Distribution behavior of cobalt, selenium, and tellurium between nickel-copper-iron matte and silica-saturated iron silicate slag

The distribution coefficients (D _X) of cobalt, selenium, and tellurium between nickel-copper-iron matte and silica-saturated iron silicate slag were determined as a function of matte and slag compositions, temperature, and the partial pressure of oxygen. The effect of slag additives, such as CaO, MgO, and Al₂O₃, on the distribution behavior of the minor elements was also investigated. Analysis of the data indicated that D _Co, D _Se, and D _Te were strongly dependent on the matte grade and slag additives. The effect of slag additives on the solubility of Co, Se, and Te in slag was discussed in terms of various experimental conditions. Cobalt distribution coefficients were found to decrease with increasing oxygen partial pressure, indicating the oxidic dissolution of cobalt in the slag. Based on the experimental results and available thermodynamic data, the activity coefficients of CoS in the nickel-copper-iron matte were estimated as a function of mole fraction of FeS in the matte at 1250 °C. Meanwhile, the distribution coefficients of both selenium and tellurium increased when raising the partial pressure of oxygen, implying that there was molecular dissolution of selenium and tellurium in the slag within the oxygen partial-pressure range investigated in this study.     

Tellurium distribution in copper anode slimes smelting

Tellurium is a common minor constituent of copper anode slimes. The distribution of tellurium between the phases during slimes smelting is an important consideration, both in terms of metal quality and the capture of the oxidized tellurium. In this work, the oxidation by oxygen at 1100 °C of a silver-copper selenide matte containing 2 pct tellurium has been examined. The distribution of tellurium between the phases was determined as the extent of oxidation increased, and the system was modeled using a computational thermodynamics package. Oxidized tellurium was found to report to the slag, with none being removed with the gas. The thermodynamic model predicted, to an acceptable level, the tellurium content of all phases as oxidation progressed. It was used to show that oxidation by air rather than oxygen results in higher residual tellurium levels in silver metal and that the lower the smelting temperature, the greater the extent of tellurium elimination from silver to the slag.     

Thermodynamic prediction of melting of copper-electrolyte slime

Balance calculations of multicomponent equilibrium compositions in the gas–liquid–solid system under oxidizing smelting of the copper-free copper-electrolyte slime, during which sulfur, selenium, and tellurium dioxides transfer into the gas phase, while compounds of lead, copper, antimony, iron, and aluminum are concentrated in the composition of the silicate slag, are performed with the help of the Outotec’s Chemical Reaction and Equilibrium Software HSC Chemistry program. It is established that, under optimal conditions of oxidizing smelting of the charge (100 kg) of the electrolyte slime (O₂ ≈ 0.9 kg, SiO₂ ≥ 6%, CaO ~ 3%, t = 1200°C), lead, antimony, and arsenic almost completely transfer into the silicate slag, while copper and silver (above 91%) transfer into the matte. Selenium is distributed between the gas phase (49.8%), matte (24.1%), and metallic phase (26.1%), while tellurium is distributed between sublimates (14.4%), silicate slag (8.4%), and matte (77.2%).     

The distribution of silver,gold, platinum and palladium in metal-matte systems

The distribution of silver between molten metal and matte was determined at temperatures of 1150 to 1250°C. The partition coefficient (K_Ag-ratio of wt pct silver in matte to wt pct silver in metal) was 0.46 and was essentially independent of silver concentration, temperature, iron content and oxygen and SO₂ partial pressures over the ranges studied. Only the presence of nickel significantly affected K_Ag, causing it to rise from 0.46 to 1.16 within the region of liquid immiscibility. Outside this region all silver was intimately associated with chalcocite, rather than the heazel woodite or metallics, formed during solidification. Studies on other precious metals showed that K_Au=8×10^?3, K_Pd=6×10^?3 and K_Pt=4×10^?4 in the Cu?S system at 1200°C. Application of these results to actual operations is discussed, as is the chemical behavior of precious metals during matte smelting.     

Distribution of Gold and Silver between Copper and Matte

The distribution coefficients of silver and gold between copper and matte phases have been measured at 1400 and 1500 K. For 0.07 to 0.13 wt pct silver and 0.0022 to 0.0042 wt pct gold in ironfree matte, the distribution coefficients of silver and gold are independent of concentration. For iron-bearing matte, the distribution coefficients of silver and gold are correlated with iron content of the matte. From the measured values of the distribution coefficients of silver and gold, the activity coefficients of AgS_0.5 and Au in copper-saturated matte have been calculated. The following correlations express these results: log γ°_AgS0.5(1) = -425/T - 0.074 + 0.09N_FeS, log γ°_Au(1) =-7620/T + 7.25 forT = 1400 to 1500 K and N_FeS, mole fraction of FeS = 0 to 0.28. The present values of the activity coefficients of AgS_0.5 must be used exclusively in conjunction with the following Gibbs free energy of formation: 2Ag(l) + 1/2S₂(g) = Ag₂S(l), ΔG° = -23960 + 10.295T (cal/mol). M. Nagamori, formerly Associate Professor of Metallurgy at The University of Utah.     

Volatilization of bismuth in copper matte converting —computer simulation

A computer model has been developed to simulate the behavior of bismuth in copper matte converting at 1100 to 1300 °. The rate equation is integrated numerically by dividing a continuous process of matte converting into a great number of microsteps, in each of which the volatilization of Bi-bearing gases is thermodynamically calculated by assuming a steady state. The bubbles of offgas consisting of SO₂ and N₂ are assumed to be saturated with the vapors of BiS, Bi, BiO, and Bi₂. However, the partial pressures of BiO and Bi₂ are found to remain negligible at all stages of converting. BiS is the most volatile species over the slag-making stage with low grade mattes, but its volatility decreases markedly, becoming negligibly low over white metal. When the copper content of the initial matte is known together with the weight of matte, converting temperature and blowing rate of tuyere air, the present computer model can predict the Bi contents in all the phases involved (gas, slag, matte, copper) at any given time. The predictions by the present computer model are compared with the known commercial data from various smelters around the world. The agreements between the computer predictions and the commercial data are excellent in all cases, so that the present computer model can be used to monitor and optimize the bismuth elimination in the actual industrial operations of copper matte converting. Formerly Associate Professor, Department of Metallurgical Engineering, University of Utah, Salt Lake City, UT 84112.     

Cobalt distribution during copper matte smelting

Many smelter operators subscribe to the “precautionary principle” and wish to understand the behavior of the metals and impurities during smelting, especially how they distribute between product and waste phases and whether these phases lead to environmental, health, or safety issues. In copper smelting, copper and other elements are partitioned between copper matte, iron silicate slag, and possibly the waste gas. Many copper concentrates contain small amounts of cobalt, a metal of considerable value but also of some environmental interest. In this work, the matte/slag distribution ratio (weight percent) of cobalt between copper matte (55 wt pct) and iron silicate slag was thermodynamically modeled and predicted to be approximately 5. Experiments were performed using synthetic matte and slag at 1250 °C under a low oxygen partial pressure and the distribution ratio was found to be 4.3, while between industrial matte and slag, the ratio was found to be 1.8. Both values are acceptably close to each other and to the predicted value, given the errors inherent in such measurements. The implications of these results for increasingly sustainable copper production are discussed.     

Selenium partitioning between slag and matte during smelting

Copper concentrates usually contain a number of minor as well as precious elements, the control of which in copper smelting processes is often a key to the quality of the anode copper produced and may also have a bearing on the overall economics of the process. During copper smelting, the copper concentrates are partially oxidized to form slag and matte. The molten slag and matte are separated from each other in the settler. The matte being heavier in density settles at the bottom of the furnace and slag being lighter in density floats over the matte and is eventually discarded off. During the separation, selenium is distributed between slag and matte. Selenium is a value added by-product of copper process. The lower recovery of selenium from the copper process is attributed to the high loss of selenium to the discarded slag. Knowledge of the distribution and form of selenium in slag and matte is very important in the control of the selenium loss, although to date very little is known regarding their distribution. The samples of slag and matte were collected from the smelter exit before their separation. Selenium was added in different proportions in the sample. The experiments involving slag-matte separation were performed at 1250°C for 4 hours of soaking time under inert atmosphere in a vertical tubular furnace. The distribution of selenium and the mechanism by which selenium is dissolved in matte and slag have been established by this study.     

Effects of O,Se, and Te on the rate of nitrogen dissolution in molten iron

The effects of oxygen, selenium, and tellurium on the rate of nitrogen dissolution into molten iron have been investigated at 1973 K using an isotope-exchange reaction and the results are summarized as follows. The rate constant of nitrogen dissolution measured at lower oxygen concentration ([mass pct O] < 0.015) is larger than previously reported ones under an atmospheric pressure and agrees well with the value from desorption rate under reduced pressures. Selenium and tellurium retard the nitrogen dissolution into liquid iron more significantly than oxygen, and the degree of the retarding effect is in the order of tellurium, selenium, and oxygen. The adsorption coefficients are calculated to be K_O = 144, K_Se = 1120, and K_Te = 1640 with respect to [1 mass pct solute] from present results. A model that surface active elements and nitrogen are adsorbed on the same site at the interface and the dissociation reaction of nitrogen molecule on the site represented by the equation is the rate-determining step reasonably expresses the retarding effect of the surface active elements on the reaction rate on the assumption that all sites at the metal surface have a uniform adsorption energy for each solute.     

Activities of As,Sb, Bi,and Pb in copper mattes

The transportation method was used to determine the activity coefficients of the minor impurity components As, Sb, Bi, and Pb in homogeneous copper mattes (Cu-Fe-S) as functions of the Cu/Fe mole fraction ratio and of the sulfur content of the matte at 1200 °C. All matte samples contained about 0.2 wt pct As, Sb, Bi, and Pb. The activity coefficients were calculated on the basis of primary experimental data and available thermodynamic values of the gas components, which exist over the mattes. The sulfur-to-metal ratio, which controls the activities of the main matte constituents, was found to be the most important factor influencing the activities. When the sulfur-to-metal ratio of the matte changed from sulfur deficit to sulfur excess, the activity coefficient of As varied from 0.52 to 38, Sb from 3.3 to 82, Bi from 75 to 3.4, and Pb from 25 to 0.079 in the matte. The activities of AsS_1.5, AsS, SbS_1.5, BiS_1.5, and PbS had negative deviations from the ideal behavior.     

Distribution equilibria and slag chemistry of DON smelting

Equilibrium fluxing chemistry and metal value distributions of nickel matte smelting in the one-step direct nickel matte technology have been determined experimentally at 1350–1450°C in MgO-bearing iron silicate slags at silica saturation. The aim was to approach the detailed smelting chemistry at typical concentrations 2.5–10?wt-% iron in MgO-bearing iron silicate slags at silica saturation by quenching and X-ray microanalysis. The results obtained under controlled P(O₂) and P(S₂) as well as constant P(SO₂)?=?0.1?atm show that copper and nickel solubilities in the slag as well as matte-to-slag distributions favour matte when the slag is modified by magnesia. At the same time, along with increasing magnesia content of the slag, its iron activity is affected by the dissolution of MgO in the slag, and iron concentration of the formed nickel matte is lowered considerably, and its sulphur concentration increased at constant oxygen and sulphur pressures of the gas phase.     

Precious Metal Distributions in Direct Nickel Matte Smelting with Low-Cu Mattes

Base metal (Cu, Fe, and Ni) and trace element (Ag, Au, Co, Pd, and Pt) distributions between low-iron nickel mattes with [Ni]:[Cu] = 4 (w/w) have been studied at 1623 K to 1723 K (1350 °C to 1450 °C). We equilibrated small slag–matte samples with CO–CO₂–SO₂–Ar atmospheres in pre-selected \( P_{{{\text{S}}_{2} }} \)–\( P_{{{\text{O}}_{2} }} \) points, maintaining silica saturation by fused silica crucibles. The slags studied contained about 0 to 8.5 wt pct MgO. The matte–slag distribution coefficients L ^m/s[Me] were obtained from assays by electron probe X-ray microanalysis for the matte and by laser ablation-ICP-mass spectrometry for the slag. The measured L ^m/s[Me] values were clearly dependent on iron concentration of the matte and on MgO concentration of the slag, with values on the order of 10⁴, 10⁵, and 10⁴ for gold, platinum, and palladium, respectively, in the 5 wt pct iron in matte experiments. The obtained data for silver were scattered, due to volatilization, resulting in depletion of most silver and its escape from matte to gas phase during the 3-hour equilibration period. The matte-to-slag distribution coefficient for silver was estimated to be L ^m/s[Ag] = 100 to 400. We also measured the distributions of the base metals Cu and Ni in the same conditions as the trace elements.     

Activities of As,Sb, Bi,and Pb in copper mattes— Effect of O,Ni, and Co

The effects of oxygen, nickel, and cobalt on the activity coefficients of As, Sb, Bi, and Pb in copper mattes were measured at 1200 °C (1473.15 K) using the transportation method. The transportation experiments concerning the effect of oxygen were carried out as a function of the SO₂ content (1 to 100 vol pct) in the carrier gas and using high- and low-grade matte samples, ≈80 and ≈40 wt pct Cu, respectively. The prevailing sulfur and oxygen partial pressures were evaluated on the basis of matte and carrier gas compositions. The effect of the SO₂ pressure on the activity coefficients was found to be very small compared with the effect of the sulfur pressure, whereas the effect of the SO₂ partial pressure on the vaporization behavior, especially of As, was very significant, due to the additional vaporization of As as AsO gas molecules, which caused an increase in the As removal rate. At a higher oxygen partial pressure than 10^−8.5 atm (3.2·10⁻⁴ Pa) a noticeable decrease in the Sb activity coefficients was observed due to the oxidation. This did not, however, decrease the Sb removal rate, since the relative proportion of the oxide gas molecules in the gas phase increased simultaneously. The interactions between dissolved Ni or Co and the impurity elements were investigated by doping (1 wt pct) the high grade (Cu ≈75 wt pct) matte samples with Ni or Co. At stoichiometric and sulfur-deficient matte compositions, Ni and especially Co decreased the activity coefficients of As and Sb, but did not have any effect on the activity coefficients of Bi and Pb, compared with the corresponding sulfur content in the Ni- and Co-free mattes. For mattes of higher sulfur content Ni and Co did not show any marked effect on the activity coefficients of As, Sb, Bi, and Pb. A. ROINE, formerly with Institution of Process Metallurgy, Helsinki University of Technology, SF-02150, ESPOO, Finland     

Development of Kinetic Model for Reactions Between Cu-Containing Multicomponent Slag and Liquid Sulfide Using Coupled Reaction Model

Copper smelting slag contains less than 2 mass pct of Cu oxide and 30–50 mass pct of Fe_xO. Each year, the grade of copper ore decreases, while the amount of slag generated in the copper smelting process increases. In this study, a coupled reaction model to simulate the reaction between multicomponent slag and FeS-based matte was developed using reported thermodynamic data and double-film theory for the recycling of copper smelting slag. The activity coefficients of oxides in the multicomponent slag were calculated using a regular solution. The activity coefficients of Cu₂O in the slag and those of FeS, Cu₂S, and CaS in the FeS-based matte used previously reported data. The behaviors of Cu in slag and matte were confirmed by comparing the simulated results and the reported solubility of Cu in the slag in the temperatures ranging from 1473 K to 1573 K. In addition, the effect of the input amount of FeS on the copper content of the slag was verified by comparing the results of reaction model to experimental results. Using the reaction model, the influences of the initial ratio of FeO/SiO₂ of the slag, temperature, and matte composition on the behaviors of Cu in the slag and matte were investigated.     

Thermodynamic consideration and phase evolution during oxidation of tungsten–copper electrical contactor scraps

Present studies account the feasibility studies on isothermal oxidation of W–Cu hard metal electrical contractor scraps for recycling by roasting-leaching method. This was investigated as one of main processes to produce friable oxidized product amenable to subsequent leaching process. Oxidation is facilitated using scrap turnings instead of solid W–Cu contactor rods. The alloy oxidizes to Cu_xO, WO_x and CuWO₄ upon heating in the temperature range 400–1000°C under oxygen flow. Apart from oxidized W and Cu phases, significant amount of Cu nuggets formed initially at 450°C that rose gravimetrically up to 750°C, and then disappeared at higher temperature. The maximum weight gain was about 22% compared to initial weight when oxidation was carried out at 750°C. Oxidation beyond the temperature of 750°C corresponded to significant loss of tungsten by evaporation of WO₂ · (OH)₂ gaseous product. Thermal oxidation of W–Cu metal electrical contractor tip scraps produced porous and friable oxidized product of W and Cu.     

从难处理贵金属酸泥中分离回收硒和碲

提出从贵金属酸泥中分离硒和碲的工艺。采用碱浸出时碲的浸出率能够达到77.7%,硒的浸出率为38.78%;中和过程中中和渣含碲72.88%,碲的沉淀率达到98%,硒的浸出率仅为4.3%,还原过程中还原效率达到99%以上,产出粗硒含硒81.55%。     

Thermodynamics of the miscibility gap in the Ag-Se system

The miscibility gap in the Ag-Cu-Se system plays a central role in the smelting of copper anode slimes for the recovery of silver; however, its position in the Ag-Se and Cu-Se component binary systems is poorly defined. In this work, the miscibility gap in the Ag-Se system has been accurately defined by holding samples at selected temperatures, then quenching them and analyzing the two phases. The miscibility gap has been shown to extend from 6.7 to 25.0 pct at the monotectic temperature of 890 °C. As the temperature increases to 1150 °C, the boundaries do not converge very rapidly. The limiting activity coefficient of Ag₂Se in molten silver was calculated to be 7.8 at 1100 °C, confirming earlier work. The limiting activity coefficient of hypothetical liquid selenium at the same temperature was found to be approximately 0.008. Finally, the activity of hypothetical liquid selenium in the liquids on either side of the miscibility gap, from the monotectic temperature to 1150 °C, was mapped.     

High-temperature phase relations and thermodynamics in the silver-tin-sulfur system

The SnS activities in liquid Ag₂S-SnS liquid mattes were obtained at 1100 °C and 1200 °C by the dew-point method. Negative deviations were observed, and the liquid matte solutions were modeled by the Wilson equations. Part of the liquid boundaries of the Ag₂S-SnS phase diagram were derived from the model equations, yielding a eutectic temperature of 528 °C at x _SnS=0.38. The phase diagram of the pseudobinary Ag₂S-SnS was also verified experimentally by quenching samples equilibrated in evacuated and sealed silica capsules. Solubility limits of the components at the narrow-terminal solid-solution ranges were determined around the eutectic temperature. Within the Ag-Sn-S ternary system, the boundaries of the immiscibility region, together with the tie-line distributions, were established at 1200 °C. Activities of Ag, Sn, and S along the miscibility gap were calculated by utilizing the bounding binary thermodynamics, phase equilibria, and tie-lines.     

Physicochemical properties of matte-slag melts taken from vanyukov’s furnace for copper extraction

The properties of liquid slag and matte were studied in the autogeneous extraction of copper which occurs in the Vanyukov’s furnace, applied in the Balkhash copper-smelting plant (Balkhash Group of Mining and Metallurgical Enterprises, Kazakhstan). The density and surface tension of the melts were measured using the maximum-bubble pressure method, and the viscosity of the melts was measured by the rotational method. These properties were determined in the temperature interval from 1350 °C to 1550 °C. The temperature coefficients of the surface tension, density, and viscosity were determined, and the technological significance of results obtained is considered.     

Experimental Investigation of Gas/Slag/Matte/Tridymite Equilibria in the Cu-Fe-O-S-Si System in Controlled Gas Atmospheres: Experimental Results at 1473 K (1200 °C) and <Emphasis Type="Italic">P</Emphasis>(SO<Subscript>2</Subscript>) = 0.25 atm

Experimental studies were undertaken to determine the gas/slag/matte/tridymite equilibria in the Cu-Fe-O-S-Si system at 1473 K (1200 °C), P(SO₂) = 0.25 atm, and a range of P(O₂)’s. The experimental methodology involved high-temperature equilibration using a substrate support technique in controlled gas atmospheres (CO/CO₂/SO₂/Ar), rapid quenching of equilibrium phases, followed by direct measurement of the chemical compositions of the phases with Electron Probe X-ray Microanalysis (EPMA). The experimental data for slag and matte were presented as a function of copper concentration in matte (matte grade). The data provided are essential for the evaluation of the effect of oxygen potential under controlled atmosphere on the matte grade, liquidus composition of slag and chemically dissolved copper in slag. The new data provide important accurate and reliable quantitative foundation for improvement of the thermodynamic databases for copper-containing systems.