Assessment of slag and copper equilibrium in Vaniukov two-zone converter

L. B. Tsymbulov*
Published by Maney Publishing (c) Canadian Institute of Mining, Metallurgy and Petroleum

A brand new process of blister copper production from copper matte and concentrates in the two-zone Vaniukov converter has been developed at the Gipronickel Institute facility. Thermodynamic analysis of exchange interaction has been performed for the slag melt-metal phase formed in the over-the-lance area of the Vaniukov converter reduction zone system and for slag melt-bottom phase of blister copper located in the bottom (under-the-lance) area of the Vaniukov converter system. Based on the thermodynamic analysis data, the original design of the two-zone Vaniukov converter has been proven to be able to create conditions ensuring production of blister copper of higher quality, as compared to the one-zone Vaniukov converter process, copper concentration in slag being substantially lower. Un procede entierement nouveau de production de cuivre blister dans un convertisseur Vaniukov ` a deux zones, a partir de matte de cuivre et de concentres, a ete developpe aux installations de ` ` lInstitut Gipronickel. On a effectue lanalyse thermodynamique de linteraction dechange pour le systeme 0bain de scorie-phase de metal forme dans la region au-dessus de la lance de la zone ` de reduction du convertisseur Vaniukov0 et pour le systeme 0bain de scorie-phase du bas0 du ` cuivre blister situe dans la region du bas (sous la lance) du convertisseur Vaniukov. En se basant sur les donnees de lanalyse thermodynamique, on a montre que le concept original du convertisseur Vaniukov a deux zones etait capable de creer les conditions assurant la production ` de cuivre blister de meilleure qualite par rapport au procede du convertisseur Vaniukov a une ` zone, la concentration du cuivre dans la scorie etant substantiellement plus basse.
Keywords: Vaniukov two-zone converter, Equilibrium, slag, Blister copper, Metal prills

Introduction
Recently, a brand new process for treating copper nickelcontaining mattes and copper rich concentrates in a twozone Vaniukov converter has been under development (see Fig. 1). Physically, the two-zone Vaniukov converter consists of an oxidation zone, a reduction zone and a combined siphon (lift tube) having the original design and intended for continuous discharge of blister copper and slag. Copper matte or copper rich concentrates (combined treatment is also possible), uxes and coal are charged into the converters oxidation zone. Oxygenair mixture containing 8095% oxygen is delivered via lances. The use of coal is necessary in case of heat deciency. Slag formed in the oxidation zone is delivered to the reduction

JS Gipronickel Institute, 11 Grazhdansky Prospect, Saint Petersburg 195220, Russia *Corresponding author, email lbcym@nickel.spb.ru
2011 Canadian Institute of Mining, Metallurgy and Petroleum Published by Maney on behalf of the Institute Received 7 April 2010; accepted 9 December 2010 DOI 10.1179/000844311X12949291727899

zone where the reduction process takes place in the presence of coal and gas mixture formed during combustion of gaseous or liquid fuel at oxygen deciency. Metal alloy prills, and droplets produced in the process of reduction, settle into the blister copper melt formed during oxidation processes in the converters rst zone. Then, the produced blister copper is delivered to the mixer via the siphon. In the mixer, blister copper accumulation takes place, followed by its delivery into the anode furnaces for rening. Slag formed in the reduction zone and containing a small portion of copper, a substantial portion of nickel and actually entire cobalt also enters the siphon, wherefrom it is subject to continuous discharge via the siphons plate located at the level of 20002200 mm above the converters hearth. The discharged slag is granulated and transported to nickel smelting facility for further treatment. Working areas of the converter zones are divided by water cooling partitions and are tted with separate gas removal systems. Gases of the oxidation zone containing SO2

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1 Schematic of two-zone Vaniukov converter for copper matte and concentrate smelting

are sent for elemental sulphur or sulphuric acid production, while those of the reduction zone containing CO and H2 are subject to after-burning by air or oxygenair mixture, being delivered via lances specially installed in top-row caissons (see Fig. 1), cleaned from dust and discharged into the atmosphere. As mentioned by Knyazev et al.1 and Tsymbulov et al.2 who dedicated to the development of processes for treating various types of sulphide copper and coppernickel feed in the two-zone Vaniukov converter, one of the most relevant advantages of the two-zone Vaniukov convertor is the ability of simultaneous production of marketable product (matte or blister copper) of higher quality slag formation with a lower non-ferrous metal content, as compared to the one-zone Vaniukov converter or other processes where only oxidising smelting of copper and coppernickel concentrates is performed (e.g. Ausmelt and Isasmelt processes, Outokumpu ash smelting, Inco ash smelting, Noranda, Teniente processes, etc.). Specically, work2 comparing the use of two-zone and one-zone Vaniukov converters for the process of blister copper production shows that the former makes it possible to achieve 2?53 times decrease in the copper concentration in slag and, at the same time, to improve blister copper quality at the expense of decreasing its oxygen content. The concentration of nickel that is considered as extremely undesirable impurity in the produced copper shows no increase in spite of the reduction processes taking place in the converters second zone. It was proposed that the above advantages of the twozone converter are related to the fact that slag formed in

the second zone during the reduction process is removed well before it achieves equilibrium with copper located in the under-the-lance area of the converter where no efcient agitation of slag and metal melts takes place. If the assumption is true, the Vaniukov two-zone converter allows a substantially decreasing rate of valuable component recovery into the marketable product, which, in combination with the improved quality of the marketable product, should recoup the second zone operating costs. Based on this reasoning, it is very important to learn the extent to which the composition of the reduction zone slag is determined, on the one hand, by its interaction with the bottom phase of blister copper and, on the other hand, by its interaction with the metal phase (metal prills) formed in the above-the-lance area of the reduction zone. Therefore, it is necessary to calculate the equilibrium in the reduction zone slag meltmetal prills and the reduction zone meltblister copper melt systems. For better visualisation, the essence of slag and metal melts interaction is shown in Fig. 2. To make it clear, experimental studies using a pilot two-zone Vaniukov converter have been performed accompanied by thermodynamic analysis of slag and metal melts interaction.

Experimental
Figure 2 shows a schematic sketch of the pilot two-zone Vaniukov converter built at Norilsk Nickel Severonickel Combine in 2005.

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1: oxidation zone; 2: reduction zone; 3: siphon; 4 and 5: uptakes of the reduction and oxidation zones; 6 and 7: ue ducts of reduction and oxidation zones; 8: burner; 9: slag plate; 10: tap hole for copper discharge; 11: emergency tap hole; 12 and 13: water cooled partitions; 14: lances; 15: lances for off gases after burning; 16: copper caissons; 17: embedded copper refrigerators 2 Schematic of pilot two-zone Vaniukov converter at Severonickel Combine (scheme of melts exchange interaction)

Oxidation and reduction zones hearth areas are 4?7 m2 each; the siphon hearth area is 2?0 m2, and total converter hearth area is 11?4 m2. The oxidation zone is completed with six lances (four principal and two additional ones located at the converter ank), while the reduction zone is tted with four lances. The lance design, their position, as well as the volume of air oxygen blast and fuel delivered through them, are identical to the commercial parameters, which allow making rather authentic prognosis with regard to the processes that would take place in a commercial scale converter, based on the pilot testing results. The process of treatment of copper concentrate from high matte separation (67?5Cu3?9Ni4?5Fe0?24Co 21?5S, mass-%) to blister copper can be described as follows. A combination of copper concentrate from high matte separation, uxes and coal are charged into the oxidation zone. Productivity by the treated concentrate is 4 t h21. Quartzite and limestone are used as uxes. Airoxygen and propanebutane mixtures are injected via lances. The use of propanebutane and coal is necessary for maintaining heat balance in a relatively small scale converter. Slag formed in the course of smelting, and containing oxide copper in substantial amount (y22 mass-%Cu), enters the converters reduction zone where it is reduced by a gas mixture generated during propanebutane mixture combustion in an oxygen decient environment. The objective of the reduction stage is to ensure partial reduction of oxide

copper from the slag melt. A high rate reduction of slag is unacceptable, which is imposed by the nal target of the process, namely production of blister copper conditioned by nickel content (about 0?40?5%). In the case of a high rate reduction of slag, a substantial portion of nickel and some portions of cobalt and iron will be reduced in the converters second zone. Prills of copper based metal alloy formed in the reduction zone settle into the bottom phase that is considered to be common for the zones and the siphon. As copper accumulates, it is periodically discharged via the tap hole. In this type of converter, continuous copper discharge through the siphon device is impossible since the copper ow is relatively small, which results in freezing of the siphon channel. Slag formed in the reduction zone enters the siphon wherefrom it is discharged via the siphon plate in a continuous mode. Detailed results of the pilot testing are shown by Tsymbulov et al.2 To solve the task, i.e. to determine the level of proximity to equilibrium achieved for slag meltblister copper and slag meltmetal prills systems, slag and blister copper sampling has been performed in accordance with the following procedure. In the oxidation zone, the process parameters, such as the volume of charged sulphide concentrate and uxes, oxygen and air consumption, propanebutane and coal consumption, were maintained at a constant level. Compositions of slag and copper produced at the oxidation stage

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were as follows: slag, 22?4Cu7?4Ni0?58Co17?4Fe 26?9SiO211?6CaO, mass-%; copper, 98?3Cu0?41Ni 0?005Co0?03Fe0?05S((1?5)O, mass-%. In the reduction zone, the so called oxygen consumption factor a was the only variable measured. Factor a was calculated as follows VO (%O2 )zVair |0:21 (1) a~ 2 QCxHy KCxHy where VO2 is oxygen consumption in the reduction zone, nm3 h21, %O2 is oxygen inclusion volume fraction in the process oxygen, Vair is air consumption in the reduction zone, nm3 h21, QCxHy is hydrocarbon fuel (propane butane) consumption, nm3 h21 and KCxHy is the coefcient characterising the type of fuel in terms of its meeting complete combustion conditions (for propane butane it is 5?8). In the reduction zone, the factor a was changed about once per day. Its alteration causes changes in the cleaned slag composition. However, no variations should be applied to the blast mode in the reduction zone for a y24 h period so that complete change is achieved not only in the slag bath, but also in the converters hearth phase (blister copper) being also subject to variations in composition due to changes in the second zones reduction environment. In 24 h, changes should be made to the reduction process parameters, and hardened slag of the reduction zone and blister copper at the moment of its discharge should be sampled. After sampling, the reduction mode in the second zone should be changed and the altered parameters should be maintained for no less than 24 h. Blister copper has been analysed using chemical methods. The sample of the reduction zones hardened slag has been tested using scanning electron microscopy (SEM) and X-ray spectrum microanalysis (XRSM)

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methods. Sample hardening has been performed in order to preserve the ratio of mechanic and soluble forms of non-ferrous metals present so that it meets the value of their ratio in the melt. The sample has been hardened by introducing a cooled steel bar into melt through the lance hole. Studies by SEM and XRSM have been carried out on a Tescan 5130 MN electron microscope completed with the microanalysis system. Using SEM and XRSM methods, slags have been analysed to determine the composition of the hardened oxide silicate melt (the sample base) and that of metal prills present in them. Thus, a number of slag and blister copper samples have been prepared to evaluate the level of proximity of the slag meltmetal prills and slag meltblister copper systems to equilibrium. Table 1 shows the compositions of slag and blister copper. The essence of the evaluation method can be explained based on the following thermodynamic provisions. First, if equilibrium is achieved between two phases (in our case, they are two melts slag and metal), equilibrium is achieved for any other exchange interaction taking place in these phases. Reaction (2) is the most representative example of this interaction, since its progress between metal and slag melts in a Vaniukov furnace does not give rise to any doubts NizCu2 O~2CuzNiO (2)

Second, the value of the equilibrium constant Ka can be calculated according to the following equation ln Ka ~{
0 0 0 DGT DHT DST ~{ z RT RT T

(3)

0 where DGT is the change in the reactions standard 0 Gibbs energy at temperature T; DHT is the reaction

Table 1 Compositions of structural components of reduction zones slag and blister copper for two-zone Vaniukov converter* Content/mass-% a in reduction zone 0.84 0.79 0.76 0.75 0.74 0.73 Structural component Silicate glass (slag) Metal prills (slag) Blister copper Silicate glass (slag) Metal prills (slag) Blister copper Silicate glass (slag) Metal prills (slag) Blister copper Silicate glass (slag) Metal prills (slag) Blister copper Silicate glass (slag) Metal prills (slag) Blister copper Silicate glass (slag) Metal prills (slag) Blister copper MgO 3.6 3.9 2.7 3.4 2.9 3.7 Al2O3 2.1 2.3 1.9 1.9 1.9 1.9 SiO2 29.3 32.6 35.2 36.7 35.2 36.2 CaO 9.6 10.5 18.3 17.0 17.4 14.2 Cr2O3 0.30 0.35 0.31 0.31 S 0.32 0.05 0.52 0.03 0.17 0.05 0.23 0.05 0.29 0.05 0.30 0.04 Fe 17.3 1.4 0.03 18.5 0.6 0.02 19.0 2.3 0.02 18.1 0.8 0.04 19.6 1.4 0.03 20.2 1.8 0.04 Co 0.46 0.005 0.39 0.005 0.86 0.005 0.85 0.006 0.85 0.006 0.91 0.01 Ni 7.1 0.7 0.47 7.1 2.7 0.42 7.5 4.6 0.78 7.5 4.9 0.59 8.0 11.2 0.82 7.0 14.7 0.55 Cu 20.2 97.6 98.5 14.8 96.2 98.6 6.0 92.9 98.8 6.2 94.1 98.9 5.2 87.0 98.7 6.9 83.2 98.8 O 9.7 0.53 9.9 0.88 8.2 0.42 8.1 0.49 8.6 0.44 8.7 0.72

*Silicate glass and metal prills composition has been determined by SEM and XRSM methods, while blister copper composition has been determined by chemical analysis.

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0 enthalpy change; and DST is the reaction entropy change. 0 0 For calculation of DHT and DST values, data on formation enthalpies and standard entropies of substances participating in reaction (2) at temperature T (in our case, the smelting temperature is 1673 K) can be used. The said data can be found in reference books. It should be noted that the equilibrium constant value calculated according to equation (3) envisages that the reactions components are in the aggregative state typical for the given temperature. For substances with a melting temperature of above 1673 K (Ni and NiO), corrections considering the change value of Gibbs 0 energy at smelting DGsm should be made. Third, equilibrium constant Ka can be also calculated as a ratio of activity of components in reaction (2), according to the equation

participating in reaction (2) are characterised by melting temperature below the reactions temperature level. For nickel and nickel oxides, melting temperatures exceed the reaction temperature level, which are 1728 and 2230 K respectively. 0 DGsm is calculated based on the equation
0 0 0 0 DGsm ~DHsm {TDSsm ~DHsm {T 0 DHsm Tsm

(5)

Ka ~

2 aNiO a2 XNiO XCu cNiO c2 Cu Cu ~ aCu2 O aNi XCu2 O XNi cCu2 O cNi

In correcting for undercooling, it is assumed that heat of smelting does not depend on temperature. In other words, the difference in heat capacity of substances in solid and liquid states is ignored. Out of the discussed reactions components, a correction is made for nickel and nickel oxides. At 1673 K 0 17:5 DGsm Ni ~17:5{1673 ~0:56kJ 1728
0 DGsm

(4)

NiO

~50:6{1673

where a is activity, X is molar concentration and c is activity coefcient. For all the components in reaction (2), pure components are taken as in a standard state. Thus, if the slag and metal melts are in equilibrium, and X and c are known for all the components participating in reaction (2), Ka calculated according to equation (4) should coincide with that calculated according to equation (3), with corrections for undercooling of components with melting temperature exceeding the reaction temperature being considered. Should the Ka value calculated according to equation (4) be substantially different from that calculated in accordance with equation (3), an equilibrium between metal and slag melts cannot be achieved. Based on the level of discrepancy between the Ka value due to equation (3) (let us call it actual meaning of equilibrium constant value Kact, since it will be calculated on the basis of reliable thermodynamic reference data) and that from equation (4) (let us call it a calculated value Kcalc, since it will be received from our experimental data), we shall make conclusions on the systems deviation scope relative to the equilibrium state.

50:6 ~12:6 kJ 2230

0 Then, DGsm makes 0 0 0 DGsm ~ DGsm NiO { DGsm Ni ~12:6{0:56~12:04 kJ

With corrections for overcooling considered

0 DG1673 ~{43:7z12:04~{31:7 kJ; Ka ~Kact: ~9:77

Discussion
First of all, we have to determine the Ka value of reaction (2) according to equation (3). Data on formation enthalpies and standard entropies of substances have been used by several authors.36 Since differences in values found in the said reference books are not fundamental ones, and there is no reason to give preference to any of the abovementioned reference sources, values of standard Gibbs energy calculated based on the data from the abovementioned reference books have been averaged. Naturally, there is no need for the detailed description of the said calculations 0 algorithm. They are widely known. The averaged DG1673 value for reaction (2) is 243?7 kJ, and Ka523?1. As mentioned above, the received Ka value requires correction for undercooling, since not all the substances

Based on the experimental data (see Table 1), we compare the received equilibrium constant value termed Kact with Ka values calculated according to equation (4). At that, Kcalc(1) value denotes the equilibrium in the slag meltmetal prills system, while Kcalc(2) denotes the equilibrium in the slag meltblister copper system. Table 2 shows calculation results for Kcalc(1) and Kcalc(2) values. To calculate the equilibrium constant value of the slag meltmetal prills system, concentrations of XNiO, XCu2 O , XNi and XCu have been determined using SEM and XRSM methods. For XNiO and XCu2 O , values have been determined by analysing the composition of silicate melt (silicate glass). For XNi and XCu, values have been determined by analysing metal prills present in silicate melt (see Table 1). Figure 3 shows the typical microstructure of the reduction zones hardened slag melt. Activity coefcients cNiO and cCu2 O have been calculated using FactSage 6?0 integrated thermodynamic software. Activity coefcients cNi and cCu have been taken from the earlier in house studies of metal systems containing copper and metals of iron class.7,8 According to the type of composition, metal prills can be attributed, with a high level of accuracy, to CuNiFe triple metal system (see Table 1). In estimating Kcalc values for the slag meltblister copper system, the same meanings of XNiO, XCu2 O , cNiO and cCu2 O have been taken as in calculations for the slag meltmetal prills system. Values of XNi and XCu for blister copper have been determined based on its chemical analysis. Since blister copper melt, in contrast to metal prills, contains a substantial amount of oxygen (about 0?40?9 mass-%), the use of data available for CuNi double metal systems is not correct. It is

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3 Typical microstructure of reduction zones hardened slag melt in two-zone Vaniukov converter (1: metal prill; 2: spinel)

necessary to consider the effect of the oxygen, while the inuence of S, Fe and Co on values of nickel and copper activity factors can be ignored owing to their negligible content (see Table 1). Analysis of the published data, CuNiO system studies carried out by Taskinen7 and Kemori et al.8 in particular, show that oxygen dissolved in copper exerts marked effect only on the nickel activity coefcient. Thus, the inuence of oxygen on the copper activity coefcient can be ignored. To determine Ni activity coefcient in oxygen-containing copper, parameters of interaction have been used ln cNi ~ ln c? zXNi e(Ni) zXO e(O) Ni Ni Ni c? Ni (6)

4 Dependencies of Kslagprills and Kslagblister copper on reduction potential value (oxygen consumption factor a) generated in Vaniukov furnaces reduction zone: changes of a value within range of 0?73 to 0?84 correspond to log PO2 value changes within range of 29?0 to 27?9

where is the boundary activity coefcient for nickel in CuNi system, XNi and XO are molar shares of nickel and oxygen in blister copper, and e(Ni) and e(O) are interaction Ni Ni parameters. Based on tracing ln cNi5f(XNi) dependence, e(Ni) value Ni related to CuNi metal system has been found equal to 24?55. The selected value of e(O) ~e(Ni) ~{5:18 repreO Ni sents the average of e(Ni) values taken by other O researchers.910 The value of c? has been determined Ni by averaging the most reliable data of CuNi system thermodynamic studies.11 At 1673 K, c? 54?94. Ni

For visualisation, Kcalc(1) and Kcalc(2) presented in Table 2 have been included in the plot as a function of the Vaniukov converter second zones reduction potential expressed by oxygen consumption factor a (see Fig. 4). According to the plot, the calculated constant Kcalc(1) for the silicate meltmetal prills system actually coincides, within the limit of accuracy in dening level of concentrations and activity factors values, with Kact assessed using formation enthalpies and standard entropies. It proves the fact that silicate melt and the suspended prills of metal phase formed during reduction are in a state close to thermodynamic equilibrium. On the contrary, the calculated constant value for the silicate meltblister copper bottom phase system
exchange interaction

Table 2 Molar shares, activity factors and calculated equilibrium constants for [N]z(Cu2O)52[Cu]z(NiO) in slag meltmetal prills and slag meltblister copper systems Molar shares of components ablast in reduction zone 0.84 0.79 0.76 0.75 0.74 0.73 Discussed system Slagmetal prills Slagblister copper Slagmetal prills Slagblister copper Slagmetal prills Slagblister copper Slagmetal prills Slagblister copper Slagmetal prills Slagblister copper Slagmetal prills Slagblister copper XCu2 O 0.119 0.119 0.084 0.084 0.032 0.032 0.033 0.033 0.028 0.028 0.037 0.037 XNi 0.0075 0.0051 0.0290 0.0044 0.0493 0.0083 0.0526 0.0063 0.1195 0.0088 0.1563 0.0058 XNiO 0.090 0.090 0.086 0.086 0.086 0.086 0.085 0.085 0.091 0.091 0.080 0.080 XCu 0.970 0.974 0.954 0.962 0.921 0.975 0.934 0.975 0.859 0.974 0.818 0.966 Activity factor cNi 2.818 4.350 3.837 4.070 3.394 4.380 3.583 4.360 2.800 4.350 2.468 4.170 cCu 1.004 1.010 1.006 1.010 1.018 1.010 1.011 1.010 1.045 1.010 1.074 1.01

cNiO 1.911 1.911 2.117 2.117 2.313 2.313 2.344 2.344 2.987 2.987 3.341 3.341

cCu2O 1.774 1.774 1.727 1.727 1.682 1.682 1.675 1.675 1.528 1.528 1.447 1.447

Kcalc 36.6 35.5 10.4 66.7 19.4 98.6 17.1 128.6 15.3 163.6 10.0 198.3

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5 Dependence of components activity in contacting phases of Vaniukov converter on oxygen consumption factor a

(Kcalc.(2)) is strongly different from the actual equilibrium constant value. It should be noted that the lower a value is and, consequently, the lower PO2 value is in the system, the more pronounced the difference between Kact and Kcalc(2) values becomes. Thus, for instance, at a50?84 (log PO2 527?9) when the recovery rate of oxides contained in slag, copper oxide in particular is extremely low, the reduction zone slag composition is in fact similar to that of the oxidation zone slag, and Kact and Kcalc(2) values are rather close (see Fig. 4). As a value decreases, nickel activity rises in metal prills formed in the course of reduction, which, in accordance with reaction (2), results in the decrease in copper oxide activity in slag and the increase in nickel oxide activity (see Fig. 5). Owing to the mass action law (see equation (4)), these changes in the slag composition and properties should result in the increase in nickel activity in blister copper and the decrease in copper activity. However, according to Fig. 5, nickel and copper activities in blister copper show no actual changes, thus proving an absence of any signicant interaction between slag melt and blister copper in the under-lance-area of the converter.

Hence, the non-ferrous metals content in slag melt is determined by the composition of metal suspension formed during the process of cleaning and is practically non-dependent on the content of the Vaniukov converters bottom phase formed mainly in the course of processes taking place in the oxidation zone. It should be mentioned that the above conclusion may be extrapolated to any technological process taking place in the Vaniukov converter having the design developed at the Gipronickel Institute. In particular, treatment of copper and coppernickel sulphide concentrates in the two-zone Vaniukov converter makes it possible to produce very high quality matte (Cu or CuzNi content: 7075%), with the said metals content in slag being at dump concentration.

Conclusions
Using the case of rich copper concentrate treatment to blister copper in a pilot two-zone Vaniukov converter and based on the data of thermodynamic analysis of the process, the following has been proven.

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1. The reduction zones slag and metal prills and droplets formed in the course of reduction are in a state close to equilibrium. 2. The Vaniukov converters bottom phase representing blister copper formed mainly owing to the processes taking place in the Vaniukov converters oxidation zone and the reduction zones slag contacting with the said bottom phase, fail to notably approximate the state of equilibrium for the Vaniukov converter treatments residence time, i.e. exchange interaction processes between them are highly limited. Thus, in a two-zone Vaniukov converter of the proposed design, conditions are maintained that allow simultaneously achieving a lower residual copper level in the produced slag and higher quality of the produced blister copper than it could be possible according to the equilibrium distribution. For instance, for a one-stage treatment of nickel-containing copper concentrate, the produced slag contained 22% copper, and blister copper contained 1?5 mass-% oxygen. For two-zone smelting, there was 8% copper in slag, and 0?40?9% oxygen in blister copper. A similar conclusion is also possible for the case of copper and coppernickel concentrate treatment to matte in Vaniukov converter of the same design. It is possible to produce very high quality matte (Cu or CuzNi content: 7075%) at a dump level of nickel and copper content in slag.

References
1. M. V. Knyazev, A. G. Ryabko, L. B. Tsymbulov and L. S. Tsemekhman: Two-zone Vaniukov furnace: new potential copper and nickel production, Proc. Sohn Int. Symp., San Diego, USA, August 2006, TMS, Vol. 8, 327334.

2. L. B. Tsymbulov, M. V. Knyazev, L. Sh. Tsemekhman and M. V. Knyazev: Pilot testing of a process treatment of Nicontaining copper concentrate after high-grade matte separation resulting in blister copper production in two-zone Vaniukov furnace, Proc. 6th Int. CopperCobre Conf., Toronto, Ont., Canada, August 2007, Canadian Institute of Mining, Metallurgy and Petroleum, Vol. III (Book1), 397 409. 3. A. Robie and B. S. Hemingway: Thermodynamic properties of minerals and related substances at 298,15 K and 1bar (105 paskals) pressure and at higher temperatures, US geological survey bulletin 2131, United States Government Printing Office, Washington, DC, USA, 1995, 461. 4. I. Barin, O. Knacke and O. Kubaschewski: Thermochemical properties of inorganic substances, 861; 1977, Dusseldorf, Springer-Verlag. 5. J. F. Elliot and M. Gleiser: Thermochemistry for steelmaking, Vol. 1, 296; 1960, London, Pergamon Press. 6. L. B. Pankratz, J. M. Stuve and N. A. Gokcen: Thermodynamic data for mineral technology, Bulletin 677, US Bureau of Mines, Washington, DC, USA, 1984, 355. 7. P. Taskinen: Liquidus equilibria and solution thermodynamics in copper-rich coppernickeloxygen alloys, Acta Polytech. Scand. Chem. Incl. Metall. Ser. Ch., 1981, 145, 145. 8. N. Kemori, I. Katayama and Z. Kozuka: Thermodynamic properties and solubility limits of oxygen in liquid (nickelzcopper) alloys, J. Chem. Thermodyn., 1982, 14, 167184. 9. A. D. Kulkarni and R. E. Johnson: Thermodynamic studies of liquid copper alloys by electromotive force method: part 2. The CuNiO and CuNi systems, Met. Trans., 1973, 4, 1723 1727. 10. P. Hutonen and P. Taskinen: Activity of oxygen in dilute CuNi and CuSb alloys, Scand. J. Metall., 1979, 8, 123127. 11. A. G. Morachevsky, A. G. Ryabko and L. Sh. Tsemekhman: Thermodynamics of systems and processes in nickel and copper metallurgy. Issue 1. Thermodynamics of liquid alloys in nickel copperiron system, 88; 2002, Saint Petersburg, Polytechnical University Publishing House.

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