

Table VT-VT Coefficients for gas viscosity equation (air).

Table VI-VIl Free energy of formation of matte compounds.

Table VT-VIIT Free energy of reaction for matte-slag reactions.

Table VI-Xll Equilibrium vapour pressures of the minor elements 119

Table VT-XIIT Atomic/ionic/molecular radii of matte, slag and bullion

Table VTT-T Comparison of measured and predicted gas penetration in

Table VTT-TTT Comparison of model predicted slag compositions with assays,

Table VH-TV Comparison of model predicted slag compositions with assays,

Table VTI-V Comparison of model predicted slag compositions with assays,

Table VIT-XI Comparison of model predicted slag compositions with assays

Table VII-XII Comparison of model predicted slag compositions with assays

Table VII-XTV Comparison of model predicted matte compositions with

Table VTT-XV Comparison of model predicted matte compositions with assays,

Table VuT-XVT Comparison of model predicted matte compositions with

Table VuuT-T Parameters tested in the sensitivity analysis 172

Table IX-il Conditions used in the new process 244

Figure 1.1 Schematic of the Peirce-Smith converter 4

Figure 4.8 Copper converter flue dust, x25 47

Figure 4.12 Copper converter Cottrell dust, a. sample 1, xl 00, b. sample 2,

Figure 5.8 Schematic illustration of flow around a bubble.

Figure 6.1 Schematic cross-section of an idle converter 85

Figure 6.4 Comparison of reported values of free energy of reaction 109

Figure 6.5 Comparison of reported values of free energy of formation of SbS

Figure 6.6 Comparison of reported values of free energy of formation of AsS

37 and predicted spout height

Figure 7.3 Variation of fraction sulphur dioxide reacted with tuyere

Figure 7.15 Calculated variation of mole fractions of Fe

Figure 7.17 Comparison of model predicted antimony and bismuth

Figure 8.4 Variation of average oxygen partial pressure with tuyere

other conditions given in Table V-I 165

Figure 8.13 Predicted variation of oxygen use with time 170

Figure 8.14 Predicted variation of tuyere submergence (including spout) with

Figure 8.15 Predicted variation of oxygen use with tuyere submergence