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By J. V. Atwood

The U.S. Bureau of Mines has developed a novel Double Membrane Electrolytic Cell (DMEC) that exhibits unique features for recycling contaminated metals and metal alloys. The DMEC incorporates two anionic ion exchange membranes, separating anodic and cathodic regions of the cell. The ion exchange membranes prevent significant transport of unwanted cationic impurities to the catholyte from the impure anolyte while the anion/cation balance in cell compartments is maintained through the free movement of anions between compartments. The membrane barrier makes it possible to electro refine highly contaminated materials or to electrowin from solution while utilizing alternate anode reactions. Sinceanolyte and catholyte cross contamination has been eliminated, premium cathode products are produced. The DMEC has been tested at bench, pilot, and commercial scales. Configuration of the DMEC, cell operation, scale, up efforts, and significant design factors are discussed. Two separate recycling investigations utilizing DMEC technology are presented. The first investigation examines recovery of high purity cobalt and nickel from severely contaminated super aIloy scrap. The second involves? upgrading contaminated cobalt in the U.S. Government's National Defense Stockpile. Capital and operating costs for both potential applications are presented.

Jan 1, 1995

By Dorothée Proffit

Characterization of solids containing cyanides is carried out according to recommendations and standard guidelines. Most of these procedures are based on the analysis of leachates collected either on site or after leaching in the laboratory of samples. Unfortunately, these sole results are often insufficient to identify the source of the pollution. To provide 'a more complete characterization of polluted solids, optical and electron microscopy, XRD, Mossbauer spectroscopy, and transmission infrared spectroscopy were combined to analyze leachates and raw or ground samples. This combination of techniques allows the determination of the kind of cyanoferrate complexes are present in the solid state, different from insoluble Prussian Blue, since they do not have the same extraction' behavior. The use of all these techniques to characterize solid samples combined ,to the usual analysis of solutions gives a better understanding of ' the cyanide behavior.

Jan 1, 1998

At its Copper Cliff Smelter, Inco Limited processes a bulk copper-nickel concentrate in two Inco oxygen flash furnaces, The furnace matte is converted to low iron matte for further processing, and the molten converter slag is recycled to the flash furnaces. The flash furnace slag is discarded. Natural gas or coke supplies a minor proportion of the process heat requirements, thus limiting the flash furnace matte grade to the target 45% CuNiCo. Coke addition to the furnace offers a potential means of establishing a reducing barrier on the surface of the molten bath. Such a practice would be conducive to producing sulfur deficient (partially metallized) matte. At the same iron content, the iron activity of sulfur deficient matte is higher than that of regular matte. A supernatant coke barrier could, therefore, be expected to lead to higher nickel and cobalt recoveries, reduction or even elimination of magnetite furnace bottom build-up and increased sulfur elimination as S02 in the flash furnace. Preliminary experiments were conducted in a miniplant flash furnace to investigate the effect on process metallurgy of the suggested modified scheme. This paper presents the experimental results and discusses key aspects of the possible operation of the Inco flash furnace with a coke barrier separating the freeboard from the molten bath.

Jan 1, 2003

By Andrew Case

The Port Nickel facility in Braithwaite, Louisiana, is known for pioneering hydrometallurgical processes for the 'separation and recovery of nickel, cobalt and copper. Ten years ago, in 1985, a new CRI-MET process for the recovery of molybdenum, vanadium, nickel, cobalt and alumina from spent catalysts was developed and implemented. Spent- catalysts from the petroleum industry consietute the majority of feed. These are not only a valuable-source of metals, but due to EPA regulations are frequently classified as hazardous under RCRA. Molybdenum and vanadium are selectively leached in an oxidative hydrothermal step. Alumina is then extracted in a caustic digestive leach. The unique technology produces four primary commercial products l molybdenum trioxide, vanadium oxide, aluminum trihydrate and nickel-cobalt concentrate. This paper discusses the process, modifications. during ten years of operation, and the relationship of these modifications to the future of the catalyst recycling business.

Jan 1, 1995

By M. D. Stephens

A new, one-step process for extracting titanium from titaniferrous materials has been demonstrated. In the process, depleted uranium tetrafluoride (DUF 4), a solid, is mixed with ilmenite (FeTi03) and heated to 900°C. Titanium is extracted in the vapor phase as titanium tetrafluoride (TiF4) and the DUF4 is converted to uranium-iron oxide. The process has been found to selectively fluorinate the titanium in ilmenite and is capable of producing high purity TiF 4 with very low iron content. TiF 4 can be collected by condensation or through reaction with a fluoride salt such as NH4F, KF, or NaF. The TiF4 produced from the process can be used to make titanium metal, titanium oxide, or fluorotitanate compounds. Since the fluorination process is highly selective for titanium, it avoids many of the separations and waste issues common to other titanium extraction processes.

Jan 1, 2001

By Joon H. Jang

At a selected pH, hydrothermal oxidation of chalcopyrite was carried out under controlled F+,, at elevated pressures and temperatures (172-200°C) by balancing the rate of oxygen injection against the rate of consumption. Chalcopyrite was converted to covellite (CuS) and digenite (CU1.8S) with rejection of iron and sulfur to the solution. Covellite forms in the first stage, followed by nucleation and growth of digenite in the second stage. The effects of rapid and slow injection of stoichiometric quantities of oxygen are compared. Both the covellite and digenite form a porous layer occupying the same volume as the original chalcopyrite grain. An electrochemical kinetic model is presented to correlate the observed results.

Jan 1, 1993

By C. Lupi

"The energy consumption of copper production by electrowinning, generally represents more than 1/4 of the total energy requirement in hydrometallurgical traditional process (roasting, leaching, purification and electrowinning). The considerable saving can be achieved just in this step that requires about 2.2 kWhlkg of the produced copper. To save energy the cell voltage, or more appropriately its anodic component, can be reduced: that is because the anodic voltage represents the main component of cell voltage and so it is largely responsible for the excessive energy consumption in copper sulphate electrowinning.In this work some ways are studied to lower the anodic voltage. First the cobalt ions were added to the sulphate solution in order to study the catalytic effect on oxygen discharge. Then lead alloys anodes (Pb-Ag, Pb-Sb-Ag and Pb-Ca) were used to promote a better oxygen evolution as a result of a different anodic surface. Their behaviour was compared with the PbSb traditional ones. Finally, as already pointed out by several authors for zinc electrowinning, ethylene glycol was employed as anodic depolariser in order to verify its effectiveness in the case of copper electrowinning. By combining all the above-mentioned ways, energy saving ranging from 20% to 27% is achieved.All the tests were carried out on a laboratory pilot-plant for long time to simulate the industrial conditions. The obtained copper deposits were observed by SEM to highlight their morphology."

Jan 1, 1997

By H. Y. Sohn

The purpose of this article is to analyze critically and quantitatively the effect of chemical equilibrium on the overall rates of fluid-solid reactions. It is shown through a mathematical analysis that a reaction with a small equilibrium constant (a positive standard free energy of reaction) is more likely to be rate-controlled by pore diffusion or mass transfer than a reaction with a large equilibrium constant. The overall reaction rate of the former also tends to be slow. Furthermore, the apparent activation energy of such a reaction approaches the standard enthalpy of reaction (Mf'), rather than the true activation energy of the chemical reaction. The Law of Additive Reaction Times developed by the author is shown to apply to equilibrium-limited fluid-solid reactions and to be useful in quantitatively analyzing the behavior of such reactions.

Jan 1, 2003

By Richard D. Hangi

Process mineralogy techniques are uniquely applicable to industrial problems related to the extractive metallurgy of nickel, cobalt, and associated metals. Reflected 1ight microscopy, together with selected determinations by scanning electron microscopy-energy dispersive spectrographic analysis and electron probe microanalysis, provides the means to identify the ore minerals cobalt and nickel ores, determine the abundance of each ore mineral, assess the extent of intergrowth between the cobalt and nickel minerals and other ore and gangue minerals in the ores and concentrates, and predict the potential success of cobalt and nickel extraction by grinding, flotation, pyrometallurgical, and hydrometallurgical treatments. In addition, the extent of locking of the cobalt and nickel minerals with each other and with the gangue minerals can be directly observed by reflected light microscopy. Where ores have been treated by hydrometallurgical procedures, reflected light microscopy can serve to determine the causes of excessive leach consumption. Finally, the partitioning of cobalt and nickel between high-temperature synthetic phases produced by pyrometallurgical treatment can be precisely determined by process mineralogy techniques. Case histories from cobalt and nickel deposits illustrate the value of applied mineralogical techniques in the study of cobalt and nickel ores, beneficiation, hydrometallurgial, and pyrometallurgical products.

Jan 1, 1993

By Timothy W. Ellis

This paper presents the basic theory of operation, physical chemistry and phase equilibria which allow the development of liquid-liquid extraction circuits based on metallic solvents. The incorporation of reduction and reduction/diffusion processes into the process 'scheme is discussed and a detailed description of ,several liquid-liquid extraction schemes are developed. A synopsis of experimental results obtained using this: method to separate rare earth and other metal based materials will be given.

Jan 1, 1996

By Niko Hellstén

To capture efficiently the valuable trace metals from nickel slag using electric furnace, it is important to study their distributions between the slag and metallic phases in the furnace. It is impossible to calculate accurately these distributions without experimental measurements. Therefore, in this work, selected trace metal distributions and phase equilibria between K2O containing iron-silicate slags and a metallic Ni-Fe-Cu alloy in nickel slag cleaning furnace conditions were studied. The experimental method developed and applied during the work, involved a modified quenching technique that included equilibration of the samples in semi-sealed quartz ampoules in an inert atmosphere and metallic Fe saturation. The use of the semi-sealed quartz ampoule prevents the escape of volatile elements from the sample during equilibration. Chemical compositions of the phases and the trace elements were analysed by EPMA. From the measured compositions, the trace metal distribution coefficients between the molten Ni-Fe-Cu alloy and slag were calculated.

By O. Durand

The Cerro Verde Hydrometallurgical Plant, located at Arequipa in the southern part of Peru, started its operation in 1977 with a design capacity of 33,000 MT/year of copper cathodes. The plant has treated 61,055,000 MT of ore mainly oxides with a content of 1.01% total copper and 0.67% of soluble copper. The leaching plant has three pads that produce 4.0 gpl copper solution. The solvent extraction plant has four trains with three extraction stages, two stripping stages with a single mixer in all stages. The mixer-settlers are 316 stainless steel and the pumps are vertical turbines. The flowrates of 1,300 gal/mil of aqueous and 1,300 gal/min of organic at a 1/1 ratio. The electrowinning plant contains 208 commercial cells and 18 starting sheet cells. Each cell has 47 anodes and 46 cathodes. In addition to describing the hydrometallurgical plant, this paper also mentions efforts directed at reducing costs and improving operations. The initial results from leaching secondary sulfides, which started October 1985, are also discussed.

Jan 1, 1987

By N. S. Raghavendran

Based on the weld pool length and width calculations due to an empirical model (1) for submerged arc weld metal, an elegant quantitative definition of tandem submerged arc welding is established. On the basis of this theoretical consideration optimum welding parameters for joining 25 mm thick low carbon steel plate in two passes by tandem wire submerged arc welding have been experimentally found out. An assessment of the metallurgical quality of weld metal and the dependence of mechanical propenies on pool overlap has been made. Also the solution of Rosenthal (2) etc. for a moving point source of welding, which was used as a guide line in formulating the empirical model for the calculations of weld pool dimensions, is compared with the solution of empirical model for submerged arc weld pool dimensions.

Jan 1, 1990

By C. Burton Clark

The important role of the petrographic microscope in the petrology of refractories is discussed, based on 45 years of industrial experience by the author. Highlights of his career are used to illustrate improvements in equipment and techniques during the period. Two specific investigations are described which emphasize the interrelated use of the petrographic microscope with other instruments such as the x-ray diffractometer and scanning electron microscope. Emphasis is placed on the use of phase equilibrium diagrams for guidance in predicting and interpreting reactions that occur under non-equilibrium conditions in the manufacture and use of refractories.

Jan 1, 1982

By Richard B. Diver, Mark D. Allendorf, Daniel E. Dedrick, James E. Miller, Roy E. Hogan, Andrea Ambrosini, Eric N. Coker, Anthony H. McDaniel, Nathan P. Siegel, Gary L. Kellogg

"Converting carbon dioxide and water to hydrocarbons is an attractive option for storing solar energy and, coupled with appropriate CO2 capture technology, for recycling carbon and impacting atmospheric CO2 concentrations. For any process, high solar-to-fuel efficiency is necessary for large scale viability and favorable economics. Thermochemical approaches for solar-to-fuel conversion are potentially highly efficient as they avoid the inherent limitations of photosynthesis and also sidestep the solar-to-electric conversion necessary to drive electrolytic reactions. Solar-driven two-step metal-oxide-based thermochemical cycles for producing the components of syngas, CO and H2, from CO2 and H2O are the basis of the “Sunshine to Petrol” project. Multi-cycle production of both H2 and CO has been demonstrated over several iron- and cerium-based compositions fabricated into monolithic pieces both in the laboratory and at the National Solar Thermal Test Facility. These compositions are being developed for deployment in a unique and continuous solar-driven reactor prototype, the counter-rotating-ring receiver reactor recuperator or CR5.IntroductionThe interconnected challenges posed by increasing global competition for petroleum and the increasing concentration of atmospheric carbon dioxide are now widely recognized. Meeting these challenges requires recognition that although hydrocarbon fuels are ideal energy carriers, they can no longer be thought of as primary energy sources. It is necessary to take the realistic view that our conventional fossil fuels are in fact “stored sunlight” in the form of “sequestered carbon.” This view leads to a search for options to use and store sunlight more directly.Sunshine to PetrolIn combusting hydrocarbons we unlock the energy for utilization, but we also release the carbon to the atmosphere. However, nature teaches us that with an appropriate persistent energy source, e.g. solar irradiation, it is possible to effectively reverse the combustion process and “reenergize” CO2 and H2O back into hydrocarbon form."

Jan 1, 2010

By A. D. Damodaran

Batch scale and continuous rotary kiln carbothermic metallisation of ilmenite followed by different down-stream treatments such as catalytic rusting, acidic chloride leaching, oxidation-leaching etc. has given rise to a high grade synthetic rutile (98% TiO2). Rotary reactor metallisation experiments had concurrently given important information with respect to mean residence time, dispersion number, hold-up and axial velocity profiles of the solids bed. A mathematical model based on law of additive reaction times has indicated that Boudouard reaction becomes faster than reduction reaction at higher conversions. A possible use of high grade synthetic rutile in paint industry and metallised ilmenite as welding electrode flux material are discussed.

Jan 1, 1992

By Vinod K. Sikka, René Cooper

"Cohoes, New York 12047 Intermetallics are an attractive class of advanced materials. The aluminide intermetallics offer advantages including: (1) lower density, (2) oxidation resistance, (3) carburization resistance, and (4) interesting mechanical properties because of their ordered crystal structure. Even though the attractive properties of the aluminides and other intermetallics have been known for nearly four decades, their practical applications have not been developed for two reasons: (1) the poor ductility (in some cases, both ambient and high temperatures) and (2) the lack of processability into meaningful components. Recent advances such as ductilization of Ni3Al by small additions of boron and the knowledge that environmental effects are the major cause of poor ductility in Fe3Al and FeAl systems have brought the intelmetallics into the forefront of research and their commercial applications. This paper has described a method for melting Ni3AI-based alloys that successfully utilize the exotherrn for the formation of NiAl from the elemental materials. The reaction-synthesis method has also been utilized for the production of NiAI and NiAI-based alloy powders from the elemental powders. The reaction-synthesized powders of NiAI and NiAI-based alloys were consolidated by hot extrusion and evaluated for tensile properties over a temperature range from room temperature to 1050ºC. The powder-processing conditions have been found to have more influence on the ductile-to-brittle transition temperature of NiAI than the powder-production method.IntroductionIntermetallics are an attractive class of advanced materials [1-11]. The alum in ide interrnetallics offer advantages including: (1) lower density, (2) oxidation resistance, (3) carburization resistance, and (4) interesting mechanical properties because of their ordered crystal structure. Even though the attractive properties of the aluminides and other interrnetallics have been known for nearly four decades, their practical applications have not been developed for two reasons: (I) the poor ductility (in some cases, both ambient and high temperatures) and (2) the lack of processability into meaningful components. Recent advances such as ductilization of Ni3Al by small additions of boron and the knowledge that environmental effects are the major cause of poor ductility in Fe3Al and FeAl systems have brought the intermetallics into the forefront of research and their commercial applications. The paper will briefly review the processing techniques being pursued for the commercial applications of Ni3Al-based intermetallics. The major emphasis of the paper will deal with synthesis of Ni3Al and NiAI intelmetallics."

Jan 1, 1994

By Yanhui Liu, Xuewei Lv, Pingsheng Lai, Chenguang Bai

The purpose of this paper is to study the effect of slag basicity on the Si content in stainless steel master alloys prepared by smelting reduction of Fe-Ni-Cr sinters. Theoretical analysis focusing on the gas, slag and alloy phases of the smelting reduction process at 1600°C was carried out by thermodynamic calculation software----FactSage, showing that the increase of CaO within the slag can result in the decrease of Si within the master alloy. Experiments were also carried out in vacuum melting furnace at 1600°C , and chemical analysis method was used to detect Si content in the alloys. When the MgO content is 9.00%, the experimental results were consistent with the calculated values. However, when the MgO content rises up to 14%, the content of Si in the alloy reaches the maximum when SiO2 equals to 22.81%.

Jan 1, 2016

By T. Ueno

Naoshima Smelter & Refinery of Mitsubishi Materials Crop. commissioned a new Mitsubishi continuous copper smelter in May 1991. Process offgas volume of the conventional reverberatory furnace line, one of the previous smelters having been shut down, was very large and thus two acid plants had been operated. It was expected that the offgas volume would be reduced at the new smelter to about a half of the sum of those from previous two 1 smelters and the sulfur dioxide strength would be increased. So various alternatives were studied to minimize the operation cost. And it was decided to utilize both of the plants with minor modifications by diluting the gas either with air or with dilute gases. The acid plants now receive offgases from the new copper smelter, a sintering machine of a lead smelter and a decomposer of waste acid. The paper discusses plant design, operation, improvements and modifications realized in relation with the retrofitting of the copper smelter.

Jan 1, 1992

The effect of change in slag composition upon metal losses to the slag and the relationship between slag composition and slag matte separation was investigated at 1400°C. The synthetic slags containing CaO, MgO, SiO2,, A1,0, and FeO were similar to those employed in the electric furnace smelting of sulphide Cu-Ni concentrates containing PGM (Precious Group Metals) from the Merensky Reef of South Africa. The matte with a grade of 9.3% Cu and 16.0% Ni was a typical electric furnace product. The results indicated that the Cu and Ni solubility in the slag increases with the increase of the basicity ratio and CaO and MgO contents of the slag. At constant CaO/MgO ratios the rise in basicity decreases the metal losses. When FeO and SiO2 contents of the slag are kept constant, the substitution of MgO with CaO decreases the metal losses. The relationship between slag composition and matte-slag separation was found to depend primarily on the basicity ratio and the FeO content of the slag. The net effect comes from a strong interaction of the two in such a way that increasing basicity and decreasing FeO contents deteriorate the clean separation of the two phases.

Jan 1, 1994