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By S. J. Gerdemann

The U.S. Bureau of Mines is studying the kinetics of wet oxidation of sphalerite concen- trate (ZnS) as a possible process for a gravity-pressurized reactor (GPR). At tempera- tures in excess of 200' C, a sphalerite water slurry will react with 0, to form zinc sul- fate (ZnSO,). However, the pressure required to keep the water from boiling at these temperatures has kept this reaction from becoming a viable continuous process. The GPR can easily obtain the high pressures required for this reaction. The reaction rate is complicated by the solubility of 0, in water and the further oxidation of ZnSO, to insoluble zinc oxysulfate (Zn4(OH),S04.4H20). The effects of pressure, temperature, and particle size on the rate of reaction were investigated. Reaction rate was found to be limited by the amount of oxygen in solution. However, at 250" C and 1500 psia, over 90 pct of the zinc was solubilized in less than an hour. The conditions for maxi- mizing the Zn++ in solution, while minimizing oxysulfate formation, are discussed.

Jan 1, 1993

By Ma Keyi, Yang Xianwan, Zhu Xiaoyun, Guo Zhongcheng, Zheng Yanping

"The oxidation of the Multifunctional Electrodeposited RE-Ni-WP- SiC Composites at high temperature is investigated. The results show that during high temperature oxidation the relationship between the mass change of pure Ni , Ni-W-P, Ni-W-P-SiC or RE-Ni-W-P-SiC coating and the oxidation time follows a mixed curve, i.e. it is approximately a linear relationship when the oxidation time is less than 60 mins while it is a power function relationship when the oxidation time is over 60 mins. The order for the oxidation rate of the four coatings is Ni> Ni-W-P> Ni-WP- SiC>RE-Ni-W-P-SiC. The mass change of Ni-W-P, Ni-W-PSiC or RE-Ni-W-P-SiC coating increases exponentially with a rise of oxidation temperature. The high temperature-oxidation resistance of RE-Ni-W-P-SiC composite coating is 3-4 times that ofNi-W-P alloy coating. The cross section morphologies and Xray diffraction patterns indicate that the high temperature oxidation resistance of RE-Ni-W-P-SiC composite coating is better than any other coatings.1. IntroductionWith the rapid development of modem industries the products in engineering industry are continually challenged by the requirements of long-term and stable working at higher temperature, pressure, speed and under adverse conditions. Consequently, the surface properties of the products, such as the resistance to oxidation at high temperature, the resistance to wear and the resistance to corrosion, should be improved continually."

Jan 1, 2000

By C. M. F. Viera

In this work the properties of a clayey ceramic incorporated, up to 10 wt.%, with three types of wastes from a water treatment plant was evaluated. To determine the physical and mechanical properties such as linear shrinkage, water absorption and diametrical compression, specimens were prepared by 18 MPa uniaxial pressure and then fired in laboratory furnace at 700oC. The results indicated that the wastes incorporation changed the properties of the clayey ceramic. From the results it was found it possible to recycle these wastes into clayey ceramic in low amounts to avoid deleterious effect on the quality of the fired product.

Jan 1, 2008

The oxidation of ferrous ions by oxygen in sulphate solutions is a very slow process, but it tills long been known that the addition of sulphur dioxide increases the rate of reaction very significantly. The kinetics and mechanism of the process were investigated in the laboratory and the results confirmed the advantage of adding small amounts of sulphur dioxide to the oxygen stream for the removal of iron from solutions. The effect of various parameters on the overall rate of iron oxidation and precipitation was studied. In particular, temperature, acidity and composition of the gas mixture were considered and the optimum conditions for the precipitation of goethite were determined.

Jan 1, 1991

By R. Padilla

Enargite (Cu3AsS4) occurs normally associated with copper sulfides, mainly chalcopyrite. When the enargite content in chalcopyrite concentrates is high, direct smelting of the concentrate presents problems related to environmental pollution and contamination of the final metallic copper. Leaching processes are viable alternatives to treat copper concentrates with high content of enargite. Consequently, in this paper, the pressure leaching of enargite in sulfuric acid-oxygen system is discussed. The leaching rate was studied in the range 160 to 220 °C and partial pressures of oxygen of 74 to 200 psi. The enargite dissolution increased substantially with temperature increase. Complete dissolution of enargite was obtained at 220°C, and 100 psi of oxygen pressure in 90 min. The shrinking core model controlled by surface reaction was used to analyze the kinetics of enargite dissolution. Activation energy of 70 kJ/mol was obtained for the temperature range 160 to 220 oC.

Jan 1, 2008

By A. Elizabet Serna

The weak acid is a by product obtained in a pre-treatment of gases from a copper smelter prior to sulfuric acid manufacture and the main components of this weak acid are: sulfuric acid. copper, arsenic. antimony, bismuth and iron. Usually, this effluent is neutralized with lime and the solid residues are stored in a landfill as a hazardous waste. This work was directed at determining the optimal conditions to recover copper from weak acid using a cementation process before the neutralization of the effluent. The variables investigated are: Effluent temperature, iron scrap amount and acid concentration versus reaction time. The results of these experiments show that the cementation process of copper and the co-cementation of impurities such as arsenic, antimony and bismuth were in accord with the theory of the electrode potentials.

Jan 1, 1996

By John A. Mavrogenes

The Texaco gasification system developed at the Monte Bello pilot plant efficiently bums petroleum-coke thereby producing syn-gas and electricity. This system produces more electricity than conventional burners, yet the only by-products are pharmaceutical grade sulfur and V -rich slag. Vanadium is known to exist in multiple valence states in compounds which possess a wide range of melting points and physical properties. Consequently, it becomes important to carefully regulate oxygen fugacity throughout the system in order to control vanadium valence state. Vanadium phase equilibria is presently poorly understood, in large part because of the multiple oxidation states of vanadium (-I, 0, +2, +3, +4, and +5) and the difficulty of unequivocally identifying the valence state(s) in many compounds. The operation of these gasifiers at approximately 1400°C is well above the melting point of V20S but considerably below the melting temperature of V02 and V 203. If J02 can be regulated to keep the burner within the V 205 field, slag material would more likely remain molten and more easily flow out of the bottom of the burner. In pure V oxides. the oxidation state is readily determined by microprobe analysis. where V20S (V+5) is 56% V, V02 (V+4) is 61.4% V, and V203 (V+3) is 68% V. However, V valence in multi-element phases (especially phases containing other elements of variable valence) cannot be resolved by microprobe analysis alone. Petroleum-coke gasification slags collected from within the gasifier under different oxidation conditions were studied by electron microprobe analysis (EMPA). X-ray diffraction (XRD). X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. Raman spectrometry in conjunction with microprobe analysis was found to resolve the valence of vanadium in the phases of these slags. Raman spectra collected from homogeneous single phase V-oxide standards in vacuum at low temperatures (-150°C) yielded peaks characteristic to each valence state. Gasifier slag samples are, however, much more complicated. Oxidized samples contain: fine grained (Ca. Mg, Fe. V) oxide matrix of variable composition, (Fe. V, Ni) spinel. (Fe, AI, V, Ni, Mg) spinel, V205laths, AI-Si glass blebs and Ni sulfides. Reduced samples contain: crystalline Ca-siIicate matrix, subhedral to euhedral (V, Fe, Mg, AI) spinel, subhedral V02, Fe and Fe-Ni sulfides, Fe-Ni alloys, and complex Ca-oxide matrix. The different spinel assemblages, the characteristic V-oxides and the distinctly different character of the matrices makes the oxidized and reduced slags readily discernible.

Jan 1, 1995

By Gabriel Riveros

Fire refining of copper consists of two stages copper oxidation and copper reduction. Very frequently the capacity of the anode furnace is determined by the rate of copper reduction. The analysis of factors affecting the rate of the oxygen reduction from a liquid copper with solid carbon or injected hydrocarbons pointed out the role of the mass transfer in a liquid copper in final stage of the reduction. Experimental results of copper reduction with graphite and injected natural gas in laboratory- scale crucibles showed two stages of the reduction process with a sharp change of the controlling mechanism. The estimated dynamic surface area of gas bubbles based on the measured bubble frequency and the gas flowrate allowed for the detennination of the reaction constant as a degree of the partial pre-combustion of the air/natural gas mix. The variation of the used reductant as a function of the oxygen concentration and temperature has been evaluated based on the detennined kinetic model. The intensification of copper reduction in fire refining has been discusses on the basis of obtained kinetic data and analysis of various factors detennining the time of reduction.

Jan 1, 2003

By J. W. Holzenthaler

Teams continue to play a major role at the Phelps Dodge Mining Company El Paso Operations, especially during the present time of low copper prices. The El Paso Operations' teams have taken the initiative during this copper market downturn and have helped reduce operating costs significantly. Because of this, Phelps Dodge El Paso Operations has continued to grow within the team process by creating a total, non- exempt salaried workforce. In the last year alone, the El Paso Operations have implemented three major initiatives to accommodate the team process. The first was the creation of "guiding principles", a policies and procedures handbook. Second was the "zero and beyond" safety initiative. Third was team compensation. In addition, the Copper Products Company has now adopted a work-team environment, following the lead of the refinery.

Jan 1, 1999

By R. Togashi, S. Kuramochi, T. Yamada

In 1972, the Akita Zinc Co., Ltd. commenced operations with an annual capacity of 86,000 tonnes of electrolytic zinc, and it has operated with an annual capacity of 156,000 t-Zn since 1974. The business surroundings for non-ferrous metals production have become more severe with the high Yen rate for the dollar and low domestic demand in the last few years. Consequently, the company tried to survive with some improvements and succeeded to reduce operating costs and to improve profitability as follows: 1) expansion of its production capacity to. 196,000 t-Zn annually, 2) saving man-power by the introduction of fully-automated machines for cathode handling in the cellhouse, 3) improvement of the hematite process by means of the recovery of rare-metals. These improvements made Akita Zinc a competitive refinery in the modern world. We have been trying to improve the operations more and more. One of the challenges is to purify the iron oxide made in the hematite process by applying an As removal process, which is coming into operation in the near future.

Jan 1, 2000

By Dong Hoon Han

The simultaneous sulfation by sulhr dioxide and oxygen of CaO and MgO in calcined CMA (calcium magnesium acetate) were investigated. he experiments were carried out in the temperature range from 700 to 830 "C and at the SO2 concentrations of 0.3 to 1 mol %. The oxygen concentration was kept at 5 %. Each sample was calcined completely before the temperature was lowered to the sulfation temperature. According to the ranges of partial pressure of sulhr dioxide and temperature, there exist three regions for the sulfation reaction: region I in which neither oxide is sulfated, region I1 in which only CaO is sulfated, and region 111 in which both oxides are sulfated. It was shown that the MgO in calcined CMA is sulfated at a rate comparable to that of CaO by forming a mixed sulfate phase. Thus, unlike MgO contained in other desulhrization materials, the MgO content in calcined CMA can be fully utilized for flue gas desulhrization.

Jan 1, 1999

By Kunibert Hanusch

Copper in recycling material is accompanied by various groups of metals: 1) Metals which are much more negative than copper, such as Fe, Al, Si, P, Be They are mainly removed by fire refining during the recovery of copper and leave the process in form of slag. 2) Metals which are more positive than copper or difficult to separate by fire refining and which are partly reduced together with the copper. These metals are for example As,. Sb, Ni, Ag, Pb, Zn, Sn. They are enriched in intermediate products and recovered from these or remain for their major part in the fire-refined copper and can be separated by electrolytic refining and recovered from the electrolyte or anode slime. This report describes the process of Hüttenwerke Kayser AG in Germany and illustrates how considerable returns of material are partly required to separate or recover associated metals. They are finally removed in saleable products.

Jan 1, 1995

By Gabriel Riveros

Fire refining of copper consists of two stages copper oxidation and copper reduction. Very frequently the capacity of the anode furnace is determined by the rate of copper reduction, The analysis of factors affecting the rate of the oxygen reduction from a liquid copper with solid carbon or injected hydrocarbons pointed out the role of the mass transfer in a liquid copper in final stage of the reduction. Experimental results of copper reduction with graphite and injected natural gas in laboratory-scale crucibles showed two stages of the reduction process with a sharp change of the controlling mechanism. The estimated dynamic surface area of gas bubbles based on the measured bubble frequency and the gas flowrate allowed for the determination of the reaction constant as a degree of the partial pre-combustion of the air/natural gas mix. The variation of the used reductant as a function of the oxygen concentration and temperature has been evaluated based on the determined kinetic model. The intensification of copper reduction in fire refining has been discusses on the basis of obtained kinetic data and analysis of various factors determining the time of reduction.

Jan 1, 2003

By Corby G. Anderson

For over a century, the Sunshine Mine in Idaho has been a major producer of silver. An estimated 335,000,000 troy ounces of silver has been mined. This has established the Sunshine Mine as the largest single source of silver in the world. Because the dominant silver containing mineral is tetrahedrite, a copper and antimony sulfide, normal metallurgical treatments to recover the precious metal are not practical. Thus, over the course of the company's history, novel, hydrometallurgical technologies have been developed on-site to handle complex, precious metal containing materials. Recently, the use of Sunshine technology has been extended to the recycle of secondary materials. As well, the use of Sunshine technology by other organizations for treatment of both primary and secondary feedstocks containing precious and base metals is an area of growing interest. This paper will provide an overview of Sunshine hydrometallurgical technologies including the applicability of Sunshine technology to the recycling of precious and base metals.

Jan 1, 1995

By Cindy L. Williams

"The Blue Star subdistrict in the Carlin Trend, Nevada, includes multiple mines with 33.9 t Au in reserve and past production totaling 89 .1 t Au. The deposits are characterized by zoned alteration mineralogy and gold grades. From orebody centers outward the zones include: 1) a silicified core with erratic gold grade; 2) adjacent mill-grade (> 1.37 Au git) intense quartz-sericite-pyrite alteration; 3) enveloping leach-grade (0.21 Au g/t to 1.37 Au git) weaker sericite-kaolinite-quartzpyrite alteration; 4) surrounding decarbonatized and intensely argillized waste and leach grade ore; 5) pervasively decarbonatized waste rock; and 6) peripheral waste with weak decarbonatization and local propylitic alteration. Zoned alteration extends as much as 1500 m beyond orebodies.Understanding Blue Star subdistrict zoned alteration assemblages and gold grades has increased geologists' ability to provide practical and economically significant information to geotechnical engineers, mine planners and drill and blast personnel. Alteration influences geotechnical pitslope design because each assemblage has distinct rock strength. Geotechnical engineers use three-dimensional models of incompetent alteration types as a foundation for pit-slope design. In the drill and blast cycle, hard and soft alteration types require modified practices (powder column, blast hole spacing, delay design etc.) for optimum blast energy distribution. Further, geotechnically instable alteration types require careful blast procedures to prevent backbreak whic~ damages ultimate walls. In addition to mine planning and mining applications, zoned alteration assemblages extending beyond orebodies provide a useful exploration guide. Metallurgical character also varies with alteration type. Intensely quartz-sericite-pyrite altered or silicified ore has relatively high partical-size dependency and poor leach recoveries. Moderately sericite-kaolinite-quartz-pyrite altered rock, in contrast, shows little size dependency and good leach recoveries.The author sincerely thanks L. Schutz, P. Williams, C. Clode, W. Trudell, P. Herrera, M.DKunkel, M. Goings and numerous other Newmont geologists, metallurgist, engineers and support staff who made this paper possible."

Jan 1, 1997

By U. M. Mutnti

In order to meet the stringent market requirements for high purity cobalt, ZCCM commissioned the VIR plant in December 1982. The plant comprises a 4.1 tonne/heat vacuum induction furnace with a rated annual capacity of 2,500 MT of barstock. In the VIR furnace, molten cobalt is held under vacuum at 1600°C resulting in the removal of more volatile impurity elements by distillation. Operations todate have demonstrated that Pb, Zn and Cd have good distillation rates in excess of 95%, leading to cobalt containing 1 ppm or less of the above elements. Removal of other impurities such as Se, Bi is about 65% with the finished product still assaying around 1 ppm of each of these elements. Vacuum refining of cobalt offers an economic route for producing higher grades of cobalt from the type of concentrates and treatment processes available within ZCCM. The consistency of VIR cobalt quality has been confirmed by ZCCM and some of its alloy customers.

Jan 1, 1988

By Ray Y. Lin

Chemical vapor deposition of tungsten carbide on the surface of steel has been investigated at temperatures between 400 and 550C in an atmosphere containing tungsten hexafluoride, hydrogen and benzene. The tungsten fluoride flow rate was maintained at 20 ml/min. The hydrogen flow rate was at 100 ml/min. The benzene concentration varied from 1.15 to 5.56% in the reaction gas. It was observed that the higher the temperature, the faster the deposition rate for tungsten carbide. But the dependence of the deposition rate on the benzene concentration was not systematic. From the x-ray diffraction analysis, it was observed that W, W2C and WC are all presented in the coating. The amount of each phase presented in the coating depends on the temperature and, to a less extent, on the benzene concentration. The microhardness measurement has also been done for all CVD carbide coatings obtained in this study.

Jan 1, 1992

By Louis J. Cabri

The ion microprobe (dynamic SIMS technique) is a very sensitive instrument for the quantitative determination of trace concentrations of precious metals (often at the ppb level) occurring in common sulfide minerals, either chemically-bound or as discrete particles too small for resolution by SEM. The technique involves sputtering a 250 x 250 Jim area of the grains to a depth of about one ILm and analysing the secondary ions emitted from a circular central region in the sputter crater with a 62.5 I'm diameter. The combination of quantitative mineral-specific sub-ppm analyses together with depth-profiling and the ability to produce secondary ion maps of trace precious metals makes this a very powerful technique in quantifying the precious metal distribution in refractory and other sulfide ores and process products. The technique is particularly well-established for analysis of gold-and platinum-bearing ores and process products.

Jan 1, 1996

The physico-chemical principles of chloride hydrometallurgy are reviewed to rationalise the complex chemistry in chloride-based processes for metal sulphides in terms of the predicted Eh-log[Cl-] relationships, measured changes in activity of H+, Mz+, Cl- and solubility of Ag(I), Cu(I), Cu(II), Pb(II), Ni(II), Au(III), Sb(III) and Bi(III). These changes reflect the nature of chemical speciation, competing effect of hydration/hydrolysis and chloro-complexation,composite effect of increasing acid and/or salt concentration and decreasing water activity. Rate data for the dissolution of PbS and ZnS in HCl containing Fe(III) or Cu(II) are compared and contrasted to highlight the effect of acid and chloride concentration, water activity, and the nature of oxidant. It is shown that LiCl, NaCl and HCl influence the kinetics of oxidative PbS leaching based on their effect on solubility of PbCl2 co-precipitated with elemental sulphur on the mineral surface. Evidence for the beneficial effect of Cu(II) in sulphide leaching is discussed.

Jan 1, 2003

By Satoshi Yamashita, Noboru Masuko

"Newly prepared bipolar membrane is promising to become a key material of an electrolyser for a production process of strong reducing solvent. This research is basic research for using bipolar membranes as electrolysers of reducing agents, Cr(II), TI(III) and V (II) on the laboratory scale. In this report, a bipolar membrane was tried with an electrolyser, reducing chromic chloride to chromous chloride. An analysis of mass balance demonstrates advantages of it over the former electrolyser equipped with an anion and/or. cation exchange membrane. The effects of current density and concentration of Cr(lll) on the reduction rate of Cr(II) and the current efficiency were examined No deterioration of the bipolar membrane resulted from the electrolytic reduction of Cr(III). IntroductionRecently, bipolar membrane that was the development subject for a long time in the industry of ion exchange membranes has met the stage of the practical application at last [l]. The expectation of the application to the hydrometallurgy field increases. We took up the manufacturing of the strong reducibility solvent as part of the application of bipolar membrane to hydrometallurgy technology. This laboratory has much experience in the electrolytic reduction of Cr (II) aqueous .solution such as chromous sulfateusing bipolar membrane were compared in theory to chromous chloride aqueous solution manufacturing of the strong reducibility solvent. The advantage of applying bipolar membrane by substituting ion exchange membrane is described, and the experimental result is reported."

Jan 1, 2000