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Transformation of Chalcopyrite in the Roasting Process of Copper

Concentrate in Fluidized Bed Reactor

Article  in  JOM: the journal of the Minerals, Metals & Materials Society · May 2011
DOI: 10.1007/s11837-011-0078-2

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 Nonferrous Pyrometallurgy
Transformation of Chalcopyrite
in the Roasting Process of Copper
Concentrate in Fluidized Bed Reactor
Mira B. Cocić, Mihovil M. Logar, Saša Lj. Cocić, Snežana S. Dević, and Dragan M. Manasijević
This work presents the results of in-
vestigation process of copper concen-
trate roasting in fluidized bed reactor
with the aim of studying the transfor-
mations of copper concentrate min-
erals as well as to check the accor-
dance with theoretical predictions. The
roasted samples were examined using
chemical analysis, x-ray diffraction,
and mineral microscopy.
INTRoduCTIoN
The roasting of chalcopyrite concen-
trates presents a very important step in
the copper extraction during the tra-
ditional smelting-refining process, as
well as in advanced processes in cop-
per metallurgy.1,2 The roasting process
of sulfide copper concentrates in the
fluidized bed reactor is an oxidation
process and represents the first stage
in a traditional pyrometallurgical pro-
cess of copper extraction in the Cop-
per Mining and Smelting Complex Bor
(Serbia), so the importance of accurate
and quality process control is an under-
standable precondition for the correct
treatment in the following stages of the
copper extraction.
Numerous research has investigated
the chalcopyrite oxidation process, its
mechanism and reactions involved.
These references deal with pure chal-
copyrite mineral oxidation and with the
oxidation process of chalcopyrite con-
centrates, also. Studying the process
of chalcopyrite concentrates roasting,
many researchers concluded that the
chalcopyrite oxidation is not developed
by its disintegration into simple copper
and iron sulfides, but by the formation
of bornite stage.3–11 The chalcopyrite
transformation into bornite is theoreti-
cally explained by reaction diffusion
that could be seen on an example of
oxide roasting the chalcopyrite grains
Vol. 63 No. 5 • JOM
“on core.”12 During this roasting meth-
od, copper is concentrated into grain
How would you…
…describe the overall significance
of this paper?
This work deals with the process of
chalcopyrite concentrate roasting in
a fluidized-bed reactor. The roasting
of chalcopyrite concentrates presents
a very important step in copper
extraction during the traditional
smelting-refining process as well
as in advanced processes in copper
metallurgy. To achieve maximum
efficiency, minimum pollution of
the environment, and to get a high
quality product it is necessary
to examine the mineralogical
transformations of primary ore
minerals during roasting.
…describe this work to a
materials science and engineering
professional with no experience in
your technical specialty?
This paper focuses on an investigation
of mineral transformations that
occur during the roasting process
in the oxidation environment of
the fluidized-bed reactor. During
the roasting of copper sulfide
concentrate, complete dissociation of
pyrite and partial dissociation of the
chalcopyrite to bornite and pyrrhotite
occurs, while part of chalcopyrite
remains unchanged because of the
short reaction time. Control and
regulation of the process parameters
during roasting provides the desired
composition of copper matte in the
reverberatory furnace.
…describe this work to a layperson?
The roasting process used for sulfidic
concentrates of copper is one of the
most important and the most complex
of all the pyrometallurgical unit
operations. This process is carried
out by heating the sulfides in air or
in oxygen. This paper analyzes the
transformation of minerals during the
process of roasting in the fluidized-
bed roaster.
www.tms.org/jom.html
Research Summary
core, and cover consists of iron oxide.
Change of chalcopyrite grain structure
depends on oxidation time. After a
short time of roasting, a layer of iron
oxide is formed on a grain surface, un-
til in the second layer the chalcopyrite
is concentrate; the third layer is unre-
acted core of starting material. After
an extended roasting time, the surface
layer also consists of oxide; the second
and third layers are enriched with cop-
per sulfide–bornite, the fourth layer
is less enriched with copper sulfide–
chalcopyrite, and the fifth is unreacted
core of starting material. A completely
roasted chalcopyrite grain consists of
an oxide layer (surface layer) and core
enriched with sulfide bornite.
Levenspiel13 illustrated a model of
unreacted core that describes the pro-
cess of partial oxidation roasting. By
this model, it is predicted that oxida-
tion reaction is first developed on the
outer surface of a particle. The reaction
zone then gradually moves towards the
center of solid particle, and it could
leave completely reacted reactant and
solid product of reaction. At every
moment, there is an unreacted core of
material that decreases during reaction,
while total size of particle is unchange-
able. According to Ćirković,14 a theo-
retical model of chalcopyrite oxidation
assumes a concentric grain structure
(Figure 1) with increase in transfor-
mation rate from center to periphery
where the core stays unchanged. Figure
1 presents a model of spherical chalco-
pyrite grain that is exposed to oxygen
action from air in conditions of oxide
roasting. Bornite and pyrothine are
formed as solid reaction products. The
size of the unreacted core depends on
the concentration of supplied oxygen,
diffusion rate through layer of formed
product and time of grain presence in
55
 eXPeRIMeNTal MeThods
reaction area.14
The chalcopyrite concentrate, from the traditional pyrometallurgical process of cop- The bornite stage appearance as a re-
per extraction in the Copper Mining and Smelting Complex Bor (Serbia) was the start- sult of transformation in terms of chal-
ing charge. The roasting of chalcopyrite concentrate in a fluidized bed reactor (Smelt- copyrite oxidation roasting is described
ing Complex Bor) was done using the following standard process conditions: flow of in detail.3,7,8,15 The chemistry of chalco-
process air 24,000–25,000 Nm3, flow of cooling water 1–2 m3/h, process temperature pyrite (CuFeS2) oxidation in fluidized
670ºC, time of roasting 90 sec, where charging capacity varied 45–55 t/h.
layer in the temperature interval from
After the roasting operation, roasted samples of effluent and overflow were taken.
600 to 720ºC can be represented by the
Dishes for sampling were hermetically closed to prevent oxidation of the effluent com-
ponents, and for the aim of obtaining good results in chemical analysis. Reactions 1 and 2.15,16
To realize the set task regarding the transformation products during roasting, a de-
tailed investigation of samples was carried out by the use of suitable methods: chemical 5CuFeS2+2O2=Cu5FeS4
analysis, x-ray diffraction, and ore microscopy. The samples were chemically analyzed
using standard procedures. X-ray diffraction analysis of tested samples was carried out +4FeS+2SO (1)
on a SIEMENS device with Cu-anticathode and filtrated emission by Ni-filters at volt-
age of 40 kV and current intensity of 20 mA. The used literature data in comparison of 5CuFeS2+5O2=Cu5FeS4
calculated values of interflat distances were taken from the card file of ASTM and the
Joint Committee on Powder Diffraction Standard. Ore microscopy was carried out on +4FeS+2FeO+4SO2 (2)
the Leitz-Ortolux microscope in reflected light.
The value of Gibbs free energy in
the investigated temperature range for
Reaction 1 is –∆G = 503–510 kJ/mol,
Table I. Chemical Composition of the Investigated Samples
and for Reaction 2 –∆G = 1328–1317
Partial Chemical Analysis (wt.%) kJ / mol, which confirms the high ther-
Sample Cu SiO2 Fe CaO S Fe3O4 modynamic probability of their occur-
rence.
Charge 1 14.76 10.42 26.44 5.77 34.85 0.34 The aim of this study is to experi-
Calcine 1 16.97 15.85 33.23 1.32 20.3 10.66 mentally investigate mineralogical
Overflow 1 1.1 7.2 2.105 45.005 0.8 0.44 transformations in chalcopyrite con-
Charge 2 12.86 16.26 25.97 3.19 29.55 0.39 centrate during roasting in fluidized
Calcine 2 14.93 20.57 30.07 1.32 18.89 8.99
bed reactor and to compare obtained
results with the developed theoretical
Overflow 2 0.795 17 1.73 41.56 0.6 0.54
models of copper concentrate roasting.
Charge 3 19.41 11.37 29.18 — 32.72 0.27
See the sidebar for experimental meth-
Calcine 3 20.68 16.53 30.58 — 19.5 10.31 ods.
Overflow 3 4.165 20.65 5.005 33.14 0.6 3.1
ResulTs aNd dIsCussIoN
Charge 4 18.8 11.17 27.37 3.16 29.7 —
Calcine 4 21.32 14.53 33.51 1.67 19.9 11.57 The results of chemical analysis
Overflow 4 6.12 32.84 7.68 24.37 4.18 2.27 and x-ray diffraction analysis of ten
samples of charge, calcine and over-
Charge 5 19.88 11.46 30.72 1.79 31.48 —
flow, taken during the period of one
Calcine 5 22.72 14.14 30.86 1.45 21.08 8.61
month, are shown in Tables I and II.
Overflow 5 1.93 33.97 2.51 30.74 1.18 0.52 It can be seen that variations in the
Charge 6 18.8 12.77 26.72 2.57 31.38 — chemical composition of analyzed
Calcine 6 19.96 13.41 29.04 1.58 19.5 8.07 charge samples. It could be said that
Overflow 6 1.22 29.69 3.77 31.74 1.28 0.52 the calcine, representing roasted cop-
Charge 7 15.8 13.06 26.67 2.83 33.07 — per charge, contains qualitatively the
Calcine 7 16.1 20.64 30.35 2.46 19.6 9.39
same elements as starting charge, but
their quantitative values are complete-
Overflow 7 1.68 29.99 2.57 33.08 0.39 0.64
ly changed. The increased content of
Charge 8 16.96 11.02 27.23 2.33 32.08 —
quartz in the overflow appears due to
Calcine 8 18.8 13.89 31.97 1.75 20.88 9.31 the presence of a high quantity of air,
Overflow 8 0.98 23.33 1.26 38.44 0.79 — and decreased number of blowers,
Charge 9 15.7 12.28 26.3 2.66 31.88 — which cause that part of quartz from
Calcine 9 18.4 14.32 31.89 1.5 21.47 9.39 the bed to be transferred with air. Min-
Overflow 9 1.08 25.93 1.45 30.07 0.69 0.12 eral composition is the visible change
because in the process of the roast-
Charge 10 15.34 12.25 27.64 3.75 33.07 —
ing charge, pyrite (FeS2) and a part of
Calcine 10 18.06 13.84 32.67 1.52 22.06 9.34
chalcopyrite (CuFeS2) from the charge
Overflow 10 0.95 22.7 1.26 36.43 0.44 — dissociate in the roasting process and

56 www.tms.org/jom.html JOM • May 2011

move into more stable copper and iron
sulfides: bornite (Cu5FeS4) and pyrrho- Table II. Quantitative Mineralogical Content was Determined by the Use of Powder Cell
tite (FeS). A part of chalcopyrite is un- Analysis (KMS) Based on X-ray Diffraction Analysis
changed during roasting due to a lack Chalcopyrite Magnetite Bornite Pyrrhotite Pyrite Quartz Anhydrite Calcite
of time for its transformation. Sample* (%) (%) (5) (%) (%) (%) (%) (%)
Based on optical characteristics of
1 42.3 — — — 29.95 27.74 — —
minerals, mineralogical identification
of samples was carried out. The follow- 1a 56.6 21.49 7.91 14 — — — —
ing content was determined in the ore 1b — — — — — 12.71 12.47 74.82
samples of charge: chalcopyrite, pyrite, 2 26.86 — — — 17.63 55.52 — —
rarely covellite, chalcocite, magnetite, 2a 75.96 12.12 1.55 10.33 — — — —
galenite, and sphalerite. In samples of 2b — — — — — 26.14 8.87 64.99
calcine, the following appear: chalco- 3 68.61 — — — 16.75 14.64 — —
pyrite, bornite, pyrrhotite, pyrite, mag-
3a 66.81 18.69 3.48 11.03 — — — —
netite, marcasite, digenite, chalcocite,
3b — — — — — 38.67 6.34 54.99
covellite, sphalerite, galenite, ruthile,
hematite, and cuprite. There are no ore 4 67.73 — — — 15.32 16.95 — —
minerals in the samples of overflow. 4a 67.29 20.03 5.59 7.09 — — — —
The samples of calcine are the most 4b — — — — — 39.55 1.42 59.02
important for us. A description of the 5 57.88 — — — 18.68 23.44 — —
minerals present in calcine is: 5a 64.13 15.66 12.26 7.95 — — — —
Chalcopyrite: (CuFeS2) appears 5b — — — — — 50.75 9.73 39.52
in partly regular to irregular grains of
6 49.96 — — — 15.66 34.38 — —
various sizes from some mm to 100
mm. Larger grains are rarely present. It 6a 69.73 15.65 4.28 10.35 — — — —
often forms solid solution with bornite. 6b — — — — — 56.49 5.23 38.27
Disintegration of solid solution results 7 41.51 — — — 23.79 34.7 — —
into chalcopyrite and bornite, where
7a 61.54 19.77 3.68 15.01 — — — —
somewhere bornite was transformed
7b — — — — — 42.84 10.61 46.56
into digenite. This transformation de-
velops from the rim to the central parts 8 54.35 — — — 17.08 28.58 — —
of grain, although the laminar separa- 8a 65.57 11.22 9.92 13.29 — — — —
tion are present or bornite appears in a
8b — — — — — 46.07 8.27 45.02
form of irregularly distributed veins. It
is present in the form of separation in 9 58.12 — — — 25.13 16.74 — —
sphalerite very rarely. Fine size grains 9a 62.68 16.88 6.17 14.28 — — — —
of chalcopyrite are intergrown with py- 9b — — — — — 39.45 9.76 50.79
rite very rarely, until somewhere it is
10 39.38 — — — 25.3 35.33 — —
included into pyrite.
Pyrrhotite: (FeS) mainly appears 10a 58.96 14.24 10.01 16.79 — — — —
in sponge-like aggregates of spherical 10b — — — — — 59.02 5.32 35.66
form. Due to the fact that it is not pres- * Samples:1 – 10 Samples of Charge; 1a –10a Samples of Calcine; 1b – 10b Samples of Overflow
ent in a charge, it is obvious that it was
formed in the roasting process by trans-
formation of starting minerals.
Bornite: (Cu5FeS4) appears in irreg-
ular grains (size about 15 mm). It pres- O2
ents a product of disintegration of solid FeS
solution where chalcopyrite and born-
ite are formed, and then somewhere
bornite was transformed into digenite.
CuFeS2
Rarely aggregates of bornite–digenite
have an edge of cuprite. It also appears
independently.
Pyrite: (FeS2) also appears in partly Cu5FeS4 SO2
regular to irregular grains. It is rarely
Figure 1. Theoretical mecha-
included in chalcopyrite, and pseudo- nism of chalcopyrite oxida-
morphoses of ghetite on pyrite are even tion.14
more rare (pseudomorphoses appear

Vol. 63 No. 5 • JOM www.tms.org/jom.html 57


Bn
Cp
0.1 mm
a b
Bn
Cp
0.03 mm
c d
Figure 2. Micrograph of: (a) chalcopyrite (Cp) with separation of bornite (Bn) in sample
Calcine 1, (b) chalcopyrite (Cp), pyrrhotite (Pn) and chalcopyrite with separation of bornite
(Bn) in sample Calcine 1, (c) chalcopyrite (Cp) and chalcopyrite with separation of bornite
(Bn) in sample Calcine 1, (d) bornite (Bn) with an edge of digenite (Dg) in sample Calcine
1, (granulometric fraction + 0.075 mm).
due to the increased concentrations
where surplus of oxygen is present as
well as due to high temperatures).
Magnetite: (FeFe2O4) appears in
irregular grains. It is most often asso-
ciated with waste. It is very rarely in
association with hematite and chalco-
pyrite.
Marcasite: (FeS2) is a rare mineral
and it is always in association with pyr-
rhotite. Marcasite presents a product of
pyrrhotite transformation.
Digenite: (Cu1,8S) is rarely present.
It appears in irregular grains or sponge-
like aggregates, and as an edge around
bornite. Probably it appears as a prod-
uct of the roasting process.
Chalcocite: (Cu2S) is present very
rarely in independent grains of irregu-
lar form where those grains very often
include the waste minerals.
Covellite: (CuS) appears as a sec-
ondary mineral in irregular fragments
or life-like aggregates. Mainly, it is
independent until it is less present em-
bedded into chalcopyrite.
Sphalerite: (ZnS) and galenite
(PbS) are very rare minerals. Some-
where they are intergrown, one with
the other, until they are very rarely
58
Pn
Bn
Cp
0.1 mm
Bn
Dg
0.1 mm
present as separation of chalcopyrite in
sphalerite.
Goethite: FeOOH is a rare mineral.
It appears as a product of pyrite trans-
formation.
Hematite: (Fe2O3) is also a rare
mineral, and it appears both in charge
or as a product of roasting process.
Cuprite: (Cu2O) is a rare mineral.
Sometimes it appears as an edge around
rare aggregates bornite–digenite.
Based on the obtained results of
chemical and mineralogical analysis of
copper roast it could be concluded that,
during the roasting in the fluidized bed
reactor, transformation of chalcopyrite
does not follow the model of spheri-
cal zonarity. The obtained results show
that mineralogical transformations
do not proceed from periphery to the
center of the grain, but in the form of
laminar separations. This is illustrated
in the micrographs, given in Figure 2.
In the roasting process, higher sul-
fide copper and iron minerals (chal-
copyrite and pyrite) transform into
lower sulfides, and disassociated sulfur
oxidizes to sulfur dioxide. During the
roasting of chalcopyrite–pyrite charge
in the fluidized bed reactor, a complete
www.tms.org/jom.html
disassociation (transformation) of py-
rite and partial transformation chalco-
pyrite to bornite and pyrrhotite is de-
veloped, because the retaining time of
particles in reaction area is very short,
so due to this the roasting of sulfide
copper concentrates in fluo-solid reac-
tor is incomplete.
Roasted copper concentrate contains
approximately the same elements as
concentrate except its chemical content
is changed. Quantity of sulfur from sul-
fide is significantly decreased, quantity
of oxide is increased and evaporable
compounds from some harmful sub-
stances are decreased.
Results of experimental investiga-
tions show certain variations regarding
data in the literature.17 Contrary to the
previous models of roasting process,
there is no chalocite in effluents. Chal-
copyrite in present conditions in the
reactor does not transform into chal-
cocite. Therefore, it is necessary to
study the processes of oxidation and
transformation of complex copper and
iron sulfides in the roasting process
that enables recognition of real model
of process in fluo-solid reactor.
In the production process, the real
picture of development of the transfor-
mation process is completely different
than the theoretical models12–14 case
to case, some different morphological
forms of transformation are noticed:
laminar separations, separation along
privileged directions, etc.
CoNClusIoN
• In the roasting process of copper
concentrate charge in the fluid-
ized bed reactor, pyrite, and a
part of chalcopyrite are disas-
sociated and transformed into
more stable copper and iron
sulfides: bornite and pyrrhotite,
and a part of chalcopyrite remain
unchanged.
• Development of bornite from
chalcopyrite is along privileged
directions but not concentric
from periphery to the center.
• Reactions of mineral transforma-
tion are not complete, i.e. they
are developed only partially,
which is the result of insufficient
time, unsuitable temperature or
not filling the other parameters
as well as for example the grain size.
JOM • May 2011
 aCkNowledgeMeNTs
This work was written with financial
aid from the Ministry for Science and
Environment Protection and it is a part
of Project 176010.
References
1. S. Prasad and B.D. Panday, Minerals Engineering,
11 (8) (1998), pp. 763–781.
2. N. Štrbac et al., Sulphides-thermal, The Thermo-
dynamic and Kinetic Analysis (Bor, Serbia: Technical
Faculty Bor, 2005), pp. 39–64.
3. T. Rosenqvist, Metall. Trans. B, 9B (1978), pp.
337–351.
4. M. Spivak, P.A. Isakova, and A.G. Loparev, "Himija
i Tehnologija molibdena i volframa" Tezisi dokladov IV
Vsesojuznogo soveščanija Taškent, FAN (1980), p. 16.
5. A.Yazawa, Metall. Trans. B, 106 (1979), pp. 307–321.
Vol. 63 No. 5 • JOM
View publication stats
6. Č-H. Čžun et al., Metallurgizdat, 31 (1958), pp.
327–336.
7. E.V. Margulis, Žurnal prikladnoj himii, 34 (1961), pp.
2164–2171.
8. P.N. Bakirdžiev and I.S Grozdanov, Cvetnie Metalli,
4 (1986), pp. 42–45.
9. M. Cocić and P. Šukletović, “Mineralogical Transfor-
mation in Copper Concentrate Roasting in Fluo-solid
Reactor,“ XXX October Conference on Mining and
Metallurgy, ed. Donji Milanovac (Serbia, 1998), pp.
108–112.
10. M. Cocić, “Quantitative Determination of Transfor-
mation Products in the Copper Concentrate Roasting
Process in Fluo-solid Reactor” (Ms. Thesis, University
of Belgrade, 2005).
11. M. Cocić et al., JMM, 43B (2007), pp. 71–78.
12. V.I. Smirnov and A.I. Tihonov, “Obžig mednih rud i
koncentratov,” Metallurgija, Moskva (1966), pp. 49–52.
13. Octave Levenspiel, Chemicals Reaction Engineer-
ing (New York: John Wiley & Sons, Inc., 1972).
14. M. Ćirković, “Theoretical and Experimental Study
of the Process of Roasting Copper Sulphide Con-
www.tms.org/jom.html
centrates in the Reactor with Fluidizatio Layer using
Oxygen-enriched Air” (Ms. Thesis, University of Bel-
grade, 1999).
15. M. Ćirković et al., EPD Congress 1999, ed. B.
Mishra (Warrendale, PA: TMS, 1999), pp. 933–944.
16. M. Ćirković, J. Marinković, and D. Vučurović, Met-
allurgy, 3 (1999), pp. 227–336.
17. S. Janjić, “Crystallographic and Mineralogical In-
vestigation of Copper Sulphides Minerals and Prod-
ucts of Piromatallurgic Processing in Bor Copper
Smelter” (Ph.D. thesis, University of Belgrade, 1978),
pp. 101–110.
Mira B. Cocić, assistant, and Dragan M.
Manasijević, professor, are members of the Tech-
nical Faculty in Bor, and Mihovil M. Logar, a pro-
fessor with the Faculty of Mining and Geology, are
with the University of Belgrade, Bor, Serbia; Saša
Lj. Cocić, senior geologist, Avala Resources, Bor;
and Snežana S. Dević, expert associate, are with
the Institute IMS in Belgrade. Mrs. Cocić can be
reached at mcocic@tf.bor.ac.rs.
59