Effect of CaO Addition on Iron Recovery from Copper Smelting Slags by Solid Carbon

We investigated the effect of flux (lime) addition on the reduction behavior of iron oxide in copper slag by solid carbon at 1773 K (1500 °C). In particular, we quantified the recovery of iron by performing typical kinetic analysis and considering slag foaming, which is strongly affected by the thermophysical properties of slags. The iron oxide in the copper slag was consistently reduced by solid carbon over time. In the kinetic analysis, we determined mass transfer coefficients with and without considering slag foaming using a gas holdup factor. The mass transfer of FeO was not significantly changed by CaO addition when slag foaming was ignored, whereas the mass transfer of FeO when slag foaming was considered was at a minimum in the 20 mass pct CaO system. Iron recovery, defined as the ratio of the amount of iron clearly transferred to the base metal ingot to the initial amount of iron in the slag phase before reduction, was maximal (about 90 pct) in the 20 mass pct CaO system. Various types of solid compounds, including Mg₂SiO₄ and Ca₂SiO₄, were precipitated in slags during the FeO reduction process, and these compounds strongly affected the reduction kinetics of FeO as well as iron recovery. Iron recovery was the greatest in the 20 mass pct CaO system because no solid compounds formed in this system, resulting in a highly fluid slag. This fluid slag allowed iron droplets to fall rapidly with high terminal velocity to the bottom of the crucible. A linear relationship between the mass transfer coefficient of FeO considering slag foaming and foam stability was obtained, from which we concluded that the mass transfer of FeO in slag was effectively promoted not only by gas evolution due to reduction reactions but also by foamy slag containing solid compounds. However, the reduced iron droplets were finely dispersed in foamy and viscous slags, making actual iron recovery a challenge.     

Influence of gold content on copper oxidation from silver-gold-copper alloys

In the final stages of the smelting of copper anode slimes, a silver alloy, known as “doré,” is produced. Oxidation refining is used to remove copper since this element interferes with subsequent electroparting of the small amounts of gold and platinum group metals in the doré. The gold content of doré can be greatly increased by gold scrap additions and this may affect the minimum achievable copper content of doré. In this work, silver-gold-copper alloys were oxidized by injecting pure oxygen at 1100 °C in the absence of any slag cover. For the gold contents expected in practice, the equilibrium copper content of the doré did not increase significantly as the gold content increased. However, at the other extreme of composition, the equilibrium copper content was a very strong function of the silver content of the gold bullion. The activity coefficient of copper in silver-gold alloys was calculated and compared to those predicted from a ternary subregular solution model of the system Ag-Au-Cu. Satisfactory agreement was found.     

Entrainment behavior of copper and copper matte in copper smelting operations

In copper smelting, the loss of copper to the slag due to entrainment is largely influenced by the flotation of copper metal and/or matte in the slag phase. To evaluate this behavior, the surface tension of copper as a function of temperature and oxygen pressure and the interfacial tension of the copper-iron matte-slag system as a function of matte grade were measured. From the surface and interfacial tension values, the spreading and flotation coefficients of the copper, matte, and slag system were calculated. Ternary interfacial energy diagrams were also con-structed using these data. It is shown that matte droplets containing higher than 32 mass pct Cu will not form a film on rising gas bubbles when they collide in the slag phase. However, matte droplets will attach to gas bubbles upon collision and thus can be floated over the entire range of matte composition. Spreading of copper on bubbles is not possible at oxygen pressures between 10⁻¹² and 10⁻⁸ atm. Flotation of copper by gas bubble in slag is possible at oxygen pressure higher than 10⁻⁹ atm. However, it is feasible for rising matte droplets (attached to rising bubble) to trap and float copper irrespective of the matte grade.     

Study on Formation Mechanism of CaO-SiO<Subscript>2</Subscript>-Based Inclusions in Saw Wire Steel

Attempts were made to elucidate the formation mechanism of CaO-SiO₂-based inclusions in saw wires by both laboratory experiments and industrial trials. The key point was to make clear the origin of CaO in such oxide inclusions. Probable origins of [Ca] in steel were first discussed, which can be taken into steel from the steel-slag reaction or ferrous alloy. As a result, slag-steel chemical reaction equilibrium was carefully evaluated at 1873 K (1600 °C) to classify the changes of dissolved aluminum ([Al]), total magnesium (Mg), and total calcium (Ca) in steel and the caused composition variations of inclusions. With the rise of slag basicity from 0.5 to 1.8, [Al] was remarkably increased from 0.00045 to 0.00139 mass pct, whereas Mg varied in the range of 0.00038 to 0.00048 mass pct. By contrast, Ca was constantly kept below 0.00003 mass pct. Accordingly, Al₂O₃ and MgO in inclusions witnessed obvious rises from 5 to 23 mass pct and from 2 to 8 mass pct, respectively. By contrast, inclusions were free of CaO when slag basicity was below 1.5. With slag basicity further increased to 1.8, CaO witnessed a negligible rise to only 1.0 mass pct on average. This phenomenon agreed well with thermodynamic calculations, which revealed that chemical reaction between steel and CaO in slag (for example, between [Si] and CaO) was weak to hardly supplying sufficient [Ca] to steel to increase CaO in inclusions. Ca contained in ferrous alloys as contaminations was not the cause of CaO-SiO₂-based inclusions, either. The industrial trial results indicated that CaO-SiO₂-based inclusions have been readily produced in short time just after BOF tapping. Also, a percentage of them changed slightly with the proceeding of refining. Based on the good agreement of laboratory, industrial, and thermodynamics calculations results, it can be reasonably concluded that CaO-SiO₂-based inclusions in saw wire were exogenous particles from entrapped/emulsified top slag, but not products of slag-steel-inclusion chemical reactions.     

Interfacial tensions of liquid Fe-Ni alloys and stainless steels in contact with CaO-SiO2″AI2O3-based slags at 1550 °C

In the present work, the interfacial tensions of Fe-Ni alloys in contact with slags of the CaO-Al2O3-SiO2 system were measured at 1550 °C. Nickel additions to the alloy were found to decrease interfacial tension. The effects of alumina and titania additions to the slag on the interfacial tension of the Fe-20 wt pct Ni alloy were determined: alumina was found to increase the interfacial tension by a small amount, while titania was found to decrease it drastically. Using the present interfacial tension data for the CaO-Al2O3-SiO2 system and the ones measured by Jimbo and Cramb, Girifalco and Good’s interaction coefficient (ϕ) was determined as a function of the slag composition using regression analysis and was found to be a useful means of correlating interfacial tension data. The interfacial tension of an Fe-20 wt pct Ni-2.39 wt pct Al alloy in contact with a CaO-Al2O3-SiO2 slag was found to decrease drastically in the first 60 to 75 minutes of the experiment due to the dynamic effects of mass transfer. Slight lowering of interfacial tensions of industrial stainless steels due to sulfur transfer from liquid metal to slag was also observed. The equilibrium interfacial tensions of type 304 stainless steels were found to be more dependent on the slag chemistry than on the nickel and chromium content of the alloy. Formerly Graduate Student, Department of Materials Science and Engineering, Carnegie Mellon University, Pittsburgh, PA     

The effect of solidification microstructure on the corrosion behavior of a columnar aluminum-copper alloy

The morphological and kinetic nature of corrosion of directionally solidified aluminum-4.5 wt pct copper alloy in the as-cast, solutionized and solutionized-and-aged conditions in air-saturated aqueous 3.5 wt pct NaCl solution were evaluated. In the solutionized and solutionized-and-aged conditions the intergranular attack and pitting are similar to those occurring in solutionized wrought alloys; the extent of attack at long times increases with increasing severity of solidification rate. The as-cast alloy exhibits a cored dendritic structure with significant formation of interdendritic nonequilibrium eutectic. Extensive inter dendritic corrosion of the α-phase containing more than 3.2 wt pct copper is seen; α containing less than 3.2 wt pct copper and the θ-Al₂Cu phase are cathodic. Corrosion of the as-cast alloy is parabolic with time and increases with increasing severity of solidification rate in proportion to the amount of nonequilibrium second phase.     

Effect of copper content on mechanical properties and fracture behaviors of Al-Li-Cu alloy

A series of Al-Li-Cu alloys with copper content of 0 to 6 wt pct and lithium content of 2.5 wt pct were studied. The results showed that copper plays an important role in grain refining, homogenization, and aging, and significantly influences the mechanical properties and fracture behaviors of the alloys. With the addition of copper, the hardness and peak-aging time increase, and the tensile strength gradually increases to a maximum value with copper content of about 3 wt pct and decreases after that. However, elongation decreases constantly, and the crack roots increase and lead to early crack. The mechanism of mechanical properties and fracture behaviors of Al-Li-Cu alloy is also discussed.     

Reaction equilibria in the production of manganese ferroalloys

A laboratory investigation has been carried out to determine slag/metal and slag/metal/gas equilibria relevant to production of manganese ferroalloys. The metal phase was normally composed of MnSi-C_sat alloys, but in some experiments, the alloys contained up to 15 wt pct Fe. Different slag systems were used: MnO-SiO₂, MnO-SiO₂-CaO, MnO-SiO₂-Al₂O₃, and quaternary MnO-SiO₂-CaO-Al₂O₃ with fixed CaO/Al₂O₃ weight ratios of 1.5 and 3. The experiments were normally made in CO gas atmosphere at temperatures ranging from 1450 °C to 1600 °C. The results give comprehensive information about equilibrium relations.Partial andcomplete equilibria are illustrated in equilibrium diagrams. Partial equilibrium is a situation in which equilibrium is established with respect to certain variables but not to others, in this case, between slag and metal but not with the gas phase. The effect of temperature was found to be of minor importance for the partial slag/metal equilibrium, whereas the complete slag/metal/gas equilibrium is considerably influenced by both temperature and CO pressure. As expected, increasing temperature and decreasing CO pressure will reduce the equilibrium MnO content of slags. The influence of alumina addition to the slag phase and of iron to the metal phase is also discussed.     

Vacuum distillation of copper matte to remove lead,arsenic, bismuth,and antimony

Vacuum-refining experiments were carried out on copper matte melts, containing 35 to 73 pct Cu, to measure the removal rates of lead, bismuth, arsenic, and antimony over the temperature range of 1373 to 1523 K under pressures in the range of 50 to 130 Pa. High rates of refining, controlled by mass transport in the liquid phase, were achieved for all impurities in melts containing up to 65 pct Cu and for chamber pressures less than 100 Pa. After 40 to 60 minutes of treatment, lead elimination was between 70 and 96 pct, bismuth elimination was between 88 and 98 pct, arsenic, elimination was between 60 and 93 pct, and antimony elimination was between 40 and 92 pct. The overall mass transfer coefficients for vacuum refining for the impurities considered fell in the range of 5×10⁻⁵ to 2×10⁻⁴ m s⁻¹. The values were insensitive to small changes in melt temperature but decreased with increasing pressure above 250 Pa. Also, the rates of refining were seen to be influenced by the sulfur and oxygen activity in the melt. The evaporation and subsequent elimination of the impurities were mathematically modeled by extending previously published models beyond consideration only of evaporation of monomers to consideration of the evaporation of monomers and dimer compounds. The model showed that due to the contributions to the refining by evaporation of each of the metallic, oxide, or sulfide vapor species, arsenic and antimony exhibited a maximum in refining rates atP _{o 2} andP _{s 2} potentials corresponding to matte grades of about 55 pct copper, whereas lead showed a minimum at about the same matte grade, and bismuth showed a continuously decreasing rate of refining with increasing matte grade. The model was also used to simulate the refining behavior of copper matte melts. An example of a commercial-scale operation is given.     

Removal of Boron from Silicon-Tin Solvent by Slag Treatment

To eliminate B effectively from Si for its use in a solar cell, a novel process involving the slag refining of molten Si with Sn addition was investigated. The partition ratio of B between CaO-SiO₂-24 mol pct CaF₂ slag and Si-Sn alloy at 1673 K (1400 °C) was determined by the chemical equilibrium technique. It was found that the partition ratio of B was remarkably increased with the increase in Sn content of alloy, which attributes to the increase in activity coefficient of B as well as the oxygen partial pressure. The partition function was accounted as much as 200 when the alloy composition was Si-82.4 mol pct Sn, which was much higher than the reported values in the range of 1 to 3. The required amounts of slag used for B removal from Si-30, 50, and 70 mol pct Sn melts were only 15.6 pct, 6.5 pct, and 1.2 pct of that used for the removal of B directly from MG-Si without Sn addition in a single slag treatment.     

Kinetics of oxide formation in liquid copper and silver

The process of formation of oxide phases in liquid copper and liquid silver has been studied by pumping oxygen into the liquid alloy with the use of a solid-electrolyte electrochemical cell. The oxygen potential at the electrolyte-metal interface is monitored simultaneously by the electrochemical cell. A wide range of effects were observed ranging from the very rapid formation of a layer of oxide at the electrolyte-metal interface to what appears to be homogeneous nucleation of the oxide in the metal. The results may help to explain some of the difficulties that sometimes have been observed in using this type of cell to measure the oxygen potential of a liquid metal. The results indicate that a supersaturation ratio of about 9 is necessary for homogeneous nucleation of iron oxide (most probably Fe₃O₄(s)) in liquid copper containing 0.01 to 0.07 pct iron. The interfacial tensionσ _{Cu-Fe 3}O₄ is calculated to be 0.74 J/m². In experiments with higher concentrations of deoxidant (0.2 pct Fe in Cu and 0.2 to 0.4 pct Ni in Ag) equilibrium precipitation of oxides apparently predominates over homogeneous nucleation for the experimental conditions employed. A mathematical model which partly explains the different effects observed is presented.     

Copper losses and thermodynamic considerations in copper smelting

A relationship between copper in slag and copper in matte during copper sulfide smelting has been derived using industrial data from 42 plants employing blast furnaces, reverberatory furnaces, flash furnaces, and Mitsubishi smelting furnaces together with the available thermodynamic equilibrium data for Cu-Fe-S-O, FeO-SiO₂, and Cu-Fe-S systems and laboratory slag-matte equilibrium information. A copper smelting diagram showing oxygen potential; sulfur potential; and copper, magnetite, and sulfur contents in slag during the smelting of different grades of copper mattes is developed for mattes containing less than 70 pct copper. The data presented can be used to determine the entrained copper losses in slag. Further, by combining the calculated value of the entrained matte with the corresponding plant data for the sulfur content of the slag, it is possible to derive the dissolved sulfur content of the slag. These calculated values were in excellent agreement with the experimentally determined sulfide capacity of fayalite slags. It is shown that there is no need to assume the presence of dissolved copper sulfide species in industrial slags. The existing equilibrium data that relate the copper content of slags to oxygen potential adequately describe the copper losses in industrial slags.     

Flotation of nonmetallic inclusions during argon injection into the tundish of a continuous-casting machine. Part 2

The mixing of metal and slag where argon bubbles enter the atmosphere is analyzed by physical modeling. The best results are obtained with bubbling injection at a rate of 10–12 L/min, when the bubble diameter on reaching the slag phase is 3.25 mm. The mass of the metal droplets captured in the slag is 0.6 g; their speed in the slag phase is 1 m/s; the penetration depth is 3 cm; and the residence time is 0.4 s. That corresponds to optimal refining of the steel in the tundish. With the given injection parameters, the streamlines entrain steel at a rate of around 50 L/min (350 kg/min).     

从冶炼铜渣中进一步提取金银的湿法工艺研究

湿法冶炼中氰化金泥杂质元素含量的波动,容易造成冶炼副产品铜渣中的贵金属含量过高,从而影响到黄金精炼的回收率,直接关系到企业的经济效益。为了更有效地回收贵金属,提高企业经济效益,利用金银与其他贱金属的电位差异,通过加入氧化剂调整体系电位,以此达到金银与贱金属分离的目的。从铜渣中进一步提取贵金属工艺采用控电位氯化技术分离出杂质铜-废液置换铜-含金银渣进一步除杂分出金-剩下含银渣铸阳极板银电解回收银,来处理含金品位高的铜渣能够最终实现金、银、铜的分离,提高黄金冶炼回收率。     

Equilibria between liquid Mn-Si alloys and MnO-SiO2-CaO-MgO slags

The activity of silicon in manganese-silicon melts was determined at 1500°C. The results are in general agreement with the thermodynamic data of the iron-silicon system. Equilibria between manganese-silicon melts and slags containing MnO, SiO₂, CaO, and MgO were studied at 1400 and 1500°C in silica and magnesia crucibles. An empirical relationship easy to use in practice was derived, expressing the manganese and silicon distribution ratio between slag and metal as a function of the slag basicity. This relationship describes equilibria pertinent to the silicothermic reduction of manganese oxide and the production of silicomanganese. The present knowledge of the activities in the slag and metal phase is adequate to explain the experimental results. The presence of up to about 10 pct CaF₂ in the slag makes it possible to maintain a higher slag basicity and therefore a lower activity of silica, resulting in lower silicon contents in the metal. Iron contents of up to about 20 pct in the metal cause a slight increase in the silicon content of the metal under otherwise similar conditions. The effect of 1 to 2 pct carbon in the metal on the equilibrium was roughly estimated and found to be almost negligible.     

The mineralogical characterization of tellurium in copper anodes

A mineralogical study of a «normal» commercial copper anode and six tellurium-rich copper anodes from the CCR Refinery of the Noranda Copper Smelting and Refining Company was carried out to identify the tellurium carriers and their relative abundances. In all the anodes, the major tellurium carrier is the Cu₂Se-Cu₂Te phase which occurs as a constituent of complex inclusions at the copper grain boundaries. In tellurium-rich anodes, the molar tellurium content of the Cu₂Se-Cu₂Te phase can exceed that of selenium. Although >85 pct of the tellurium occurs as the Cu₂Se-Cu₂Te phase, minor amounts are present in Cu-Pb-As-Bi-Sb oxide, Cu-Bi-As oxide, and Cu-Te-As oxide phases which form part of the grain-boundary inclusions. About 1 pct of the tellurium content of silver-rich anodes occurs in various silver alloys, but gold tellurides were never detected. Surprising is the fact that 2 to 8 pct of the total tellurium content of the anodes occurs in solid solution in the copper-metal matrix, and presumably, this form of tellurium dissolves at the anode interface during electrorefining.     

The kinetics of deoxidation of copper and copper alloys by carbon monoxide

The kinetics of deoxidation of molten copper, Cu-50 pct Ag and Cu-60 pct Sn alloys were studied. The solid electrolyte EMF technique was used to measure the oxygen content as a function of time. The gas was introduced as bubbles emitted from various-sized orifices placed in the melt. Liquid phase mass transfer control is implied by the results for deoxidation in the range 0.05 pct oxygen down to 0.005 pct, where the chemical reaction rate is inferred to become significant in controlling the overall rate. Hughmark’s mass transfer correlation is tested and found to be useful in predicting the liquid phase mass transfer coefficient. This paper is based on a portion of the Dissertation submitted by C. R. NANDA to the Graduate School of the University of Wisconsin in partial filfillment of the requirements for the Ph.D, degree. The research was conducted while the authors were, respectively, Research Assistant and Associate Professor in the Department of Minerals and Metals Engineering, University of Wisconsin, Madison, Wis.     

Model of Silicon Refining During Tapping: Removal of Ca,Al, and Other Selected Element Groups

A mathematical model for industrial refining of silicon alloys has been developed for the so-called oxidative ladle refining process. It is a lumped (zero-dimensional) model, based on the mass balances of metal, slag, and gas in the ladle, developed to operate with relatively short computational times for the sake of industrial relevance. The model accounts for a semi-continuous process which includes both the tapping and post-tapping refining stages. It predicts the concentrations of Ca, Al, and trace elements, most notably the alkaline metals, alkaline earth metal, and rare earth metals. The predictive power of the model depends on the quality of the model coefficients, the kinetic coefficient, τ, and the equilibrium partition coefficient, L for a given element. A sensitivity analysis indicates that the model results are most sensitive to L. The model has been compared to industrial measurement data and found to be able to qualitatively, and to some extent quantitatively, predict the data. The model is very well suited for alkaline and alkaline earth metals which respond relatively fast to the refining process. The model is less well suited for elements such as the lanthanides and Al, which are refined more slowly. A major challenge for the prediction of the behavior of the rare earth metals is that reliable thermodynamic data for true equilibrium conditions relevant to the industrial process is not typically available in literature.     

Hydrogen embrittlement of ultra-pure alloys of the inconel 600 type: Influence of the additions of elements (C,P, Sn,Sb)

The mechanical behavior of very high purity nickel base alloys of the Inconel 600 type that were simultaneously charged with hydrogen and deformed in tension was investigated. Experimental results show that this procedure decreases markedly the fracture strain of the pure 76 pct Ni-16 pct Cr-8 pct Fe alloy; cracks are observed after two to four pct elongation, and the fracture is completely intercrystalline. Hydrogen embrittlement appears as an intrinsic property of the Ni-Cr-Fe system in the sense that the grain boundary cohesion decreases when the purity of the alloy increases. The presence of carbon or phosphorus in the alloys increases grain boundary cohesion. The addition of metallic elements such as antimony or tin has relatively little effect on intergranular embrittlement.