Combustion of Particles of Copper Concentrate in A Stagnant Gas

COMBUSTION OF PARTICLES OF COPPER CONCENTRATE
IN A STAGNANT GAS FURNACE
by
ANABEL THOMAS
B.Sc. UNIVERSIDAD NACIONAL AUTONOMA DE MEXICO, 1982.
A THESIS SUBMITTED IN PARTIAL FULFILMENT OF
THE REQUIREMENTS FOR THE DEGREE OF
MASTER OF APPLIED SCIENCE
in
THE FACULTY OF GRADUATE STUDIES
(Department of Metals and Materials Engineering)
We accept this thesis^as conforming to the required standard
THE UNIVERSITY OF BRITISH COLUMBIA
March, 1999.
ANABEL THOMAS, 1999.

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. 1 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.
Department of
The University of British Columbia

Vancouver, Canada
March Zl .
nl
Date Wf.
DE-6 (2/88)
ABSTRACT
Two copper concentrates, "La Escondida" and "La Caridad", were oxidized in a stagnant gas-
flow reactor to examine and compare their combustion behavior. "La Escondida" concentrate
is a high grade copper (49 % Cu) concentrate based on chalcocite (CU2S) and pyrite (FeS2),
while "La Caridad" contains pyrite (FeS2), chalcopyrite (CuFeS2), chalcocite (CU2S) and
covellite (CuS) with 29.5 % Cu. The effects of oxygen partial pressure, temperature, and
particle size on the reaction behaviour of each concentrate were studied.
The reaction products were analyzed for copper, iron, and sulfur to determine the fraction of
original sulfur remaining as a measure of the extent of reaction and the Cu/Fe ratio as a
measure of copper volatilization. X-Ray Diffraction was employed to identify the phases
present and Scanning Electron Microscopy (SEM-EDX) and Optical Microscopy were used to
determine the particle morphology and chemical analysis of the individual particles.
The results show that although La Escondida does not contain chalcopyrite, in the individual
particles both pyrite and chalcocite are present and form chalcopyrite before ignition, leading
to oxidation behaviour similar to that of La Caridad concentrate. The extent of reaction was
found to increase with increasing oxygen concentration, temperature and particle size.
ii
TABLE OF CONTENTS
ABSTRACT ii
LIST OF FIGURES v
LIST OF TABLES ' viii
NOMENCLATURE ix
GLOSSARY xi
ACKNOWLEDGEMENTS xii
1 INTRODUCTION 1
2 LITERATURE REVIEW 6
2.1 Thermodynamics 6
2.2 Kinetics and Transport Phenomena 11
i) Prior to ignition: Thermal decomposition and gas
solid oxidation 11
ii) Ignition 12
iii) Post ignition: Gas-liquid oxidation 13
2.2.1 Studies on combustion of Chalcopyrite and Pyrite 13
2.2.1.1 Effect of particle size, temperature and oxygen
concentration 15
2.2.1.2 Ignition temperature 17
2.2.1.3 Time to attain ignition, oxidation time and
oxidation rate 17
2.2.1.4 Particle temperature and vaporization 19
2.2.1.5 Particle fragmentation 19
2.2.2 Studies of oxidation of chalcocite 22
2.3 Chemical and morphological changes 25
i) Prior to ignition 25
ii) Ignition 29
iii) Post ignition 29
3 SCOPE AND OBJECTIVES 32
4 EXPERIMENTAL 33
4.1 Experimental set-up 33
4.2 Procedure 33
4.3 Variables studied 36
iii
4.4 Preparatory tests 36
4.5 Reproducibility of the results 38
4.5 Characterization of the two concentrates
4.5.1. "La Escondida" concentrate 40
4.5.2. "La Caridad" concentrate 40
5 EXPERIMENTAL RESULTS 45
5.1 Observations of reacting particles 45
5.2 Sulfur removal 45
5.3 Copper-Iron ratio 52
5.4 X Ray Diffraction Analyses 55
5.5 Microscopic examination 59
5.5.1 Transformation stages in solid state 67
6 DISCUSSION 72
6.1 100 % 0 and 50 % 0 - 50 % N atmosphere
2 2 2 72
6.2 90 % S 0 - 10 % 0 atmosphere
2 2 78
6.3 100 % N atmosphere
2 80
6.4 Vaporization of copper 82
7 CONCLUSIONS 83
REFERENCES 86
iv
LIST OF FIGURES
Fig. 1.1: Inco oxygen flash furnace 3
Fig. 1.2: Outokumpu oxygen-enriched air flash furnace 4
Fig. 1.3: Flash smelters in the world 5
Fig 2.1: Standard free energies of formation of oxides and sulfides of iron
and copper 8
Fig. 2.2: Predominance diagram for Cu-Fe-S-O system at 827 C 10
Fig. 2.3: Apparatus used by Jorgensen 14

Fig. 2.4: Effect of particle size on the oxidation of chalcopyrite concentrate in air at
700 C 15
Fig. 2.5: Effect of the experimental temperature on the combustion of 37-53 pm

chalcopyrite concentrate in air 16
Fig. 2.6: Effect of the oxygen concentration of the atmosphere on the combustion of
chalcopyrite concentrate in oxygen-nitrogen mixtures at 700 C and 37-53 prn screen
size fraction 16
Fig. 2.7: Effect of temperature on the oxidation rate of various sulfides of 37 - 53 pm

in air 18
Fig. 2.8: Model for fragmentation proposed by Kim 21
Fig. 4.1: Experimental apparatus 34
Fig.4.2: Temperature profiles 37
Fig. 4.3: Calculated residence time of particle sizes 39
Fig. 5.1 (a) Photograph of La Escondida 325 mesh and (b) La Caridad 500 mesh
reacting in a 100 % 0 atmosphere at 600 C
2 46
Fig. 5.2: Effect of temperature on the sulfur remaining after combustion of 500 mesh
and 325 mesh La Escondida and La Caridad at 100 % 0 2 48
and 325 mesh La Escondida and La Caridad at 50 % Q - 50 % N
2 2 49
and 325 mesh L a Escondida and L a Caridad at 90 % S 0 - 10 % 0 2 2 50
and 325 mesh L a Escondida and L a Caridad at 100 % N 2 51
Fig. 5.6: Copper-iron ratio for L a Escondida concentrate 53

a) La Escondida 500 mesh particle size
b) La Escondida 325 mesh particle size
Fig. 5.7: Copper-iron ratio for L a Caridad concentrate 54

a) L a Caridad 500 mesh particle size
b) L a Caridad 325 mesh particle size
Fig. 5.8: S E M image of reaction products of 325 mesh L a Escondida concentrate after
reacting in a 100 % oxygen atmosphere at 600 C 60
Fig. 5.9: S E M image of reaction products of 325 mesh L a Caridad concentrate after
reacting in a 50 % oxygen - 50 % nitrogen atmosphere at 700 C 60
Fig. 5.10: S E M image of cenosphere of iron oxide found in the reaction products of
325 mesh L a Escondida concentrate for a 50 % 0 - 50 % N atmosphere at 800 C
2 2 61
Fig. 5.11: S E M image of cenosphere of Cu S found in the reaction products of

2
500 mesh L a Escondida for 100 % 0 at a temperature of 900 C

2 61
Fig. 5.12: Particle of Cu S covered with iron oxide with separated inclusions of
2
CuFe C4 found in L a Caridad 325 mesh after reacting in a 50 % 0 - 50 % N

2 2 2
atmosphere at 800C. Image obtained by backscatter mode 62
Fig. 5.13: S E M image of a particle of pyrrhotite and particles of CuFe C4 C u F e 0 and

2 2
Fe oxide found in the reaction products of La Escondida 325 mesh after reacting in a
50 % 0 - 50 % N atmosphere at 600 C. Image obtained by backscatter mode
2 2 62
Fig. 5.14: Optical microscope image of a drop of Cu S with veins of metallic copper
2
found in L a Caridad after reacting in a 50 % O -50 % N atmosphere at 800 C

2 2 64
Fig. 5.15: S E M images of (a,b,c) compact crust of spheres with high silica content,
and (d) immiscibility between oxides and sulfides accentuated by the silica.
La Escondida 500 mesh after reacting in a 100 % 0 atmosphere at 600 C
2 65
Fig. 5.16: Optical microscope image of a sphere of bornite with inclusions of metallic
copper found in La Escondida 325 mesh after reacting in a 90 % S 0 - 10 % 0 2 2
atmosphere at 600 C 66
vi
Fig. 5.17: Particle of C112S with rim of iron oxide. La Caridad 325 mesh at 100 % N2
and 700 C. SEM backscatter mode 68
Fig. 5.18: Particle of FeS with rim of iron. La Caridad 325 mesh at 100 % N and
2 2
700 C. SEM backscatter mode 68
Fig. 5.19: a) Particle of pyrite dissociating to pyrrhotite and b) pyrrhotite with

butterfly shape La Caridad +200 mesh at 20 % 0 - 80 % N and 500 C.
2 2
SEM backscatter mode 69
Fig. 5.20: Optical microscope image of a particle of chalcopyrite dissociating to bornite

and then to digenite-chalcocite. La Caridad + 200 mesh after reacting in a
20 % 0 - 80 % N atmosphere at 500 C
2 2 70
Fig. 5.21: Optical microscope image of chalcopyrite formed at the junction of particles
originally consisting of pyrite and chalcocite. Chalcopyrite then transforms to bornite
and chalcocite forming a four-colour particle 71
LIST OF TABLES
Table 2.1: Proportions of copper and sulfur found in copper sulfides 6
Table 2.2: Principal reactions in the smelting of copper concentrates 7
Table 2.3: Approximate ignition temperatures for concentrates in air 17
Table 4.1: Particle size distribution of La Escondida concentrate 41
Table 4.2: Chemical and mineralogical composition of La Escondida Concentrate 41
Table 4.3: Image analysis of La Escondida concentrate 42
Table 4.4: Particle size distribution of La Caridad concentrate 43
Table 4.5: Chemical and mineralogical composition of La Caridad concentrate 43
Table 4.6: Image analysis of La Caridad concentrate 44
Table 5.1: Phases present for 100 % O2 atmosphere 56
Table 5.2: Phases present for 50 % 0 - 50 % N atmosphere

2 2 56
Table 5.3: Phases present for 90% S 0 - 10 % 0 atmosphere

2 2 57
Table 5.4: Phases present for 100 % N atmosphere

2 57
Table 6.1: Types of particles in La Escondida concentrate 73
viii
N O M E N C L A T U R E
Symbol Definition
A Surface area of particle
C Specific heat of fluid
c P
Specific heat of particle
DAB Diffusivity of a gas mixture
d p
Particle diameter
g Gravitational acceleration
h Heat transfer coefficient
K Equilibrium constant
kg Thermal conductivity of fluid
kp Thermal conductivity of particle
M, M , A M B
Molecular weights
P Pressure
pS0 , pS ,
2 2 p02
Partial pressure of SO2, S2, O2
R Gas constant
r Radius of particle
T Temperature
T s
Gas temperature
Ti Initial temperature
t Time
Up, Velocity of particle

Ug Velocity of gas
VA, VB Molecular volumes
V Volume of particle
Greek
AG Change in free energy
77 Fluid viscosity
p p Density of particle
p g Density of gas
x
GLOSSARY
Bornite Cu FeS
5 4
Chalcocite Cu S
2
Chalcopyrite CuFeS 2
Copper ferrite - Cupro spinel CuFe 0 2 4
Covellite CuS
Delafossite CuFe0 2
Digenite Cu . S (average Cui.gS)

2 x
Fayalite Fe Si0
2 4
Galena PbS
Hematite Fe 0
2 3
Magnetite Fe 0
3 4
Pyrite FeS 2
Pyrrhotite Fei. S (average Feo.9S)

x
Sphalerite ZnS
Troilite FeS
ACKNOWLEDGMENTS
I would like to take this opportunity to express my profound respect to Dr. J. K. Brimacombe
who was not only an oustanding metallurgist but also an exceptional person.
I am indebted to Drs. John Grace and Indira Samarasekera for their invaluable guidance and
support throughout this project.
I would like to thank Patrick Wenman, Larry Wong, Mary Mager and Rudy Cardeno for their
technical support during the project.
I wish to thank Grant Caffery, Pierre Constantineau and Grant Morgan for their invaluable
discussions.
I am grateful to BHP Copper and Mexicana de Cobre, S.A. for providing samples of
concentrates.
Xll
1 INTRODUCTION
1 INTRODUCTION
In the late 1940's and early 1950's, the International Nickel Co. (Inco) and Outokumpu Oy
independently introduced flash smelting processes. The Inco process (Fig. 1.1) was based on the
use of industrial oxygen, while the Outokumpu process (Fig. 1.2) utilized air. By the late 1970's,
the Outokumpu process had evolved to a mixture of air and oxygen, a change that allowed the
smelters to increase their capacity by approximately 50 %. There are currently over forty
Outokumpu flash smelting furnaces in operation producing about 40 % of the world's primary
copper [1]. A map showing flash smelters is shown in Fig. 1.3 [2].
In the Outokumpu flash furnace, concentrate and silica are introduced into a stream of air enriched
with oxygen in a hot chamber called the "reaction shaft". As the particles and air flow downward
through the reactor, the particles undergo controlled partial oxidation which is accompanied by a
large evolution of heat which melts the the particles; then they fall as a rain in the "settler". In the
settler, two different liquids are separated, matte and slag. Matte is a sulfidic phase consisting of
iron sulfide and copper sulfide. Slag is an oxidized phase with iron oxide and fayalite ( Fe2Si0 ).
4
The major advantage of the flash processes is the use of the heat of reaction to melt and partially
oxidize the sulfides without, or almost without, extra fuel. In addition, a gas stream is generated
which is rich in S O 2 so that it can be treated to produce sulfuric acid, liquid S O 2 or elemental
sulfur. The disadvantages are the large production of dust requiring equipment for collection and
recycling and the high copper content of the slag necessitating further treatment.
1
1 INTRODUCTION
The concentrate burner is considered to be the heart of the furnace. Its function is to introduce
concentrate, silica and process air into the furnace creating a well distributed particle-gas
suspension. Various designs of concentrate burners are used to minimize the generation of dust
and to obtain a better slag.
La Escondida concentrate comes from a mine in Chile which belongs to BHP Copper. It is an
unusual concentrate because of the high grade of copper (49 % as chalcocite, Q 1 2 S ) It also
contains pyrite ( F e S 2 ) and it is treated in a flash smelter in San Manuel Arizona where operational
problems result when the the amount of La Escondida exceeds blending proportions in excess of
20 %. These problems are associated with build-up of unreacted concentrate at the bottom of the
reaction shaft and uptake shaft of the furnace.
For these reasons, a program of study has been undertaken to study the oxidation characteristics of
this concentrate. The present work consisted of an experimental examination of the oxidation
behaviour of single particles of La Escondida concentrate, and comparison with La Caridad, a
concentrate with 29.5% Cu, consisting of chalcopyrite ( C u F e S 2 ) , pyrite (FeS ), chalcocite (Cu S)
2 2
and covellite (CuS). This concentrate is also treated in a flash furnace.
2
1 INTRODUCTION
Matte
Fig. 1.1 Inco oxygenflashfurnace [2]
3
1 INTRODUCTION
Dry Concentrate
and Flux
Fig. 1.2 Outokumpu oxygen-enriched airflashfurnace [2].
4
1 INTRODUCTION
1 Asarco Inc. (Inco type furnace) Hayden USA 1983

2 Magma Copper Co. San Manuel USA 1 9 8 8
3 Mexicana de Cobre S.A. La Caridad Mexico 1986
4 Phelps Dodge Corporation Hidalgo USA 1976
5 Phelps Dodge Corp. (Inco type furnace) Hurley USA 1984
6 Inco Limited (Inco type furnace) Sudbury Canada 1953
7 Caraiba Metais S.A. Camacari Brazil 1982
8 Rio Tinto Minera S.A. Huelva Spain 1975
9 Norddeutsche Affinerie A G Hamburg W. Germany 1972
10 Kombinat Gorniczo-Hutniczy
Miedzi (direct copper production) Glogow Poland 1978
11 Outokumpu Oy Harjavalta Finland 1949
12 Outokumpu Oy (Ni) Harjavalta Finland 1959
13 Combinatu] Chimico Metalurgic Baia Mare Romania 1966
14 MDK G Damianov Srednogorie Bulgaria N A
15 Karadeniz Bakir Isletmeleri A.S. Samsun Turkey 1973
16 Bamangwato Concessions Ltd. ( N i ) Selebi-Phikwe Botswana 1973
17 Almalyk Copper Smelter (Inco type
furnace) Almalyk USSR 1968
18 Norilskii GornoMetallurgicheskii
Kombinat Norilsk USSR 1981
19 Norilskii Gorno-Metallurgicheskii
Kombinat (Ni) Norilsk USSR 1981
20 Hindustan Copper Ltd. Khetri India 1974
21 Hindustan Copper Ltd. Ghatsila India 1971
22 China National Technical Import Co. Guixi China 1986
23 Korea Mining and Smelting Co. Ltd. Onsan Korea 1979
24 Nippon Mining Co. Ltd. Saganoseki Japan 1970
25 Nippon Mining Co. Ltd. Saganoseki Japan 1973
26 Sumitomo Metal Mining Co. Ltd. Toyo Japan 1971
27 Hibi Kyodo Smelting Co. Ltd. Tamano Japan 1972
28 Furukawa Mining Co. Ltd. Ashio Japan 1956
29 Nippon Mining Co. Ltd. Hitachi Japan 1972
30 The Dowa Mining Co. Ltd. Kosaka Japan 1967
31 Philippine Associated Smelting and
Refining Corp. Leyte Philippines 1983
32 Western Mining Co. Ltd. (Ni) Kalgoorlie Australia 1972
33 Peko Wallsend Metals Ltd. Tennant Creek Australia 1973
34 Peko Wallsend Metals Ltd. Mount Morgan Australia 1972
3 5 O l y m p i c D a m
Australia 1 9 8 8
3 6 C h u q u i c a m a t a
Chile 1 9 8 5
37 D i s p u t a d a d elos C o n d e s Chile 1 9 9 5
3 8 K e n n e c o t t U S A 1 9 9 5
39 A s a r c o ( C o n t o p t y p e )
U S A 1 9 9 3
Fig. 1.3. Flash Smelters in the world [2], updated from [1]
5
2 LITERATURE REVIEW
2 LITERATURE REVIEW
Copper sulfide minerals can be considered to consist of combinations of normal-valency
sulfides, e.g. Cu S and FeS, and of compounds such as CuS and FeS in which part of the
2 2
sulfur is particularly reactive (called pyritic sulfur). The proportions of pyritic sulfur are given
in Table 2.1.
Table 2.1: Proportions of copper and sulfur found in copper sulfide minerals [3].
Mineral Composition wt % Cu wt % total S wt % pyritic S
Chalcopyrite CuFeS 2 34.6 34.9 8.7

Bornite Cu FeS
5 4
63.3 25.5 3.2
Covellite CuS 66.5 33.5 16.8
Chalcocite Cu S 2 79.8 20.2 0
Pyrite FeS 2
0 53.4 26.7
2.1 Thermodynamics
The main reactions that occur in the smelting of concentrates and their heats of reactions are
listed in Table 2.2. When a concentrate consisting of chalcopyrite, pyrite and/or covellite is
smelted, the concentrate decomposes endothermically according to reactions 1, 2 and 3, and
the sulfur liberated (pyritic sulfur) is burnt spontaneously (reaction 4). Then FeS oxidizes first
producing FeO and Fe30 (reactions 5 and 6). Together with the concentrate, blended silica
4
combines with the FeO according to the reaction 7 to produce fayalite (Fe Si0 ). If some Cu S
2 4 2
reacts to Cu 0, the excess FeS reduces the Cu 0 formed to Cu S (reaction 11). In this way,
2 2 2
Cu S is not oxidized until the completion of the oxidation of FeS. Then Cu S reacts with
2 2
6
2 LITERATURE REVIEW
oxygen to produce Cu 0 and Cu (reactions 8 and 9). The Cu 0 formed, however, reacts with
2 2
the Cu S to form Cu (reaction 10).

2
Table 2.2 Principal reactions in the smelting of copper concentrates.
Heat of reaction at 1400 C

,' (kcal/mol)
Dissociation reactions:
1) 2 CuFeS - Cu S + 2 FeS + 1/2 S

2 2 2( s ) 43.0 (U
2) 2FeS -> 2 FeS + S

2 2f(rt 67.9 (M
3) 4 CuS - 2Cu S + S 2 2(e) 44.7 0,2
Oxidation reactions:
4) S + 2 0 -> 2 S 0
2 2 2 -172.5 (2
5) 3 FeS + 5 0 - Fe 0 + 3 SOz 2 3 4 -44.1 (3
6) FeS + 1.5 0 - FeO + S0 2 2 -115.6 (3
7) 2 FeO + Si0 - Fe2Si0 2 4 13.9 (2
8) Cu S + 1.5 Oz -> Cu 0 + S0
2 2 2 -82.0 (2
9) Cu S + 0 - 2 Cu + S0
2 2 2 -52.7 (2
10) Cu S + 2Cu 0 -> 6Cu + S0

2 2 2 6.0 (2
11) Cu 0 + FeS -> Cu S + FeO

2 2 -33.6 (2
1) Data for 800 K (527 C).

2) The metallurgy of copper. International Copper Research Association.
3) Thermodynamic properties of elements and oxides. L.B. Pankratz, U.S.B.M. Bull. 672.
4) Thermodynamic data for inorganic sulphides, selenides and tellurides. K.C. Mills
The standard free energies of formation of oxides and sulfides of iron and copper are shown in
the Fig. 2.1 which is an Ellingham diagram. Important considerations on the smelting of
copper concentrates are better appreciated by reference to this diagram [3]:
7
2 LITERATURE REVIEW
400 800 1200 1600 2000

Temperature, *C
Fig. 2.1 Standard free energies of formation of oxides and sulfides of iron and copper [3].
1) CuS and FeS2 are unstable at temperatures higher than 550 C and 690 C due to their
higher sulfur vapour pressures [4].
2) Cu S and FeS have approximately the same stability at smelting temperatures, but the
2
much greater stability of FeO as compared with Cu 0 is the reason why FeS is preferentially
2
oxidized.
3) FeO is made even more stable by combination with Si0 to form a Fe Si0 slag.
2 2 4
4) The oxidation of FeO to Fe30 is promoted by low temperature and low S i 0 contents of
4 2
the charge.
8
2 LITERATURE REVIEW
Predominance diagrams for Cu-Fe-S-O system have been constructed by various authors [5, 8].
A sulfur-oxygen potential diagram at 827 C is shown in Fig. 2.2 where the stable regions and
related conditions for each species can be seen.. The equilibrium partial pressures of S 0 are 2
expressed with inclined, straight lines based upon the equilibrium:
1/2 S ) + 0
2 (g 2 (g) = S0 )
2 (g
log K = log pS0 - 1/2 log pS - log p 0 2 2 2
K 8 2 7 C =
10 134
In this manner, the progress of the oxidation can be predicted following the 0.1 atm isobar for
S0 . With increasing oxygen potential, the order of the reactions is: chalcopyrite first
2
decomposes to bornite and magnetite, then it forms Cu S + 2 Fe C>4.

3 Further oxidation gives
CuFe0 + Fe 0 , then CuFe0 + CuFe 0 and finally CuFe 0 + CuO.

2 2 3 2 2 4 2 4
The slope of the lines of the diagrams is determined by the stoichiometry of the reactions in
consideration and the lines move with temperature due to the changes of free energy. Thus, for
680 C the products of oxidation are CuS0 and Fe 0 and for 1000 C are CuFe0 and
4 2 3 2
CuFe 0 . 2 4
9
2 LITERATURE REVIEW
log p s 2 Mm)
Fig. 2.2 Predominance diagram for Cu-Fe-S-0 system at 827 C [5].
2.2 Kinetics and transport phenomena
In the flash furnace, dry concentrate particles and flux (silica) are entrained in a stream of
oxygen-enriched air introduced through the concentrate burner. The concentrate particles are
first heated by convection and by radiation from the furnace walls, until the oxidation reactions
generate more heat than can be dissipated through heat losses to the atmosphere. The particle
temperature then rises rapidly reaching the melting point while they fall through the reaction
shaft [6].
10
2 LITERATURE REVIEW
Each size fraction has a different residence time and degree of reaction. Kenmori et al [7]
measured oxygen pressures in the molten particles of a copper flash furnace (Toyo Smelter) by
means of a galvanic cell (Fe, FeO / Zr0 + MgO / O ) observing the following:
2
- Most of the oxygen contained in the process air is consumed in the upper part of the
reaction shaft by the particles that easily ignite and by the smaller particles.
-These particles become overoxidized, whereas the big particles experience
underoxidation.
-The collision of particles results in underoxidized particles reacting with overoxidized
ones.
The following is a general description of the stages that particles experience during their flight
in the reaction shaft.
i) Prior to ignition: Thermal decomposition and gas-solid oxidation.
When the particles are heated, endothermic reactions occur first with the loss of pyritic sulfur
by vaporization. The release of labile sulfur from particles may act as an igniter or initiater for
oxidation reactions. The oxidation of the dissociated sulfur is highly exothermic, and the heat
from the reaction causes a further rise in particle temperature.
In the initial particle heating phase, gas-solid oxidation reactions occur which are chemical
reaction controlled. Chaubal and Sohn [8] studied the overall kinetics of the oxidation of
chalcopyrite in the absence of heat and mass transfer effects, obtaining data which were well
11
2 LITERATURE REVIEW
correlated by the pore-blocking kinetic model at temperatures below 600 C. The pore-blocking
kinetics is not normally encountered. However, in porous solids, the formation of a product
layer in volume than the reactant (in this case, sulfates) can cause partial blockage of the pores.
At higher temperatures first order kinetics described the progress of the oxidation.
ii) Ignition
The ignition temperature is the temperature at which the particles start to react rapidly. At the
ignition temperature, the particle temperature jumps from a low temperature steady state to a
high temperature steady state. The ignition temperature is not a unique property of any given
material, but depends on a balance between the rates of heat gain and heat loss to the particle
and therefore on the surroundings, as well as the particle properties.
By conducting experiments in a laminar-flow furnace with nickel sulfide concentrate,
Jorgensen [9] found that the effect of gas preheating was more important than the
temperature of the walls and concluded that the predominant heat transfer mechanism during
the heating of the particle to the ignition temperature is conduction from the gas rather than
radiation from the enclosure.
The oxidation of chalcopyrite and pyrite is greatly influenced by the structural transformations.
Jorgensen [10] suggested that the structural changes of chalcopyrite and pyrite are responsible
for the ignition. Transformation of chalcopyrite into an intermediate solid solution and pyrite
into pyrrhotite with an open porous structure allows ready access to oxygen, leading to
ignition. These transformations are considered in Section 3.
12
2 LITERATURE REVIEW
iii) Post ignition: Gas liquid oxidation.
Once the particle reaches the ignition temperature the oxidation reactions are very vigorous.
These reactions are exothermic, releasing more heat than can be transferred to the surroundings
and the temperature therefore rises rapidly until the melting point is reached.
Kim [11] proposed that the melting of the particles starts in the inner sulfide core and proceeds
outwards because sulfides have lower melting points than oxides while the heat of fusion of
oxides is higher than that of the sulfides. The melting of particles during the reaction affects
the mechanism and the kinetics of the oxidation reaction changes from a gas-solid reaction
stage to gas-liquid reaction stage. Some of the oxygen is dissolved into the melt, while the rest
reacts with the sulfur to form SO2. As the particle reacts, the fraction of the product increases
and this has a retarding effect on the reaction rate.
2.2.1 Studies of chalcopyrite and pyrite combustion
Jorgensen and co-workers [12-18] at CSIRO, Australia pioneered studies of kinetics of flash
smelting using a laminar-flow furnace. Their apparatus is shown in Fig. 2.3. It consists of a
heated vertical reactor where particles of concentrate are injected into an air stream. The
reaction products are collected isokinetically in a second concentric pipe located at a given
distance below the feed pipe. The velocity of the gas through the furnace and the distance
between the injector and the collector are regulated to give the desired residence time.
They studied the effect of temperature, time, particle size and gas composition on the
percentage of original sulfur remaining defined as:
13
2 LITERATURE REVIEW
%S , x%Fe f ,
%SulJur (mxmal = x 100%
In general, the overall reaction has three distinct stages: the first part is a period during which
the reaction rate of the particles increases as they heat up to the ignition temperature; the
reaction is chemically controlled. The second part exhibits a relatively constant rate of reaction
during which most of the reaction occurs; the rate of reaction is now controlled by diffusion
of oxygen through the gaseous boundary layer. The third part corresponds to a relatively stable
period in which sulfur removal takes place at a reduced rate; the reaction is presumably
controlled by diffusion through an oxidized layer.
Particle
feeder
Hot go*
Particle -
injector
Vacuum
Heated -
furnace
tube
Rotameter
Particle,
collector
Filter
'(fume)
High- efficiency
cyclone
(particles)
Fig. 2.3 Apparatus used by Jorgensen [18]
14
2 LITERATURE REVIEW
2.2.1.1 Effect of particle size, temperature and oxygen concentration
The influence of the difference in size fraction for chalcopyrite can be seen from Fig. 2.4. The
initial screen size of the concentrate affects the time to attain ignition, the slope of the linear
portion and the final amount of residual sulfur. For the same residence time, coarse particles
have a higher % sulfur than smaller ones.
The effect of the experimental temperature on the oxidation of chalcopyrite is shown in Fig.
2.5. At higher temperatures the time to complete combustion is shorter. Increasing oxygen
concentrations has a similar effect to increasing experimental temperature due to its effect on
the average temperature which reduces the overall time of reaction as shown in Fig. 2.6.
u i i * i i
p
ii i
0 0.08 0.16 0.24
R e a c t i o n time, sec
Fig. 2.4 Effect of particle size on oxidation of chalcopyrite concentrate in air at 700 C [16],
O 74-105, A 53-74, 37-53, x < 37 p:m screen size fractions.
15
2 LITERATURE REVIEW
0 0.04 0 0 8 012
Reaction time, sec
Fig. 2.5 Effect of the experimental temperature on the combustion of 37-53 pm chalcopyrite
concentrate in air [16], O 600, A 700, 800, x 900, 1000, A 1100, 1200 C experimental
temperatures.
Reaction time, sec
Fig. 2.6 Effect of the oxygen concentration on the combustion of chalcopyrite concentrate in
oxygen-nitrogen mixtures at 700 C, 37-53 p.m screen size fraction, O 5, A 10, 21, x 30,
60, 100 vol. % oxygen. The dashed line is for a 1 % 0 mixture at 1000 C
2
16
' 2 LITERATURE REVIEW
2.2.1.2 Ignition temperature
The ignition temperature depends on the experimental conditions as a consequence of the heat
balance within the particle. Normally, the higher the oxygen potential, the lower the ignition
temperature. In the studies with the laminar-flow furnace [19], the ignition is understood as the
conditions (temperature and p0 ) where sulfur removal rate increases rapidly. Approximate
2
ignition temperatures in air are given in Table 2.3.
Table 2.3.: Approximate ignition temperatures for concentrates in air [19].
Mineral Formula Ignition Temperature (C)
Chalcopyrite CuFeS 2
470-500
Pyrite FeS 2 550-600
Pyrrhotite Fe . S
0 9 600-800
Chalcocite Cu S 2 800-900
Cu-mattes Cu S-FeS
2 800-900
Galena PbS 550-600
2.2.1.3 Time to attain ignition, oxidation time and oxidation rate.
The time taken to achieve ignition depends upon the heating conditions and the size of the
particles. By establishing a heat balance between the particle and the gas and assuming an
ignition temperature of 550 C for chalcopyrite and pyrite, Jorgensen [16] calculated the times
to reach ignition for particles introduced into air. Calculated times are in the range of 0.01 to
0.06 seconds for particle sizes ranging from 20 to 80 p:m in a stream of preheated air at 700
C.
17
2 LITERATURE REVIEW
The average oxidation time is the time taken by the particles to complete the oxidation and it
is around 100 milliseconds for 37-53 |im particles of chalcopyrite and pyrite, but the degree of
desulfurization is more complete for pyrite. The oxidation rate, expressed as % sulfur
remaining after oxidation, and the effect of temperature on it of four concentrates is shown in
Fig. 2.7.
400 600 800 1000 1200 1400
Experimental temperature (*C)
Fig. 2.7 Effect of temperature on the oxidation rate of various sulfides of 37-53 pirn in air [18].
18
2 LITERATURE REVIEW
2.2.1.4 Particle temperatures and vaporization.
Using a two colour pyrometer, Jorgensen [15,16] measured the temperatures attained by
chalcopyrite and pyrite particles, obtaining temperatures between 1612 and 2357 C depending
on the oxygen partial pressures.
Particle temperatures of pyrite were also measured by Tuffrey et al [20] who obtained
temperatures which are much higher (max 3127 C) compared to those reported by Jorgensen.
The discrepancy is attributed to the faster rate of data acquisition system of the pyrometer used
by Tuffrey as compared with Jorgensen's. Jorgensen and Tuffrey found that there is a
limitation in the particle temperature which was ascribed to the vaporization of copper and iron
species in chalcopyrite and pyrite respectively.
In the oxidation with air of a complex copper concentrate of particle diameter 37-53 pm,
Jorgensen [21] reported that particles oxidized at high temperatures became deficient in copper
while the fume generated was enriched in copper. The amount of copper vaporized increases
with temperature, becoming appreciable at temperatures above 1000 C and at 1400 C, 41 %
of the copper was vaporized. Calculation of the vapour pressures suggest that the vapour
species can be metallic copper, Cu 0 or CuO.

2
2.2.1.6 Particle fragmentation
Particle size has been found to change during reaction. The fine fraction more or less retains its
original particle size, whereas the coarse fraction undergoes pronounced disintegration.
Jorgensen [16] found that the final particle size approached a constant value of ~ 40 pm
19
2 LITERATURE REVIEW
regardless of the starting size. Munroe et al [22] found that particles over 70 pm in diameter
tended to fragment.
Fragmentation is believed to occur due to the following factors:
- Thermal and mechanical stresses during the initial heating to ignition temperature
- "Pinching o f f during melting due to surface tension. Jorgensen [14] suggested that
during reaction, the sulfide particles become coated with an oxysulfide melt. Surface
tension and drag forces then combine to tear relatively uniform sized droplets from this
layer.
- Gas evolution during the molten stage. Kim [11] analyzed the fragmentation of
chalcopyrite in detail. A schematic diagram of the proposed mechanism is shown in Fig.
2.8. Due to the differences in the melting rates and the fusion temperatures of sulfides and
oxides, a molten sulfide core enclosed by a solid oxide crust is first formed during
oxidation. Because of the vigorous dissociation and oxidation reactions, gas evolves
within the molten core, causing the crust to explode into pieces, so that the sulfidic core is
discharged as small droplets.
Increasing oxygen concentration by reducing nitrogen affects particle melting in a different
way. The heat released by the oxidation heats less nitrogen reducing the heat losses which
results in faster heating of the particles with a lower sulfur consumption. As a result, more
sulfur is entrapped in the molten phase.
20
2 LITERATURE REVIEW
When the initial particle size is large, the relatively large molten core and the amount of
entrapped labile sulfur increases the likelihood of fragmentation. After fragmentation the
droplets are exposed to further reaction with the surrounding gas.
Original Sulfide
Fig. 2.8 Model for fragmentation proposed by Kim [11].
21
2 LITERATURE REVIEW
2.2.2 Studies of chalcocite combustion
In most of the smelters, matte, the product of the flash smelting process, is further oxidized in
Peirce-Smith converters to obtain copper metal. In 1995, the Kennecott smelter installed the
first "Outokumpu-Kennecott flash converter". In this process, granulated and ground matte,
together with oxygen, are fed into another flash furnace, named the flash converter.
As in flash smelting, flash converting is an autogenous process. The matte reacts with oxygen
at a high temperature releasing heat needed to oxidize the particles. In order not to introduce
iron into the flash converter, the concentrate is oxidized in the flash furnace until the copper
comprises approximately 75 % of the matte, i.e., it is almost solely chalcocite.
Prior to the development of the flash converter, the Glogow smelter in Poland and Olympic
Dam in Australia have been treating chalcocite concentrate and producing copper metal
directly from the flash furnace. However, there have been few studies conducted on the flash
smelting of chalcocite, either chalcocite mineral or synthetic chalcocite (matte).
Suominen et al [23], Jokilaakso et al [19] and Riihilanti et al [24] studied the behavior of
copper mattes. Otero et al [25], Morgan et al [26] and Shook et al [27], studied the
^combustion of M K concentrate (a subproduct in the smelting of copper nickel concentrates)
from Inco Ltd which contains approximately 93 % chalcocite and 5-7 % pentlandite
(Fe,Ni) S .
9 8
22
2 LITERATURE REVIEW
The ignition point of chalcocite [23] in air is much higher than for chalcopyrite and pyrite
(around 900 C). Also, the oxygen partial pressure needed for ignition of chalcopyrite is only
5 % 0*2 as compared with mattes that need 10-21 % 0 [23]. 2
Suominen et al [23] studied the combustion of mattes with different contents of Fe and Cu and
found that the higher the Fe content (less copper) the more reactive is the matte. The effect of
particle size on the combustion characteristics of mattes was also studied and it was found that
the larges particles lost significantly more copper indicating higher particle temperatures
during the flash oxidation as compared to fine fractions. Particle fragmentation was also higher
for bigger particles.
Otero et al [25] examined the combustion of M K concentrate (93 % Cu S) in a stagnant gas

2
furnace, measuring the mass loss after combustion. They observed that chalcocite reacts more
violently than chalcopyrite with a high rate of generation of dust and the amount of reaction
products recovered after combustion was significantly smaller than that resulting from
conversion of Cu S to Q 1 2 O , CuO or Cu. Shook et al [27], based on Otero's observations,

2
modelled the combustion of M K concentrate and proposed the following mechanism for the
flash reaction of chalcocite:
At temperatures below the melting point of Cu S, the reaction rate is governed by chemical
2
kinetics of the reaction:
Cu S
2 (s) + 3/2 0 g ) ->
2( Cu 0
2 (s) + S0 ( )
2 g
23
2 LITERATURE REVIEW
At the melting point of the Cu S, the solid Cu 0 produced reacts with the liquid sulfide
2 2
according to the reaction:
Cu S i)
2 ( + 2Cu 0 2 (s) -> 6Cu i) + S 0
( 2 ( g )
The Cu 0 produced is consumed and the remaining Cu S reacts directly to produce metallic
2 2
copper:
Cu S (i) + 0
2 2( g ) - 2 Cu (i) + S 0 2(g)
This reaction is highly exothermic and the boiling temperature of copper can be reached (2563
C). When the Cu S is consumed, the copper is oxidized according to the reaction:
2
2Cu i) ( + 1/2 0 2 ( g ) -> C u 0

2 (s)
which proceeds until all the liquid copper is consumed either by oxidation or by evaporation
due to boiling.
Shook et al [27] proposed two mechanisms for dust generation: chemical, which comes from
the condensation of evaporated copper, and mechanical dust coming from particle explosions.
Morgan et al [26] observed that the particle is encapsulated by an outer layer enriched in
nickel. They measured particle temperature by a two colour pyrometer finding that the
temperature exceeds the boiling point of copper (2563 C) and suggested that S0 , together 2
with the copper vapor are formed within the nickel-rich shell of the particle. The built-up
pressure is relieved through the sudden release of the vapor by an explosion resulting in
particle fragmentation.
24
2 LITERATURE REVIEW
2.3 CHEMICAL AND MORPHOLOGICAL CHANGES
2.3.1. Prior to ignition
Pyrite
Thornhill and Pidgeon [28] prepared dense sulfides of troilite (FeS) and reported that during
the oxidation of FeS dense layers of hematite and magnetite were formed on the surface of the
particle. Thereafter, there was no further increase in the thickness of the reacted layer and the
sulfide had become pyrrhotite. In this series of experiments, pyrrhotite mineral was also
roasted and a columnar reaction interface was observed oxidizing preferentially along certain
crystallographic planes.
Asaki et al [29] studied the oxidation of pellets of troilite (FeS) and confirmed the above
observations. The oxidation proceeded in three stages: initially, iron diffused to the surface
where it was oxidized to form a thin layer of Fe 0 . The chemical reaction at this stage was:
2 3
FeS - Fei. S x + x Fe
2 Fe + 3 0 2 -> Fe 0
2 3
where Fe i_ S represents non-stoichiometric pyrrhotite. The rate of reaction was controlled by

x
the diffusion of iron through the sulfide. Then the oxide layer became thicker, and there was a
magnetite layer between the unreacted sulfide and the hematite layer. At this stage, the rate of
reaction was controlled by diffusion of iron in the oxide.
When the composition of the inner sulfide core reached Fe .9S

0 due to the progress of the
oxidation, the remaining sulfide core was oxidized in an irregular fashion according to the
reaction:
25
2 LITERATURE REVIEW
3 Fe,. S + (5-2x)0
x 2 - (l-x)Fe 0 + 3 S 03 4 2
2Fe 0
3 4 + 1/2 0 2 -> 3 F e 0 2 3
Gaseous oxygen appears to diffuse through the cracks in the oxide layer into the interior of the
sulfide core where these reactions take place. Jorgensen [30] observed that the cracking of the
oxide is a result from stresses produced by crystallographic and volume mismatch between the
pyrite and the oxide.
The continuing roasting of pyrite forms Fe 0 grains which exhibit a "butterfly" texture,
2 3
inherited from the texture of pyrrhotite. Pyrrhotite reacted from pyrite develops radial fibrous
masses from which pie-shaped pieces fragment, leaving a butterfly-like shaped particle. As
these particles are further oxidized to hematite, they form butterfly-shaped hematite particles
[31].
Chalcopyrite
As an initial step of thermal decomposition [4], the structural change of chalcopyrite starts at
about 550 C and is accompanied by a slight dissociation of sulfur:
a Chalcopyrite (tetragonal) > p Chalcopyrite (cubic)
The p-chalcopyrite phase is so-called "high temperature chalcopyrite". When heated below
650 C in an inert atmosphere or under vacuum, chalcopyrite loses sulfur gradually, producing
an intermediate solid solution, CuFe S (cubanite) [4] and Cu FeS (bornite):

2 3 5 4
9CuFeS 2 -> 4CuFe S + Cu FeS

2 3 5 4 + S 2
26
2 LITERATURE REVIEW
The intermediate solid solution then reacts to form bornite according to the reaction:
CuFe S
2 3 -> Cu FeS
5 4 + 9 FeS + S 2
The diffusion of iron atoms has also been observed in mixtures of copper iron sulfide by
Asaki et al [32], Tsukada et al [33] and Tanabe et al [34]. During the oxidation of pellets of
non stoichiometric bornite mixtures, Tanabe et al [34] observed that Fe diffused from the
interior of the sulfide towards the surface where it was oxidized. The oxide layer initially
formed was so thin that the oxidation rate was controlled by diffusion of Fe from the interior of
the sulfide. Since the oxide layer grew as oxidation progressed, the rate was controlled by the
diffusion of Fe in the oxide layer. The amount of Fe in the sulfide decreased to about 90 % of
the initial quantity until the sulfide composition corresponded to the line between Cu S and
2
CusFeS in the ternary phase diagram.

4
Thornhill and Pidgeon [28] roasted chalcopyrite particles (30 - 40 mesh) in air at 550 C and
detected digenite (Cui.gS), a defect structure of Cu S. Once digenite is formed by the initial
2
burning of sulfur and iron at the surface of the chalcopyrite particle, this phase permits rapid
inward diffusion of copper and outward diffusion of iron. When the entire kernel was
converted to digenite, the copper appeared to roast in preference to the sulfur to the point at
where digenite begins to transform to covellite.
Covellite a n d Chalcocite
Covellite begins to break down to digenite (Cui.gS) and sulfur at 235 C [35] in an inert
atmosphere :
27
2 LITERATURE REVIEW
2 CuS -> Cui.gS + 0.1 Cu S 2 + 0.4 S 2
Digenite is a defect structure of chalcocite which occurs naturally as Cu . S with x ranging 2 x
from 0.12 to 0.45 and an average analysis of Cui.gS [36] .
As in the case of troilite (FeS), in the roasting of chalcocite Thornhill and Pidgeon [28]
observed a dense layer in contact with the sulfide surface, and a porous product in a
secondary layer. The sulfide kernel was converted to digenite. The proposed chemical
reactions are:
Cu S
2 + 0 2 - Cu S 18 + 0.1 Cu 0 2
Cu,. S + 0
8 2 - 0.9 Cu 0 + S 0
2 2
The conversion to digenite is another point of similarity between the behavior of troilite and
chalcocite since the digenite phase, like pyrrhotite, exists as a defect structure which permits
considerable deviation from the stoichiometry of the chalcocite.
The oxidation of Cu S results in different end-products at different temperatures [37]. At

2
temperatures above 800 C the oxidation sequence is Cu S > Cu 0 > CuO; between about
2 2
680 C and 800 C the sequence is Cu S 2 Cu 0 -> CuO -> CuO.CuS0 ; finally, at less
2 4
than 680 C the oxidation route is Cu S 2 -> Cu 0 -> CuO.CuS0

2 4 - CuS0 . 4
Kim and Themelis [38] roasted pellets of chalcocite finding also that when the pellet
temperature reaches 943 C formation of elemental copper occurs by the reaction between
Cu S and Cu 0.
2 2
28
2 LITERATURE REVIEW
2.3.2 Ignition
Jorgensen [10] suggested that ignition of pyrite and chalcopyrite is due to the structural
transformation of both minerals during oxidation. The transformation of pyrite into pyrrhotite
involves 20 % reduction in volume. The transformation of chalcopyrite into the intermediate
solid solution involves a reduction in volume of 15 %. The resulting porous open structure
allows the ingress of oxygen, leading to ignition.
2.3.3 Post ignition
Spheres, cenospheres and fragmented grains are typical of the particles obtained from the flash
reaction of chalcopyrite, pyrite and chalcocite. They result from melting and liquid-gas
reactions.
The spheres are formed by complete melting within the furnace. Cenospheres are formed by
the dissolving of oxygen in the melt and release of sulfur dioxide. Fragmented particles result
from sphere disintegration and broken cenospheres [39,40,41]. The mechanism of formation
of cenospheres proposed by Kim [11], consisting of the evolution of S O 2 inside the particle,
is also applicable to chalcocite considering that the vaporization of copper also occurs [26,27].
Otsuka and Soma [42] found two kinds of spherical particles when pyrite was oxidized: large
hollow cenospheres with smooth thin shell and smaller oxide particles (not hollow). Tuffrey et
al [20] suggested that convective transport of Fe (II) and Fe (HI) in the sulfide-oxide interface
would allow the generation of S O 2 gas, providing a mechanism for formation of the thin-wall
cenospheres found in pyrite.
29
2 LITERATURE REVIEW
Asaki et al [43] carried out experiments of oxidation where molten iron sulfide was oxidized in
a capillary tube sample holder with argon gas containing oxygen flushed across the open end of
the capillary and found that oxygen is first absorbed into the melt without removal of sulfur.
After reaching a composition very close to the FeS-FeO pseudo-binary system, the FeS was
oxidized to produce FeO:
FeS a) + 3/2 0 )
2(g - FeO D +
( S0 2(g)
The melt then became a solution of FeO and FeS with a composition from 0.22 to 0.66 mole
fraction FeO. Oxidation then proceeded according to the equation:
3FeO i) ( + 1/2 0 2 ( g ) -> Fe 0 ( )

3 4 S
Ajersch and Toguri [44], using the apparatus mentioned above, investigated the oxidation of
liquid copper and liquid copper sulfide. They found that the oxidation proceeds first with the
formation of copper followed by the formation of copper oxide after all the sulfide had been
oxidized.
Alyaser and Brimacombe [45] studied the kinetics of the oxidation of molten chalcocite baths
during top-lancing. The reaction occurred in two stages. During the first stage, the melt was
partially desulfurized accompanied by dissolution of oxygen into the liquid sulfide. Upon
saturation with dissolved oxygen (~ 1.35 % oxygen), metallic copper and S 0 gas bubbles2
were observed. Both stages were found to be limited by oxygen mass transfer in the gas phase.
30
2 LITERATURE REVIEW
Yannopoulos et al [46] studied the oxidation of small droplets of matte (mixtures of Cu S and
2
FeS) on a layer of fine silica finding that the composition of the starting matte has a strong
influence and that the oxidation of ferrous sulfide is significantly faster than the oxidation of
cuprous sulfide. Under identical experimental conditions, the rate of oxidation of low copper
grade matte (high iron content) was more than double that of high grade matte (low iron
content). In these experiments, there was evidence that fayalite is the first ferrous compound
and that fayalite decomposes to Fe 0 and S i 0 at higher oxygen concentrations.

3 4 2
31
3 SCOPE AND OBJECTIVES
It has been reported [47] that operational problems such as buid-up of unreacted concentrate at
the bottom of the reaction shaft and uptake shaft of the furnace occur in a copper smelter when
La Escondida concentrate is treated in blending proportions in excess of 20 %. La Escondida is
a high grade copper concentrate based on chalcocite ( C U 2 S ) . Previous studies on chalcocite and
chalcopyrite [25-27] found that chalcocite has higher ignition temperature and reacts much
more violently than chalcopyrite (CuFeS2), causing explosions and generating high amounts of
dust. Therefore, it is the objective of the present work to examine experimentally the single
particle combustion behavior of La Escondida concentrate and to compare it with that of La
Caridad, a concentrate consisting of chalcopyrite (CuFeS2), pyrite (FeS2), chalcocite (Cu S) 2
and covellite (CuS). La Caridad is also treated in a flash furnace.
The experimental work consisted of reacting concentrate in a stagnant gas furnace at different
atmospheres, temperatures and particle sizes. The oxidized products were then subjected to
several types of analysis: chemical analyses were performed to determine the sulfur remaining
in the sample indicating the extent of reaction and thereby giving a measure of the reaction
kinetics. The copper-iron ratio was measured to examine the degree of volatilization. X-ray
diffraction was carried out to identify the phases present. Scanning electron microscopy and
optical microscope analyses were conducted to characterize the changes in the particles during
reaction.
The experimental results are helpful in providing fundamental understanding of the flash
reaction mechanisms of La Escondida concentrate.
32
4 EXPERIMENTAL
4 EXPERIMENTAL
4.1 Experimental Set-up
The stagnant gas furnace used in the experiments is shown in Fig. 4.1. The reactor is a
cylindrical fused quartz tube of 71 mm DD, 2 mm thickness and 584 mm height which is
heated externally by a 6 kW furnace. The furnace is split into two halves which are hinged to
facilitate access and observe the ignition. A temperature controller is coupled to a type K
(chromel-alumel) thermocouple located inside the quartz tube, 100 mm below the top.
A vibrator was used to regulate the concentrate feed rate through an air-cooled feeding tube. At
the bottom, a rubber plug sealed the lower part of the furnace. A stainless steel pipe for gas
supply was inserted through the plug, while a water-cooled copper plate was installed to collect
the reaction products. In order to cool the reaction products and avoid contact with water, the
reaction products were collected in an aluminum tray immersed in water contained in a copper
cup.
Cylinders of oxygen (99% purity), nitrogen (99.95% purity) and anhydrous sulfur dioxide
(99.98% purity) were used to create different atmospheres.
4.2 Procedure
Two concentrates were tested, "La Escondida" and "La Caridad". They were first screened to
separate the particle sizes of + 400 -500 mesh and + 270 - 325 mesh. Before feeding the
concentrate, the furnace was heated to the desired temperature and the reaction tube was then
filled with the given atmosphere (100 % 0 , 50 vol % 0 - 50 vol % N , 90 % vol S 0 -10 %
2 2 2 2
0 , and 100 % N ).
2 2
33
4 EXPERIMENTAL
337mm
Termocouple
(type K)
.Refractory brick
chrome-magnesite)
Heating elements
Reaction tube
(id = 71 mm)
i i
Temperature controller
TO SCALE
Omega CN9000A
Fig. 4.1 Experimental apparatus
Note: Due to excessive condensation of SO2, with the 90 % SO2 - 10 % O2 gas mixture, the
air-cooled feeder had to be replaced by a quartz tube and the water used to cool the reaction
products had to be removed. In the presence of water and a catalyst (possibly iron or copper
oxide) S O 2 is converted to S 0 and H 2 S O 4 .
3
34
1
4 EXPERIMENTAL
Concentrate was fed at an average mass flowrate of 60 mg/min (0.0036 kg/h), with the feed
rate controlled by the amplitude of the vibrator. To minimize clustering of the concentrate, the
500 mesh fraction was dried prior to each experiment in a 1500 watt Despatch oven. The 325
mesh fraction flowed very readily so that it was difficult to control its feed rate. Therefore this
size fraction had to be hand-fed into the reactor.
To ensure that all particles were exposed to the same gas composition, the tube was flushed
continuously by a low flow of gases of the atmosphere, ranging from 90 to 180 Scm /min 3
during each experiment. This flow was low enough that it did not affect the temperature of the
furnace, yet high enough to replace the oxygen consumed during the experiment.
Solid reaction products were collected and analyzed for sulfur, iron and copper. Chemical
analyses of copper and iron were obtained by a Perkin Elmer 2100 Atomic Absorption
Spectrometer. Sulfur analyses were performed gravimetrically by precipitating the sulfur as
barium sulfate and calcining it at 700 C in a Furnatrol - Thermolyne oven. The percent of
original sulfur, normalized with respect to iron, was calculated from the formula:
%S , X%Fe f ,
%Sulfur
orimml = ^ x 100%
n8inal % S f e e d x%Fe s a m p l e
The reaction products were also examined by X ray diffraction (Philips PW 1078/50), by an
Optical Microscope (Leitz Orthoplan) and by a Scanning Electron Microscope (Hitashi S-
35
4 EXPERIMENTAL
2300). Some streak photographs were taken with a 35 mm Camera Canon EOS 650 (200
ASA).
4.3 Variables studied
Since most reactions occur between 600 and 900 C, this range of temperature was selected for
this study. However, it was also necessary to react the 325 mesh "La Caridad" concentrate at
500 C because the reactions were almost complete at 600 C.
The atmospheres studied were 100% oxygen, 50% oxygen - 50% nitrogen (volume %) and
100% nitrogen. In addition, a mixture of gases consisting of 90% sulfur dioxide and 10%
oxygen (volume %) was chosen to simulate the atmosphere in the flash furnace.
Particle sizes of + 400 - 500 mesh (+25 -38 um ) and + 270 - 325 mesh (+45 -53 um ) were
selected because these two size fractions represent major fractions of the two concentrates. To
simplify the nomenclature, particle sizes of + 400 - 500 mesh are referred to hereafter as 500
mesh while the + 270 - 325 mesh fraction is referred to as 325 mesh.
4.4 Preparatory tests
Temperatures profiles were determined to ensure that the temperature was uniform.
Temperatures were measured along the axis of the column for given settings of the
temperature controller. It was found that the temperature was uniform over a height of 160
mm for controller settings of 600 and 700 C and approximately 150 mm for settings of 800
and 900 C (see Fig. 4.2). The recorded temperature did not vary with the introduction of a
purge gas.
36
4 EXPERIMENTAL
Temperature C
1000:
900 -* * * X * K
800 Controller
Iset point:
700
600 HI m Br m- ffl- - 500 c
HS 600 C
500
-* 700 C
400 -X 800 C
300 *-900C
200 +
100
0
5 10 15 20
Distance f r o m t o p ( m m )
Fig. 4.2 Temperature profiles taken axially along the reaction tube at different controller
settings. Gas atmosphere: Air; no feeding of concentrate
37
4 EXPERIMENTAL
In order to ensure the proper gas composition, gas samples were withdrawn for analysis with a
gas chromatograph (Varian 3400) at different times during filling of the reactor. It was found
that six times the volume of gases in the reactor had to be added to remove the previous
atmosphere.
The accuracy of the gas composition depended on the accuracy of the rotameters. These
rotameters were calibrated by timing the rise of soap bubbles displaced by the gas in a burette.
A low flow rotameter was used for oxygen to create the 90 % S 0 - 10 % 0 . (volume %) gas
2 2
mixture. The residence time in the region of the isotherm was estimated based on the Stokes'
law equation:
u
~
M
=
" 8
1877
This assumes that the particles are spherical and that the purge gas creates a uniform velocity
field without appreciable turbulence. The Reynolds number obtained in the calculations of the
particle sizes ranged from 0.005 to 0.225 confirming that the creeping flow (i.e. Stokes law)
assumption is reasonable. Fig. 4.3 shows the residence time in the isothermal region as a
function of temperature. However, due to the dynamics of the particles and the fact that the
particles experience fragmentation, these residence times should only be considered as
approximate average values.
4.5 Reproducibility of the results
The gravimetric method used for the analysis of sulfur, has an acurancy of 0.5% S. However,
due to dispersion of the feed concentrate during the experiments, variations up to 1.5% S were
38
4 EXPERIMENTAL
Residence time (s)

6 i
2 +
400 500 600 700 800 900 1000
Temperature (C)
Fig. 4.3 Calculated residence time of different particle sizes in the furnace in the region of
the isotherm. Atmosphere: 100 % oxygen; purge gas flow: 90 ml/min; particle density:
4670 kg/m .3
39
4 EXPERIMENTAL
obtained. This variation in sulfur causes the % S remaining in the reaction products to vary
from 3 to 5 % depending on the % S in the samples.
4.6 Characterization of the two concentrates
4.6.1 " La Escondida" Concentrate
"La Escondida" concentrate from Chile was supplied by BHP Copper. Table 4.1 shows its
particle size distribution. The chemical composition as well as the mineralogical composition
(calculated and confirmed by XRD) are given in Table 4.2.
Image analysis of "La Escondida" concentrate with SEM was conducted by G. Caffery [48] to
determine the relative abundance of each phase, as well as the proportion of the phases in the
particles. Results of the image analysis are summarized in Table 4.3.
4.6.2 "La Caridad" Concentrate
"La Caridad" concentrate was received from Mexicana de Cobre, S.A. Table 4.4 shows the
particle size distribution, while Table 4.5 gives the chemical and mineralogical composition.
The contrast between chalcopyrite - pyrite and covellite - chalcocite with the SEM in the
backscatter mode, was not good enough to allow image analysis. Therefore it was necessary to
perform the image analysis using an optical microscope. Results are summarized in Table 4.6..
40
4 EXPERIMENTAL
Table 4 1. Particle Size Distribution of La Escondida Concentrate
Size fraction Mass

(urn) %
<25 1.1
+25 -38 51.3
+38 -45 15.4
+45 -53 14.9
+53 -63 5.4
+63 -75 4.3
>75 7.6
Total 100
Table 4.2 Chemical and Mineralogical Composition of La Escondida Concentrate
Size fraction C lemical Mineraloqica

lam) % Cu % Fe %S % Si0 %Cc2 % Pv
As received 49.0 11.9 26.7 8..0 61.4 25.5
+25-38 um 51.8 9.7 24.5 64.8 21.1
+45-53 um 50.7 14.2 29.7 _

63.6 30.9
Abbreviations: Py: Pyrite (FeS2)

Cc: Chalcocite (Cu S) 2
41
4 EXPERIMENTAL
Table 4.3 Image Analysis of La Escondida Concentrate.
500 mesh 325 mesh

Mass Proportion of Mass Proportion of
% phases in the % phases in the
particle particle
% Pv % Cc % SiO? % Pv % Cc % SiQ>
Pure Py 8.4 100 4 100
Pure Cc 35.5 100 17 100
Cc + Py 20 40 60 27 37 63
Cc + Si02 8 85 15 6 90 10
Py + Si02
2 85 15 3.5 89 11
Cc + Py + Si0 2 15 20 70 10 39 34 62 4
Pure Si02
8 100 1.7 100
Other 3.1 1.8
Total 100 100
Abbreviations Py: Pyrite (FeS2)

Cc: Chalcocite (Cu S)
2
42
4 EXPERIMENTAL
Table 4.4 Particle Size Distribution of La Caridad Concentrate.
Size fraction Mass

(um) %
<25 2
+25 -38 43.7
+38 -45 12.1
+45 -53 26.6
+53 -63 6.6
+63 -75 4
>75 5
Total 100
Table 4.5 Chemical and Mineralogical Composition of La Caridad Concentrate.
Size fraction Chemical Minera oqical

(um) % Cu % Fe % S % Si0 % Pv %Cp
2
%Cv % Cc
As received 29.5 26.9 36.9 2.4 25 50 8.7 8
+25-38 um 34.7 24.0 36.0 19 49.7 13.9 10.4
+45-53 am 25.4 31.0 41.0 _

52.1 21.9 7.9 15.7
Abbreviations Py: Pyrite (FeS2)

Cp: Chalcopyrite (CuFeS ) 2
Cv: Covellite (CuS)
43
4 EXPERIMENTAL
Table 4 . 6 Image Analysis of "La Caridad" Concentrate
500 mesh 325 mesh

Mass Proportions of phases Mass Proportions of phases
% in the particles % in the particles
Py Cp Cv Cc Py Cp Cv Cc
Pure Py 18.8 100 51.0 100
Pure Cp 42.5 100 12.4 100
Pure Cv 10.9 100 3.7 100
Pure Cc 5.9 100 11.0 100
Cp + Cv 6.6 55 45 7.5 62 38
Cp + Cc 7.3 39 61 8.3 46 54
Py + Cv - 2.1 37 63
Py + Cc - 0.3 71 29
Py + Cp 1.1 26 74 0.6 75 25
Cp + Cv + Cc 0.8 77 13 10
ZnS 3.4 -
Silica + Other 3.1 2.3
Total 100 100
Abbreviations: Py: Pyrite (FeS2)

Cc: Chalcocite (Cu S)
2
Cv: Covellite (CuS)
44
5 EXPERIMENTAL RESULTS
5.1 Observations of reacting particles
The design of the stagnant gas furnace permits a visual observation of the reacting particles.
Fig. 5.1 (a) and (b) shows sample photographs of La Escondida 325 mesh reacting at 600 C
in a 100 % O 2 atmosphere. It can be seen that the particles seem to explode ejecting pieces in
all directions. The following observations were recorded for burning particles during the
experiments:
- At 100 % 0 and 50 % 0 - 50 % N , La Caridad 325 and 500 mesh looked brighter

2 2 2
with higher luminosity than La Escondida for all conditions, indicating that higher
temperatures were reached.
- At 90 % S 0 - 10 % 0 little evidence of burning was seen in both concentrates.

2 2
- At 100 % N there was no evidence of burning.

2
5.2 Sulfur Removal
The loss of sulfur is a measure of the reactivity and of the extent of reaction. The effect of
furnace temperature on the sulfur left in the sample, after exposure to the furnace, for different
atmospheres is shown in Figs. 5.2 - 5.5.
The results for the two concentrates are plotted together in order to see their relative
combustion behavior. Sulfur remaining after exposure at 100 % oxygen is shown in Fig. 5.2 It
can be seen that the 325 mesh particle size is more reactive than the 500 mesh fraction for both
concentrates. Comparing the two concentrates at the same particle size, it is clear that La
Caridad 325 mesh is more reactive than La Escondida 325 mesh. However, La Escondida
45
appears to be more reactive than La Caridad for the 500 mesh fractions.
325 mesh La Caridad burned practically to completion at 600 C so that it was necessary to
0
burn it at 500 C. A pronounced sulfur loss occurred between 500 and 600 C.
0 0
The sulfur remaining in La Caridad and La Escondida for a 50 % oxygen - 50 % nitrogen
atmosphere is shown in Fig. 5.3. The curves show the same form as for a 100 % oxygen
atmosphere. For the 500 mesh fraction the sulfur remaining was similar for the two
concentrates and higher than for 100 % 0 .The sulfur loss for 325 mesh differed only slightly
2
at 100 % 0 2
The sulfur left in the reaction products for 90 % S 0 -10 % 0 gas composition is shown in
2 2
Fig. 5.4. Except for La Caridad of 325 mesh, the differences between La Escondida and La
Caridad are relatively small. The sulfur remaining is less affected by the particle size at lower
oxygen concentration for La Escondida concentrate. A test with La Escondida 500 mesh for a
90 % nitrogen - 10 % oxygen gas mixture was performed to see whether S 0 affects the sulfur
2
retention. The results obtained with 90 % N were lower than those with 90 % S 0
2 2 These
results are included in Fig. 5.4.
Contrary to the other conditions, the loss of sulfur for 500 mesh La Escondida and 100% N 2
(Fig. 5.5) is higher than that for the 325 mesh particle size. The maximum sulfur that can be
lost at 100% N is the pyritic sulfur contained in pyrite, i.e. 23% for 500 mesh and 27% for 325
2
mesh. La Escondida 500 mesh particle size lost the pyritic sulfur at 800 C whereas the 325
mesh retained the pyritic sulfur at 900 C.
In the case of La Caridad, the sulfur remaining at 100 % N for the 500 mesh fraction is higher
2
than for the 325 mesh fraction. La Caridad contains pyritic sulfur in chalcopyrite and pyrite
47
5 E X P E R I M E N T A L RESULTS
100 % Oxygen
% Sulfur left in the reaction products
- L E 500
mLE 325
-ALC 500
- * - L C 325
400 500 600 700 800 900 1000
Temperature C
Fig. 5.2 Effect of temperature on the sulfur remaining after combustion of 500 mesh and 325
mesh L a Escondida and L a Caridad at 100 % oxygen.
Abbreviations:
LE 500: L a Escondida 500 mesh fraction size
LC 500: L a Caridad 500 mesh fraction size
A : Sulfur content in Cu S for L a Escondida 500 mesh fraction size

2
B: Sulfur content in Cu S for L a Escondida 325 mesh fraction size

2
C: Sulfur content in Cu S for L a Caridad 500 mesh fraction size

2
D: Sulfur content in Cu S for L a Caridad 325 mesh fraction size

2
48
Temperature C
Fig. 5.3. Effect of temperature on the sulfur remaining after combustion of 500 mesh and 325
mesh L a Escondida and L a Caridad for a 50 % oxygen - 50 % nitrogen gas atmosphere.
Abbreviations:
L E 500: L a Escondida 500 mesh fraction size
L E 325: L a Escondida 325 mesh fraction size
L C 500: L a Caridad 500 mesh fraction size
L C 325: L a Caridad 325 mesh fraction size
A : Sulfur content in Cu S for L a Escondida 500 mesh fraction

2 size
B: Sulfur content in Cu S for L a Escondida 325 mesh fraction
2 size
C: Sulfur content in Cu S for L a Caridad 500 mesh fraction
2 size
D: Sulfur content in Cu S for L a Caridad 325 mesh fraction
2 size
49
Fig. 5.4. Effect of the experimental temperature on the percentage of sulfur remaining after
combustion of 500 mesh and 325 mesh La Escondida and 500 mesh and 325 mesh La
Caridad for a 90 % sulfur dioxide-10 % oxygen gas mixture.
Abbreviations:
LE 500: La Escondida 500 mesh fraction size
LE 325: La Escondida 325 mesh fraction size
LC 500: La Caridad 500 mesh fraction size
LC 325: La Caridad 325 mesh fraction size
LE 500 w/N La Escondida 500 mesh at 90 % N - 10 % 0 .
2 2 2
\
A: Sulfur content in Cu S for La Escondida 500 mesh fraction size
2
B: Sulfur content in Cu S for La Escondida 325 mesh fraction size

2
C: Sulfur content in Cu S for La Caridad 500 mesh fraction size

2
D: Sulfur content in Cu S for La Caridad 325 mesh fraction size

2
50
100 % Nitrogen
% S u l f u r left in t h e r e a c t i o n p r o d u c t s
100
- L E 500
- LE 325
- & LC 500
-K LC 325
400 500 600 700 800 900 1000
T e m p e r a t u r e C
Fig. 5.5 Effect of temperature on the sulfur remaining after combustion of 500 mesh and 325
mesh L a Escondida and L a Caridad at 100 % nitrogen.
Abbreviations:
E: Pyritic sulfur for L a Escondida 500 mesh fraction size

F: Pyritic sulfur for L a Escondida 325 mesh fraction size
G: Pyritic sulfur for L a Caridad 500 mesh fraction size
H: Pyritic sulfur for L a Caridad 325 mesh fraction size
51
which is 32.6 % for the 500 mesh and 41.8 % for 325 mesh. It can be seen in Fig. 5.5 that La
Caridad did not undergo complete thermal dissociation at 900 C for either particles size.
5.3 Copper-Iron Ratio
In order to determine whether the copper remains in the reaction products or if there is
volatilization, the ratio of copper and iron concentrations has been calculated.
Since the two concentrates have very different copper-iron ratios, it is convenient to plot the
copper-iron ratio for each concentrate for the different atmospheres and to compare the results
with the original copper-iron ratio of the concentrate.
The copper-iron ratio obtained for La Escondida concentrate is shown in Fig. 5.6. There is no
clear trend for the 500 mesh La Escondida. For 100 % 0 2 and for 50 % 0 - 50 % N , the
2 2
Cu/Fe ratio decreased by 17 % for La Escondida 325 mesh between 600 and 900 C.
As shown in Fig. 5.7, the copper-iron ratio for La Caridad 500 mesh was unaltered for 50 % 0 2
- 50% N and 90 % S 0 - 10 % 0 gas mixtures. At 100 % 0 , the Cu/Fe decreased by 18 %

2 2 2 2
with respect to the ratio in the original concentrate. For La Caridad 325 mesh, the ratio
decreased in the same proportion ( 18 %) at 50 % 0 - 50% N and 100 % N . However, for

2 2 2
the 90 % SO -10 % 0 atmosphere the ratio did not show any discernible variation. At 100%
2 2
N the Cu/Fe ratio remains essentially unaltered for La Caridad.

2
52
a)
Cu/Fe (mass %)
m-r 1 oo % O2
- A 50 % 0 2 - 50 % N 2
90 % S 0 - 10 % 0 2 2
100 % N 2
500 600 700 800 900 1000

b)
Cu/Fe (mass %)
e 100 % 0 2
-A50 % O2 - 50 % N 2
e 9 0 % SO2 - 1 0 % 0 2
* - 1 0 0 % N 2
500 600 700 800 900 1000
Fig. 5.6 Copper-iron ratio for La Escondida concentrate.

a) La Escondida 500 mesh particle size
b) La Escondida 325 mesh particle size
53
a)
Cu/Fe ( m a s s % )
100 % o 2
A50% O -50 % N
2 2
- 9 0 % SO -10% O2!
2
*-100 % N 2
400 500 600 700 800 900 1000

b)
Cu/Fe ( m a s s %)
- e 100 % o 2
- A 50% 02-50 % N 2
- e 9 0 % SO -10% <Dj 2 2
-*-100%N 2
400 500 600 700 800 900 1000
Fg. 5.7 Copper-iron ratio for La Caridad concentrate.

a) La Caridad 500 mesh particle size
b) La Caridad 325 mesh particle size
54
5.4 X Ray Diffraction Analyses
The X Ray Diffraction analyses obtained were difficult to interpret because most of the oxides
have similar diffraction patterns. For example, in the 2-theta range of 35.4 - 35.8, FeFe 0 , 2 4
CuO, CuFe 0 and CuFe0 have 100 % intensity, while CuO,

2 4 2 Feo.980, F e 0 3
2 have intensities
of 60, 80 and 70 % respectively. In order to consider these peaks, these compounds are referred
to as Oxide-Group # 1 in Tables 5.1 to 5.4.
Also, in the 2-theta range of 36.2 - 36.5, Fe Si0 , Fe 0 , Cu 0, CuFe0 have 100 % intensity.
2 4 3 4 2 2
These compounds are referred to as Oxide-Group # 2.
Tables 5.1 and 5.2 show the phases present in the reaction products for 100 % 0 2 and 50 %
0 - 50% N atmosphere. At these conditions, oxides of copper, iron and copper iron spinel
2 2
are present. Copper sulfides and metallic copper are also present. Differing from La Escondida,
La Caridad did not show a peak in oxide group # 2 . This may be because oxide group # 2
includes fayalite ( Fe Si0 ), and La Caridad contains little Si0 .

2 4 2
The phases detected for a 90% S 0 - 10 % 0 atmosphere are shown in Table 5.3 La Caridad
2 2
shows the presence of iron sulfides and pyrite, differing from La Escondida where the sulfur is
contained in copper sulfide. La Caridad 500 mesh particle size contains more chalcopyrite
(CuFeS ) than 325 mesh, while La Caridad 325 mesh contains more pyrite than the 500 mesh
2
fraction. This is because of the difference in proportions of chalcopyrite and pyrite in the
concentrate.
CuS0 was present in La Escondida 500 mesh in a bigger proportion than in the 325 mesh
4
fraction. CuS0 was also detected in the La Caridad 500 mesh fraction.
4
55
Table 5.1 Phases present for 100 % 0 atmosphere. 2
LE 500 Oxide group # 1, # 2, Cu Q, Cu S. CuFe0 , F e 0 , CuO

2 2 2 2 3
LE 325 Oxide group # 1, # 2, CuFe0 , CuO 2
LC 500 Oxide group # 1, Cu, CuFe 0 , FeFe 0 , CuO

2 4 2 4
LC 325 Oxide group # 1, Cu, CuFe 0 , 2 4 FeFe 0 , CuO 2 4
Table 5.2 Phases present for a 50 % 0 - 50 % N atmosphere.

2 2
LE 500 Oxide group # 1, # 2, C u A CuO, CuFe 0 2 4
LE 325 Oxide group # 1, # 2, Cu 0 , CuO, CuFe 0

2 2 4
_C 500 Oxide group #1, Fe 03, CuFe 0

2 2 4
LC 325 Oxide group # 1, Cu (bigger *), CuFe 0 , FeFe 0 , CuO 2 4 2 4
* compared to LC 500 and LC 325 at 100 % Q 2
56
Table 5.3 Phases present for a 90 % S 0 - 10 % 0 atmosphere. 2 2
LE 5 0 0 C u S 0 , Oxide group # 1, # 2 , Cu S, Fe 0 , Cui. S

4 2 2 3 81
LE 3 2 5 CUSO4. Oxide group # 1, # 2, FeFe 0 , Fe 0 , Cu S

2 4 2 3 2
LE 5 0 0 w/N 2
Same as LE 5 0 0 excluding CuS0 . 4
LC 5 0 0 CuFeS (bigger*), FeS (smaller*), FeS , Oxide group #1,

2 2
Cu FeS ,
5 CuS04 4
LC 3 2 5 CuFeS 2 (smaller**), FeS (bigger**), Oxide group #1
Table 5.4 Phases present for a 100 % N atmosphere. 2
LE 5 0 0 CuFeS , CuFe S , Cu FeS , Cu S,

2 2 3 5 4 2 C U L S I S , Cui. S, FeS
96
LE 3 2 5 CuFeS , CuFe S , Cu FeS Cu S, C u m S ,

2 2 3 5 4) 2 CUI. 9 6 S, FeS 2
LC 5 0 0 CuFeS (bigger*), FeS , FeS , Cui. iS

2 2 8
LC 3 2 5 CuFeS (smaller**), FeS , FeS , Cui. iS

2 2 8
* compared to LC 325
** compared to LC 500
57
Despite the fact that La Escondida contains only traces of chalcopyrite, for a 100 % N 2
atmosphere both particle sizes of La Escondida show the presence of chalcopyrite (CuFeS2) in
higher proportions than in the original concentrate indicating that chalcopyrite is formed.
Cubanite (CuFeiSs), considered as an intermediate solid solution [4] in the thermal
decomposition of chalcopyrite and bornite (Cu FeS ), is also present. This indicates that not
5 4
only is chalcopyrite formed but also some chalcopyrite is dissociated
The XRD results for La Caridad are similar for the two particles sizes. However, the amount of
chalcopyrite is larger in La Caridad 500 mesh than in 325 mesh because there is more
chalcopyrite in the 500 mesh fraction size in the original concentrate.
58
5.5 Microscopic examination
Spheres and cenospheres were found in the reaction products for 100 % oxygen and 50 %
oxygen - 50 % nitrogen atmospheres in both concentrates at all temperatures except 500 C.
Fig. 5.8 is an image of La Escondida 325 mesh after reacting in a 100 % G* atmosphere at 600
2
C. Spheres and near-spheres of different sizes with rough texture and different proportions of
Cu-Fe-S are predominant in the reaction products of this concentrate. Fig. 5.9 is an image of
La Caridad concentrate after being exposed to a 50% O -50 % N atmosphere at 700 C. The
2 2
spheres are more uniform, with some of them consisting of iron oxide due to the higher
proportion of pyrite in this concentrate. An irregular cenosphere is present at the top right hand
corner, probably originating from chalcopyrite.
Cenospheres of iron oxide were found. They have thin shells and smooth textures as seen in
Fig. 5.10. Cenospheres of copper sulfide have a rough texture. Fig. 5.11 shows a cenosphere
of copper sulfide with small particles of copper and copper sulfide inside it.
Molten drops of copper sulfide (Cu S) and bornite (Cu5FeS ) with rims of iron oxide and
2 4
inclusions of iron-cupro spinel (CuFe 04) were found in La Caridad at all temperatures except
2
500 C. Fig. 5.12 shows a SEM image in the backscatter mode where the lighter patches are
Cu S and drops of CuFe C4 appear to be separated from the iron oxide. Fig. 5.13 shows drops
2 2
of CuFe 04, CuFe0 and Fe oxide. A particle of pyrrhotite is also present.

2 2
59
Fig. 5.8 SEM image of reaction products of 325 mesh La Escondida concentrate at after
reacting in a 100 % oxygen atmosphere at 600 C
Fig. 5.9 SEM image of reaction products of 325 mesh La Caridad concentrate after reacting
in a 50 % 0 - 50 % N atmosphere at 700 C.
2 2
60
Fig. 5.10 SEM image of cenosphere of iron oxide found in the reaction products of 325 mesh
La Escondida concentrate for a 50 % 0 - 50 % N atmosphere at 800 C.
2 2
Fig. 5.11 SEM image of cenosphere of Cu S found in the reaction products of 500 mesh La
2
Escondida for 100 % 0 at a temperature of 900 C.

2
61
Fig. 5.12 Particle of C112S covered with iron oxide with separated inclusions of C u F e 02 4
found in La Caridad 325 mesh after reacting in at 50% 0 - 50% N atmosphere at 800 C.
2 2
Image obtained by backscatter mode.
Fig. 5.13 S E M image of a particle of pyrrhotite and particles of CuFe 04, CuFe0 and Fe
2 2
oxide found in the reaction products of La Caridad 325 mesh after reacting in a 50 % 0 - 50
2
% N atmosphere at 600 C.
2
62
Veins and inclusions of metallic copper were seen in drops of bornite and chalcocite in both
concentrates. Fig. 5.14 shows an example of this type of particle. A higher proportion of
metallic copper was seen for the 50 % oxygen - 50 % nitrogen atmosphere than for 100 %
oxygen. At 100 % oxygen there is more cuprite (Q12O).
The particle size of the La Escondida reaction products look significantly smaller than for La
Caridad at the same conditions. Comparing the same concentrates, the particle sizes of the
reaction products at 100 % oxygen seem to be smaller than for the 50 % oxygen-50 % nitrogen
mixtures.
When silica is present, the crust of the cenosphere is very compact, and this seems to inhibit
ingress of oxygen to the core. This is the case for the particles shown in Figure 5.15 (a) (b) (c)
and (d). In all of them the crust contains silica, and the core in (a) (b) and (c) consists of
sulfide. This type of particle is more frequent in La Escondida because of its higher silica
content than La Caridad. Fig. 5.15 (d) shows the immiscibility between sulfides and oxides
accentuated by the silica.
For a 90 % sulfur dioxide - 10 % oxygen atmosphere, a higher proportion of particles were
found unmelted in the early oxidation stage. However, some spheres and cenospheres were
also found. Spheres of bornite with inclusions of metallic copper were also seen (Fig. 5.16)
63
Fig. 5.14 Optical microscope image of a drop of Cu S with veins of metallic copper found in La
2
Caridad 325 mesh after reacting in a 50 % 0 - 50 % N atmosphere at 800 C.

2 2
Abbreviations:
Cu Metallic copper
Bn: Bornite (Cu FeS )
5 4
64
c) d)
Fig. 5.15 SEM images of (a,b,c,). compact crust of spheres with high silica content and (d)
immiscibility between oxides and sulfides accentuated by the silica. La Escondida 500 mesh
after reacting in a 100 % O2 atmosphere at 600 C.
65
Fig. 5.16 Optical microscope image of a sphere of bornite with inclusions of metallic copper
found in La Escondida 325 mesh after reacting in a 90 % S 0 - 10 % 0 atmosphere at 600 C.
2 2
Abbreviations:
5 4
Cu: Metallic Copper

Dg: Digenite
66
For a 100 % nitrogen atmosphere there was no evidence of melting. At the rims of the
particles of chalcopyrite, iron was found in a core of chalcocite suggesting that the iron of the
chalcopyrite diffused from the kernel, leaving behind a core of chalcocite (Fig. 5.17). Particles
of pyrite surrounded by an iron rim were also found (Fig. 5.18). This transformation appears to
occupy less volume causing the separation of the rim. Particles of chalcocite exposed at 100 %
nitrogen and at temperatures above 600 C disintegrate or fracture.
5.5.1 Transformation stages in solid state
It was found that burning La Escondida with 20 % oxygen at 600 C and La Caridad with 20
% oxygen at 500 C with 200 mesh particle size lead to clearer images of the transformation of
the particles in the solid state.
Fig. 5.19 (a) shows a particle of pyrite dissociating to pyrrhotite. Fig. 5.19 (b) shows a butterfly
shape particle of pyrrhotite formed from the oxidation of pyrite at low temperatures.
Fig. 5.20 shows chalcopyrite (CuFeS ), which is yellow, dissociating to bornite (CusFeS ),
2 4
which is pink in colour, and then to digenite-chalcocite (Cui.gS, Cu S) particles which are
2
blue-gray. During this transformation, chalcopyrite releases iron from the particle and ignites.
It was observed that chalcopyrite is formed at the junction of particles originally containing
pyrite and chalcocite. The presence of chalcopyrite was confirmed by the XRD results for La
Escondida. Fig. 5.21 shows pyrite transforming to chalcopyrite. Then chalcopyrite dissociattes
to bornite and chalcocite forming a four colour particle.
67
Fig. 5.17. Particle of Cu S with rim of iron found in .La Caridad 325 mesh after exposed in a
2
100 % N atmosphere at 700 C. Image obtained by SEM in backscatter mode

2
Fig. 5.18 Particle of FeS with rim of iron found in La Caridad 325 mesh after exposed in a
2
100% N atmosphere at 700 C. Image obtained by SEM in backscatter mode

2
68
a)
b)
Fig. 5.19 a) Particle of pyrite dissociating to pyrrhotite and b) pyrrhotite with butterfly
shape. La Caridad 200 mesh at 20 % 0 - 80 % N and 500 C. Image obtained by SEM in
2 2
backscatter mode
69
Fig. 5.20 Optical microscope image of a particle of chalcopyrite (yellow) dissociating to bornite
(pink) and then to digenite-chalcocite (blue-gray). La Caridad +200 mesh after reacting in a 20 %
0 - 80 % N atmosphere at 500 C.
2 2
Abbreviations:
Cp: Chalcopyrite (CuFeS )2

5 4
Dg: Digenite (Cui.gS)
70
Fig, 5.21. Optical microscope image of chalcopyrite formed at the junction of particles originally
consisting of pyrite and chalcocite. Chalcopyrite then transforms to bornite and chalcocite
forming a four colour particle. La Escondida +200 mesh after reacting in a 20 % 0 - 80 % N
2 2
atmosphere at 600 C
Abbreviations:

5 4
Dg-Cc: Digenite (Cu S) - Chalcocite (Cu S)

18 2
Py: Pyrite (FeS )

2
71
6 DISCUSSION
6 DISCUSSION
6.1 100 % 0 and 50 % 0 - 50 % N atmosphere

2 2 2
Particle size has a strong influence on the extent of reaction of the concentrates. The 325 mesh
fraction was more reactive than the 500 mesh fraction for both concentrates. This finding
differs from the trend reported by Jorgersen [16] who found that small particles react more
than larger ones. The difference probably lies in the particle residence times in the stagnant
gas flow furnace.
In Jorgensen's experiments, the distance from the feeder to the sampling collector was
adjusted to give an equivalent residence time for each particle size. On the other hand, for the
stagnant gas furnace, the length of the reaction tube is not variable and the residence time is
different for each particle size. For the particle sizes in the current study, the average residence
time for + 400 - 500 mesh (+25 -38 urn) is 3.4 s, while it is 1.2 s for +270 - 325 mesh (+45 -
53 pm). These times are long enough to allow both particles sizes to react to completion. The
time of combustion is determined by the time to attain ignition [16]. Large particles require
more time to ignite compared to small particles and if the residence time is limited, the large
particles do not have enough time to complete their oxidation. In the experiments carried out in
the stagnant gas flow furnace, particles of size 500 mesh ( +25 -38 pm) completed their
reaction sooner than the 325 mesh (+45 -53 pm) particles but the time is long enough that the
325 mesh particles also completed their oxidation. When both particle sizes have enough time
to react, the degree of reaction is determined by the composition of the particles when the
concentrates are exposed to the same temperature and gas composition.
72
^ 6 DISCUSSION
La Escondida contains two minerals (pyrite and chalcocite) with different ignition. However,
the image analysis study reveals that these two minerals are not only present alone, but also in
the same particle. La Escondida 325 mesh contains a higher proportion of these combined
particles compared with the 500 mesh fraction size. La Escondida can therefore be considered
to be a mixture of three types of particles as shown in Table 6.1:
Table 6.1: Types of particles in La Escondida concentrate
500 mesh 325 mesh
Type of particle Mass % Mass %
1) Pure Pyrite and Pyrite +Si0 2

10.4 7.5
2) Pure Chalcocite and Chalcocite + S i 0 2 43.5 23
3) Chalcocite+Pyrite and Chalcocite + Pyrite + S i 0 2 35 66
1) Particles of pure pyrite would react at their own ignition point which is between 500 and
600 C [19]. Particles of pyrite and silica would also react quickly. Yannopoulos et al [46]
showed that in the presence of silica, fayalite (Fe Si0 ) is the first oxidation product of the
2 4
ferrous species.
2) Particles of pure chalcocite would also react at their own ignition temperature (800 - 900
C) [19]. In chalcocite, silica is an inert compound that absorbs heat, retarding the reaction.
3) Combined particles of pyrite and chalcocite behave in a different way in that they react
independently. The presence of pyrite induces chalcocite to react at lower temperatures than
73
6 DISCUSSION
for chalcocite alone. It was seen in the XRD analyses and in the miscroscopic images (optical
and SEM-EDX) that chalcopyrite forms at the junction between pyrite and chalcocite (Fig.
5.21). This chalcopyrite then dissociates into bornite and chalcocite. The formation of
chalcopyrite is extremely fast, apparently faster than the dissociation of pyrite.
The synthesis of chalcopyrite normally requires long time. Habashi [4] cited the work of
Donovan and Reichenbaum who mixed copper, iron, and sulfur in stoichiometric proportions
in a sealed quartz tube placed in a stainless steel bomb and heated it for 8 - 10 hours at 900 -
1100C. Chalcopyrite can be also synthesized from the sulfides. Roberts and Williams [49]
heated a mixture of CuS and FeS at 520 C in an atmosphere of sulfur vapor (partial pressure:
10 torr) for 20 hours after which it was cooled and heated again for a further 24 hours.
One can speculate regarding the formation of chalcopyrite in the stagnant gas flow furnace.
With the combined particles of Cu S and FeS , FeS 2 2 2 losses the pyritic sulfur creating an
atmosphere of sulfur vapor surrounding the Cu S and leading to production of chalcopyrite:

2
2FeS 2(s) -> 2 F e S (s) + S 2(g)
Cu S
2 (s) + 2 FeS (s) + 1/2 S 2(g) -> 2 CuFeS 2 (s)
The overall reaction can be written as:
C u S + 2 FeS
2 (s) 2(s) -> 2CuFeS 2(s) + 1/2 S 2(g)
Due to the fact that both minerals are present together in the same particle, there is close
contact between them and the reaction can proceed much more quickly than when chalcopyrite
is synthesized from separate particles of elements or sulfides. The transformation to
chalcopyrite results in a volume reduction of approximately 27%. Note that part of the sulfur
released from the dissociation of pyrite is accommodated in the reaction. Therefore, it is
74
6 DISCUSSION
probable that the different compositions of the particles is the reason why the 325 mesh
particles are more reactive than the 500 mesh particles.
For a 50 % O 2 -50 % N atmosphere, the 325 mesh fractions of both concentrates differed only
2
slightly from those exposed to 100 % 0 atmosphere. However, for the 500 mesh size fraction
2
of both concentrates, the differences between the 100 % 0 2 and 50 % 0 2 -50 % N 2
atmospheres were significant. The composition of the atmosphere could affect the oxidation in
three ways:
- More oxygen is available at the surface of the particle for the 100 % 0 case.
2
- The chemical reaction rate is increased by the higher surface 0 concentration.

2
- Higher particle temperatures can be reached for 100 % 0 than for the 50 % 0 -50 % N
2 2 2
atmosphere because the heat released by the oxidation must also heat the nitrogen.
In the case of La Caridad the 325 mesh fraction also reacts to a greater extent than the 500
mesh fraction. According to the image analysis study, the 325 mesh fraction La Caridad
contains 51% free pyrite, 12.4% free chalcopyrite and 14.7% free covellite and chalcocite. On
the other hand, La Caridad 500 mesh contains 18.8% free pyrite, 42.5% free chalcopyrite and
16.8% free covellite and chalcocite. The composition of the concentrate has opposite
proportions of chalcopyrite and pyrite in the two particles sizes. The difference in the behavior
of 325 mesh La Caridad compared with La Caridad 500 mesh lies in the relative combustion
behavior of these two minerals, chalcopyrite and pyrite.
75
6 DISCUSSION
Although the ignition point of pyrite is slightly higher than chalcopyrite, the reaction of pyrite
at 600 C is more complete than that of chalcopyrite. According to the experiments of
Jorgensen [18] at the same conditions, chalcopyrite leaves about 30 % of unburned sulfur in
the reaction products, while pyrite almost completed the oxidation (Fig. 2.7).
When chalcopyrite ignites, what ignites first is the iron. Iron first diffuses to the rim where it
ignites, leaving a core of chalcocite by means of a series of reactions [39] :
5 CuFeS 2 > Cu FeS 5 4 + 4 Fei. S + 4x Fe + S

x 2
S 2 + 20 2 -> 2S0 2
3Fe + 2 0 2 -> F e 0 3 4
3Fe,. S +(5-2x)0x 2 - (l-x)Fe 0 + 3 S 0 3 4 2
2Cu FeS + 0 5 2 2 > 5Cu S + 2 F e , . S + 2xFe + S 0 2 x 2
Overall reaction:
6CuFeS 2 + 13 0 2 ( g ) - > 3 Cu S 2 + 2 Fe 0 3 4 + 9 S0 2
Fig. 5.12 illustrates the occurrence of F e 0 covering a drop of Cu S, thereby limiting the 3 4 2
access of oxygen to Cu S which remains as a sulfide. Some oxygen, however, may be absorbed
2
at the surface of Cu S which may then react to form Cu 0, or Cu 0 may be formed from the
2 2 2
reaction of Cu S with F e 0 at the interface. Copper oxide may in turn react with copper
2 3 4
sulfide to form metallic copper.
Cu S 2 + 2Cu 0 2 -> 6Cu + S 0 2
Metallic copper can have the form of inclusions (see Fig. 5.16) or veins (Fig. 5.14). Cu S has 2
a density of 5500 kg/m , while the density of pure copper is 7800 kg/m . This difference in
3 3
densities could make the copper run along the fractures of the Cu S, forming veins. Some 2
76
6 DISCUSSION
copper oxide reacts with Fe 0 or 3 4 Fe 03

2 (which is the most oxidized form of iron) leading to
the spheres of cuprospinel CuFe204 seen in Fig. 5.12. One reaction then is:
CuO + Fe 0 2 3 -> CuFe 0 2 4
On the other hand, the oxidation of pyrite seems to be unaffected by mass transfer through a
product layer. Pyrite loses the pyritic sulfur while iron diffuses to the rim where it is oxidized
leaving pyrrhotite:
FeS 2 -> FeS + 1/2 S 2
FeS xFe + Fei_ S x
3Fe + 2 0 2 -> Fe 0 3 4
Pyrrhotite in most cases is characterized by the appearance of "fingers" (see Figs. 5.13 and
5.19 a) which have additional surface area, allowing greater access to oxygen and hence a more
uniform oxidation. The oxidation proceeds releasing heat causing the particle to melt forming
the drops of F e 3 04 seen in Fig. 5.13.
3Fe,. S +(5-2x)0
x 2 -> (l-x)Fe 0 + 3 S 0 3 4 2
Cenospheres of Fe 0 were also observed (Fig. 5.10). The crust of this type of cenosphere
3 4
seems to have originated from iron that diffused to the rim. A mechanism of inflation of this
type of cenosphere was proposed by Tuffrey et al [20] consisting of transport of oxygen
through the oxide skin via the ferrous-ferric couple (sulfide-oxide)
It can therefore be inferred that 325 mesh La Caridad is more reactive because this size has a
major proportion of pyrite which is not controlled by a product layer. La Caridad 500 mesh,
77
6 DISCUSSION
which contains a major proportion of chalcopyrite, reacts slower because the reaction is mass
transfer controlled through the Fe304 layer.
Despite the fact that La Caridad 500 mesh and La Escondida 325 mesh are both chalcopyrite-
based concentrates, La Escondida is more reactive, probably due to the lower proportion of
iron, so that even though the iron oxidation is a highly exothermic reaction and provokes high
temperature in the particle, it also provides a layer of magnetite that protects the particle from
ingress of oxygen.
6.2 90 % S0 -10 % 0 atmosphere

2 2
The effect of the oxygen partial pressure in the experiments carried out is more noticeable for
the 90 % S O 2 - 10 % O 2 gas mixture. The differences in particle sizes for La Escondida are
smaller than for 100 % 0 and 50 % O -50 % N . For the 90 % SO - 10 % 0

2 2 2 z 2 atmosphere, it
is likely that the reaction is controlled by mass transfer through the gas boundary layer. It can
be seen from Fig. 5.4 that the sulfur remaining for La Escondida corresponds to the sulfur
content in Cu S. The iron content in La Escondida is 9.7 % and 14.2 % for 500 mesh and 325
2
mesh, as compared with La Caridad which contains 24 and 31 % Fe for 500 and 325 mesh,
respectively. With less iron and restriction of oxygen, La Escondida particles complete their
iron oxidation while the La Caridad particles do not.
It was also observed that the sulfur remaining in La Escondida 500 mesh fraction for the 90 %
N - 10 % 0 was lower than for 90 % S 0 - 10 % 0 . This can be due to two effects:

2 2 2 2
78
6 DISCUSSION
-Thermodynamically, the presence of S 0 enhances the reverse reaction, i.e. production of the
2
sulfides
-The diffusivity of oxygen in sulfur dioxide is lower than the diffusivity of oxygen in nitrogen.
According to the equation:
0.001T 1.75 1 1
p(v + vy \ M
A
+ M
B J
the diffusivity of 0 at 900 C in S 0 is 1.41 cm /sec, while this value is 2.27 cm7sec for 0 in
2 2
z
2
N at the same temperature, i.e., 1.6 times higher for N than S0 .

2 2 2
The presence of CuS0 4 was detected from XRD analyses. As seen in Section 2.1,
thermodynamically, the formation of sulfates is not only feasible, but CuS0 is the final 4
product (together with Fe 0 ) of the oxidation of chalcopyrite and copper sulfides at 680 C.
2 3
From the equilibria:
2 CuO + 2 S 0 2 + 0 2 -> 2CuS0 4
The free energy AG for the reaction is:
AG = A G + RT In [l/(pS0 p0 )]
0
2
2
2
where AG is the free energy of the reaction at the standard state and the given temperature and
the second term is the free energy at the actual conditions of pS0 and p0 . 2 2
AG represents the difference between the equilibrium and actual conditions and it is equal to 0
if the system is at equilibrium, < 0 if the reaction proceeds to the right and > 0 if it proceeds to
the left. For the 90 % S 0 - 10 % 0 mixture, AG is negative from 600 to 800 C and positive
2 2
900 C, indicating that the formation of CuS0 is favored at temperatures below 900 C.
4
79
6 DISCUSSION
From the above equilibrium considerations, AG is more negative as the S 0 concentration is

2
increased, i.e., the presence of S 0 enhances the formation of sulfates. At 90 % N - 10 % 0 ,

2 2 2
CuS0 was not detected even though there is some S 0 evolved from the oxidation reactions.
4 2
Perhaps CuS0 formed was below the detection limits of the XRD (detection limit is 5 %).
4
6.3 100 % N atmosphere

2
For a 100 % N atmosphere, fine particles of La Escondida lost sulfur faster than larger ones.
2
This is opposite to the behavior for the other atmospheres studied in which the La Escondida
325 mesh fraction was more reactive than the 500 mesh particles.
When the particles are exposed to the inert (100 % N ) atmosphere, only the thermal
2
dissociation reactions occur, and these are endothermic. To see if there are significant
temperature gradients in the particles, the Biot number was calculated, taking the thermal
conductivity of clay as a first approximation (1.3 W/ m K).
Considering the Ranz-Marshall correlation to estimate the coefficient of heat transfer
Nu = 2 + 0.6 Re 1/2
Pr 1/3
where: Nu = Nusselt number = hd /k p g
Pr = Prandtl number = C T| / k g
Re = Reynolds number = d u p /r\ p p g
80
6 DISCUSSION
For fine particles (< 50 microns) the Reynolds number is very small and Nusselt number is
approximately 2. The heat transfer coefficient is then 0.385 W/cm K for a 31.5 pm particle
2
and 0.248 W/cm K for a 49 pm diameter particle.

2
When the heat transfer coefficient is substituted into the Biot number equation with Nu = 2,
the Biot number becomes independent of particle size, i.e.:
hr k.
Biot number =
M p 3k p
The Biot number obtained is 0.016 which is smaller than 0.1 even though the conductivity of
the particle is higher than the conductivity of the clay so that the Biot number should be
smaller. A very low value of the Biot number (< 0.1) means that the internal conduction
resistance is negligible in comparison with surface-convection resistance. It is therefore
reasonable then to assume uniform temperature throughout the particle and to use the lumped
capacitance method to determine the time taken for the particles to reach a given temperature.
Hence the time is given by:
p VC T- T
hA T-T g
with p = 4567 kg/m and C = 0.84 x 10~ J/g K [8], the time obtained for a 31.5 pm particle
p
3
p
3
is 0.011 ms, while it is 0.027 ms for a 49 pm particle.
Therefore it can be inferred that the thermal inertia of the particle is not the reason that La
Escondida 500 mesh dissociates first. Both particles sizes quickly reach the temperature of the
furnace for dissociation, but the 325 mesh particles have a greater proportion of combined
81
6 DISCUSSION
particles, and the formation of chalcopyrite takes part of the sulfur released by the dissociation
of pyrite. The chalcopyrite formed does not have enough time to complete its dissociation.
6.4 Vaporization of copper
The copper-iron ratio obtained decreased in almost the same magnitude in both concentrates
(17-18 % ) indicating that the volatilization of copper was in the same proportion in the two
concentrates.
The calculated maximum particle temperatures considering complete oxidation and ignoring
heat losses are 2884 C and 3057 C for La Escondida 500 mesh and 325 mesh respectively.
Temperatures of 3436 C and 3660 C are obtained for La Caridad 500 and 325 mesh fraction
size. These temperatures are all above the boiling point of copper (2563 C), and there is
probably enough heat to provide the heat of evaporation.
La Caridad can reach higher temperatures because it contains more iron and its oxidation is
very exothermic. Iron also provides a viscous layer of Fe 04 that covers the particle,
3
preventing copper from reaching the surface. On the other hand, the iron content in La
Escondida is lower causing lower temperatures, but also less F e 0 covers the surface. With
3 4
more surface area exposed, La Escondida can have the same degree of volatilization as La
Caridad, even though La Escondida particles tend to reach lower temperatures than La
Caridad.
The layer of F e 0 probably also affects the particle size of the reaction products. Otero et al
3 4
[25] suggested that the iron contained in the reaction products of chalcopyrite may act as a
binder holding the particle together. In the current work, it was observed that the particle size
of the reaction products was smaller for La Escondida than for La Caridad, perhaps for the
same reason.
82
7 CONCLUSIONS
7 CONCLUSIONS
The following conclusions are obtained in this work:
For 100 % O2 and 50 % 0 - 50 % N atmosphere, 325 mesh particle size fraction was more
2 2
reactive than the finer 500 mesh fraction for both concentrates. The reason is the different
composition of the particle sizes:
- La Escondida 325 mesh has a greater proportion of combined particles of
FeS and Cu S that react to form chalcopyrite which has lower ignition
2 2
temperature.
- La Escondida 500 mesh has a greater proportion of free Cu S which has a

2
higher ignition temperature than chalcopyrite.
- La Caridad 325 mesh fraction is a concentrate based on pyrite, and it reacts
faster because the oxidation of pyrite seems not to be affected by mass transfer
through a product layer.
- La Caridad 500 mesh fraction is a chalcopyrite-based concentrate where the
reaction is controlled by mass transfer through the F e 0 product layer.

3 4
In spite of the fact that La Caridad 500 mesh and La Escondida 325 mesh behave as
chalcopyrite-based concentrates La Escondida 325 mesh is more reactive, probably due to the
lower proportion of iron, so that even though its oxidation is highly exothermic, it provides a
layer that protects the particle from the ingress of oxygen. This (Fe C>4 ) viscous layer not only
3
limits the access of oxygen, but it also prevents excessive volatilization of copper and
reduction in particle size.
83
7 CONCLUSIONS
At 90 % S O 2 - 10 % O2, the oxidation of the two concentrates it is supposed to be controlled
by external gas mass transfer. La Escondida with less iron can complete the iron oxidation
while La Caridad cannot.
The extent of reaction was lower for a 90 % S O 2 - 10 % 0 atmosphere than for a 90 % N - 10

2 2
% 0 atmosphere due to the presence of S 0

2 2 enhancing the reaction to the sulfides and also
due to differences in diffusivity with the diffusivity of 0 in S 0 being 1.6 times lower than
2 2
that of 0 in N .
2 2
In a 100 % N atmosphere La Escondida 500 mesh fraction had a higher degree of dissociation
2
than La Escondida 325 mesh particles probably due to the formation of chalcopyrite that
absorbs part of the sulfur released by the dissociation of pyrite
The results of the present study shows that the oxidation characteristics of La Escondida are
similar to the usual concentrates based in chalcopyrite. These are:
- The oxidation products of chalcopyrite (consisting of CU2S surrounded of Fe oxide and
drops of bornite) were also encountered in La Escondida.
- The degree of volatilization was similar for both concentrates.
- The sulfur loss at 600 C for the 325 mesh fraction size was not only the sulfur contained in
FeS but also some of the sulfur in Cu S which was mixed with FeS
2 2 2 and formed
chalcopyrite.
84
7 CONCLUSIONS
Therefore, the oxidation behaviour of La Escondida is not the reason of the problems observed
in the Smelter which can probably be related to the effect of La Escondida in the heat balance
of the furnace. The purpose of the flash furnace is the partial oxidation of the iron in the sulfide
minerals (CuFeS2, FeSa). Higher proportions of Cu S in the feed takes part of the heat released
2
by the oxidation for melting themselves.
85
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89

Combustion of Particles of Copper Concentrate in A Stagnant Gas

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Combustion of Particles of Copper Concentrate in A Stagnant Gas

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COMBUSTION OF PARTICLES OF COPPER CONCENTRATE

IN A STAGNANT GAS FURNACE

B.Sc. UNIVERSIDAD NACIONAL AUTONOMA DE MEXICO, 1982.

A THESIS SUBMITTED IN PARTIAL FULFILMENT OF

THE REQUIREMENTS FOR THE DEGREE OF

MASTER OF APPLIED SCIENCE

THE FACULTY OF GRADUATE STUDIES

(Department of Metals and Materials Engineering)

We accept this thesis^as conforming to the required standard

THE UNIVERSITY OF BRITISH COLUMBIA

ANABEL THOMAS, 1999.

The University of British Columbia

particle size on the reaction behaviour of each concentrate were studied.

LIST OF TABLES ' viii

3 SCOPE AND OBJECTIVES 32

Fig. 1.1: Inco oxygen flash furnace 3

Fig. 1.2: Outokumpu oxygen-enriched air flash furnace 4

Fig. 1.3: Flash smelters in the world 5

Fig. 2.2: Predominance diagram for Cu-Fe-S-O system at 827 C 10

Fig. 2.3: Apparatus used by Jorgensen 14

Fig. 2.5: Effect of the experimental temperature on the combustion of 37-53 pm

Fig. 2.7: Effect of temperature on the oxidation rate of various sulfides of 37 - 53 pm

Fig. 2.8: Model for fragmentation proposed by Kim 21

Fig. 4.1: Experimental apparatus 34

Fig.4.2: Temperature profiles 37

Fig. 4.3: Calculated residence time of particle sizes 39

Fig. 5.6: Copper-iron ratio for L a Escondida concentrate 53

Fig. 5.7: Copper-iron ratio for L a Caridad concentrate 54

Fig. 5.11: S E M image of cenosphere of Cu S found in the reaction products of

500 mesh L a Escondida for 100 % 0 at a temperature of 900 C

CuFe C4 found in L a Caridad 325 mesh after reacting in a 50 % 0 - 50 % N

atmosphere at 800C. Image obtained by backscatter mode 62

Fig. 5.13: S E M image of a particle of pyrrhotite and particles of CuFe C4 C u F e 0 and

found in L a Caridad after reacting in a 50 % O -50 % N atmosphere at 800 C

700 C. SEM backscatter mode 68

Fig. 5.19: a) Particle of pyrite dissociating to pyrrhotite and b) pyrrhotite with

SEM backscatter mode 69

Fig. 5.20: Optical microscope image of a particle of chalcopyrite dissociating to bornite

Table 2.1: Proportions of copper and sulfur found in copper sulfides 6

Table 2.2: Principal reactions in the smelting of copper concentrates 7

Table 2.3: Approximate ignition temperatures for concentrates in air 17

Table 4.1: Particle size distribution of La Escondida concentrate 41

Table 4.2: Chemical and mineralogical composition of La Escondida Concentrate 41

Table 4.3: Image analysis of La Escondida concentrate 42

Table 4.4: Particle size distribution of La Caridad concentrate 43

Table 4.5: Chemical and mineralogical composition of La Caridad concentrate 43

Table 4.6: Image analysis of La Caridad concentrate 44

Table 5.1: Phases present for 100 % O2 atmosphere 56

Table 5.2: Phases present for 50 % 0 - 50 % N atmosphere

Table 5.3: Phases present for 90% S 0 - 10 % 0 atmosphere

Table 5.4: Phases present for 100 % N atmosphere

Table 6.1: Types of particles in La Escondida concentrate 73

A Surface area of particle

C Specific heat of fluid

DAB Diffusivity of a gas mixture

h Heat transfer coefficient

kg Thermal conductivity of fluid

kp Thermal conductivity of particle

Up, Velocity of particle

VA, VB Molecular volumes

AG Change in free energy

Copper ferrite - Cupro spinel CuFe 0 2 4

Digenite Cu . S (average Cui.gS)