Nonferrous Pyrometallurgy

Research Summary

Transformation of Chalcopyrite in the Roasting Process of Copper Concentrate in Fluidized Bed Reactor
Mira B. Coci, Mihovil M. Logar, Saa Lj. Coci, Sneana S. Devi, and Dragan M. Manasijevi
This work presents the results of investigation process of copper concentrate roasting in fluidized bed reactor with the aim of studying the transformations of copper concentrate minerals as well as to check the accordance with theoretical predictions. The roasted samples were examined using chemical analysis, x-ray diffraction, and mineral microscopy. INTRODUCTION The roasting of chalcopyrite concentrates presents a very important step in the copper extraction during the traditional smelting-refining process, as well as in advanced processes in copper 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 process of copper extraction in the Copper Mining and Smelting Complex Bor (Serbia), so the importance of accurate and quality process control is an understandable 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 chalcopyrite mineral oxidation and with the oxidation process of chalcopyrite concentrates, 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.311 The chalcopyrite transformation into bornite is theoretically explained by reaction diffusion that could be seen on an example of oxide roasting the chalcopyrite grains
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on core.12 During this roasting method, 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 fluidizedbed roaster.

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, until in the second layer the chalcopyrite is concentrate; the third layer is unreacted core of starting material. After an extended roasting time, the surface layer also consists of oxide; the second and third layers are enriched with copper sulfidebornite, 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 process of partial oxidation roasting. By this model, it is predicted that oxidation 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 unchangeable. According to irkovi,14 a theoretical model of chalcopyrite oxidation assumes a concentric grain structure (Figure 1) with increase in transformation rate from center to periphery where the core stays unchanged. Figure 1 presents a model of spherical chalcopyrite 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
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EXPERIMENTAL METHODS The chalcopyrite concentrate, from the traditional pyrometallurgical process of copper extraction in the Copper Mining and Smelting Complex Bor (Serbia) was the starting charge. The roasting of chalcopyrite concentrate in a fluidized bed reactor (Smelting Complex Bor) was done using the following standard process conditions: flow of process air 24,00025,000 Nm3, flow of cooling water 12 m3/h, process temperature 670C, time of roasting 90 sec, where charging capacity varied 4555 t/h. After the roasting operation, roasted samples of effluent and overflow were taken. Dishes for sampling were hermetically closed to prevent oxidation of the effluent components, and for the aim of obtaining good results in chemical analysis. To realize the set task regarding the transformation products during roasting, a detailed investigation of samples was carried out by the use of suitable methods: chemical 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 on a SIEMENS device with Cu-anticathode and filtrated emission by Ni-filters at voltage of 40 kV and current intensity of 20 mA. The used literature data in comparison of 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 the Leitz-Ortolux microscope in reflected light.

reaction area.14 The bornite stage appearance as a result of transformation in terms of chalcopyrite oxidation roasting is described in detail.3,7,8,15 The chemistry of chalcopyrite (CuFeS2) oxidation in fluidized layer in the temperature interval from 600 to 720C can be represented by the Reactions 1 and 2.15,16 5CuFeS2+2O2=Cu5FeS4 +4FeS+2SO 5CuFeS2+5O2=Cu5FeS4 +4FeS+2FeO+4SO2 (2) (1)

Table I. Chemical Composition of the Investigated Samples

Partial Chemical Analysis (wt.%) Sample Charge 1 Calcine 1 Overow 1 Charge 2 Calcine 2 Overow 2 Charge 3 Calcine 3 Overow 3 Charge 4 Calcine 4 Overow 4 Charge 5 Calcine 5 Overow 5 Charge 6 Calcine 6 Overow 6 Charge 7 Calcine 7 Overow 7 Charge 8 Calcine 8 Overow 8 Charge 9 Calcine 9 Overow 9 Charge 10 Calcine 10 Overow 10 Cu 14.76 16.97 1.1 12.86 14.93 0.795 19.41 20.68 4.165 18.8 21.32 6.12 19.88 22.72 1.93 18.8 19.96 1.22 15.8 16.1 1.68 16.96 18.8 0.98 15.7 18.4 1.08 15.34 18.06 0.95 SiO2 10.42 15.85 7.2 16.26 20.57 17 11.37 16.53 20.65 11.17 14.53 32.84 11.46 14.14 33.97 12.77 13.41 29.69 13.06 20.64 29.99 11.02 13.89 23.33 12.28 14.32 25.93 12.25 13.84 22.7 Fe 26.44 33.23 2.105 25.97 30.07 1.73 29.18 30.58 5.005 27.37 33.51 7.68 30.72 30.86 2.51 26.72 29.04 3.77 26.67 30.35 2.57 27.23 31.97 1.26 26.3 31.89 1.45 27.64 32.67 1.26 CaO 5.77 1.32 45.005 3.19 1.32 41.56 33.14 3.16 1.67 24.37 1.79 1.45 30.74 2.57 1.58 31.74 2.83 2.46 33.08 2.33 1.75 38.44 2.66 1.5 30.07 3.75 1.52 36.43 S 34.85 20.3 0.8 29.55 18.89 0.6 32.72 19.5 0.6 29.7 19.9 4.18 31.48 21.08 1.18 31.38 19.5 1.28 33.07 19.6 0.39 32.08 20.88 0.79 31.88 21.47 0.69 33.07 22.06 0.44 Fe3O4 0.34 10.66 0.44 0.39 8.99 0.54 0.27 10.31 3.1 11.57 2.27 8.61 0.52 8.07 0.52 9.39 0.64 9.31 9.39 0.12 9.34

The value of Gibbs free energy in the investigated temperature range for Reaction 1 is G = 503510 kJ/mol, and for Reaction 2 G = 13281317 kJ / mol, which confirms the high thermodynamic probability of their occurrence. The aim of this study is to experimentally investigate mineralogical transformations in chalcopyrite concentrate during roasting in fluidized bed reactor and to compare obtained results with the developed theoretical models of copper concentrate roasting. See the sidebar for experimental methods. RESULTS AND DISCUSSION The results of chemical analysis and x-ray diffraction analysis of ten samples of charge, calcine and overflow, taken during the period of one month, are shown in Tables I and II. It can be seen that variations in the chemical composition of analyzed charge samples. It could be said that the calcine, representing roasted copper charge, contains qualitatively the same elements as starting charge, but their quantitative values are completely changed. The increased content of quartz in the overflow appears due to the presence of a high quantity of air, and decreased number of blowers, which cause that part of quartz from the bed to be transferred with air. Mineral composition is the visible change because in the process of the roasting charge, pyrite (FeS2) and a part of chalcopyrite (CuFeS2) from the charge dissociate in the roasting process and
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move into more stable copper and iron sulfides: bornite (Cu5FeS4) and pyrrhotite (FeS). A part of chalcopyrite is unchanged during roasting due to a lack of time for its transformation. Based on optical characteristics of minerals, mineralogical identification of samples was carried out. The following content was determined in the ore samples of charge: chalcopyrite, pyrite, rarely covellite, chalcocite, magnetite, galenite, and sphalerite. In samples of calcine, the following appear: chalcopyrite, bornite, pyrrhotite, pyrite, magnetite, marcasite, digenite, chalcocite, covellite, sphalerite, galenite, ruthile, hematite, and cuprite. There are no ore minerals in the samples of overflow. The samples of calcine are the most important for us. A description of the minerals present in calcine is: Chalcopyrite: (CuFeS2) appears in partly regular to irregular grains of various sizes from some mm to 100 mm. Larger grains are rarely present. It often forms solid solution with bornite. Disintegration of solid solution results into chalcopyrite and bornite, where somewhere bornite was transformed into digenite. This transformation develops from the rim to the central parts of grain, although the laminar separation are present or bornite appears in a form of irregularly distributed veins. It is present in the form of separation in sphalerite very rarely. Fine size grains of chalcopyrite are intergrown with pyrite very rarely, until somewhere it is included into pyrite. Pyrrhotite: (FeS) mainly appears in sponge-like aggregates of spherical form. Due to the fact that it is not present in a charge, it is obvious that it was formed in the roasting process by transformation of starting minerals. Bornite: (Cu5FeS4) appears in irregular grains (size about 15 mm). It presents a product of disintegration of solid solution where chalcopyrite and bornite are formed, and then somewhere bornite was transformed into digenite. Rarely aggregates of bornitedigenite have an edge of cuprite. It also appears independently. Pyrite: (FeS2) also appears in partly regular to irregular grains. It is rarely included in chalcopyrite, and pseudomorphoses of ghetite on pyrite are even more rare (pseudomorphoses appear
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Table II. Quantitative Mineralogical Content was Determined by the Use of Powder Cell Analysis (KMS) Based on X-ray Diffraction Analysis
Sample* 1 1a 1b 2 2a 2b 3 3a 3b 4 4a 4b 5 5a 5b 6 6a 6b 7 7a 7b 8 8a 8b 9 9a 9b 10 10a 10b Chalcopyrite Magnetite (%) (%) 42.3 56.6 26.86 75.96 68.61 66.81 67.73 67.29 57.88 64.13 49.96 69.73 41.51 61.54 54.35 65.57 58.12 62.68 39.38 58.96 21.49 12.12 18.69 20.03 15.66 15.65 19.77 11.22 16.88 14.24 Bornite Pyrrhotite Pyrite (5) (%) (%) 7.91 1.55 3.48 5.59 12.26 4.28 3.68 9.92 6.17 10.01 14 10.33 11.03 7.09 7.95 10.35 15.01 13.29 14.28 16.79 29.95 17.63 16.75 15.32 18.68 15.66 23.79 17.08 25.13 25.3 Quartz (%) 27.74 12.71 55.52 26.14 14.64 38.67 16.95 39.55 23.44 50.75 34.38 56.49 34.7 42.84 28.58 46.07 16.74 39.45 35.33 59.02 Anhydrite (%) 12.47 8.87 6.34 1.42 9.73 5.23 10.61 8.27 9.76 5.32 Calcite (%) 74.82 64.99 54.99 59.02 39.52 38.27 46.56 45.02 50.79 35.66

* Samples:1 10 Samples of Charge; 1a 10a Samples of Calcine; 1b 10b Samples of Overow

O2 FeS

CuFeS2

Cu5FeS4

SO2 Figure 1. Theoretical mechanism of chalcopyrite oxidation.14

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Cp

Bn

Pn

Bn 0.1 mm a Bn b 0.1 mm Cp

Bn Dg Cp 0.03 mm c d 0.1 mm

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 associated with waste. It is very rarely in association with hematite and chalcopyrite. Marcasite: (FeS2) is a rare mineral and it is always in association with pyrrhotite. Marcasite presents a product of pyrrhotite transformation. Digenite: (Cu1,8S) is rarely present. It appears in irregular grains or spongelike aggregates, and as an edge around bornite. Probably it appears as a product of the roasting process. Chalcocite: (Cu2S) is present very rarely in independent grains of irregular form where those grains very often include the waste minerals. Covellite: (CuS) appears as a secondary mineral in irregular fragments or life-like aggregates. Mainly, it is independent until it is less present embedded into chalcopyrite. Sphalerite: (ZnS) and galenite (PbS) are very rare minerals. Somewhere they are intergrown, one with the other, until they are very rarely
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present as separation of chalcopyrite in sphalerite. Goethite: FeOOH is a rare mineral. It appears as a product of pyrite transformation. 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 bornitedigenite. 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 spherical 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 sulfide copper and iron minerals (chalcopyrite and pyrite) transform into lower sulfides, and disassociated sulfur oxidizes to sulfur dioxide. During the roasting of chalcopyritepyrite charge in the fluidized bed reactor, a complete
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disassociation (transformation) of pyrite and partial transformation chalcopyrite to bornite and pyrrhotite is developed, 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 reactor is incomplete. Roasted copper concentrate contains approximately the same elements as concentrate except its chemical content is changed. Quantity of sulfur from sulfide is significantly decreased, quantity of oxide is increased and evaporable compounds from some harmful substances are decreased. Results of experimental investigations show certain variations regarding data in the literature.17 Contrary to the previous models of roasting process, there is no chalocite in effluents. Chalcopyrite in present conditions in the reactor does not transform into chalcocite. 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 transformation process is completely different than the theoretical models1214 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 fluidized bed reactor, pyrite, and a part of chalcopyrite are disassociated 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 transformation 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.
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ACKNOWLEDGEMENTS This work was written with financial aid from the Ministry for Science and Environment Protection and it is a part of Project 176010.
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6. -H. un et al., Metallurgizdat, 31 (1958), pp. 327336. 7. E.V. Margulis, urnal prikladnoj himii, 34 (1961), pp. 21642171. 8. P.N. Bakirdiev and I.S Grozdanov, Cvetnie Metalli, 4 (1986), pp. 4245. 9. M. Coci and P. ukletovi, Mineralogical Transformation in Copper Concentrate Roasting in Fluo-solid Reactor, XXX October Conference on Mining and Metallurgy, ed. Donji Milanovac (Serbia, 1998), pp. 108112. 10. M. Coci, Quantitative Determination of Transformation Products in the Copper Concentrate Roasting Process in Fluo-solid Reactor (Ms. Thesis, University of Belgrade, 2005). 11. M. Coci et al., JMM, 43B (2007), pp. 7178. 12. V.I. Smirnov and A.I. Tihonov, Obig mednih rud i koncentratov, Metallurgija, Moskva (1966), pp. 4952. 13. Octave Levenspiel, Chemicals Reaction Engineering (New York: John Wiley & Sons, Inc., 1972). 14. M. irkovi, Theoretical and Experimental Study of the Process of Roasting Copper Sulphide Con-

centrates in the Reactor with Fluidizatio Layer using Oxygen-enriched Air (Ms. Thesis, University of Belgrade, 1999). 15. M. irkovi et al., EPD Congress 1999, ed. B. Mishra (Warrendale, PA: TMS, 1999), pp. 933944. 16. M. irkovi, J. Marinkovi, and D. Vuurovi, Metallurgy, 3 (1999), pp. 227336. 17. S. Janji, Crystallographic and Mineralogical Investigation of Copper Sulphides Minerals and Products of Piromatallurgic Processing in Bor Copper Smelter (Ph.D. thesis, University of Belgrade, 1978), pp. 101110. Mira B. Coci, assistant, and Dragan M. Manasijevi, professor, are members of the Technical Faculty in Bor, and Mihovil M. Logar, a professor with the Faculty of Mining and Geology, are with the University of Belgrade, Bor, Serbia; Saa Lj. Coci, senior geologist, Avala Resources, Bor; and Sneana S. Devi, expert associate, are with the Institute IMS in Belgrade. Mrs. Coci can be reached at mcocic@tf.bor.ac.rs.

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