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By C. A. Nogueira, F. Margarido

"A research work has being carried out annmg at evaluating the possibility of treating simultaneously several electrochemical systems of spent batteries using the same process, in order to overcome the high costs and difficulties of selective collection and sorting. Zn-Mn02 systems, representing more than 75% of portable battery market, shall be treated in dedicated processes. The treatment assessment using a single hydrometallurgical process of the other major systems (NiCd, NiMH and Li-ion), having Ni and Co as main metals, was the aim of the research work here reported. Sulfuric acid leaching was demonstrated to be adequate for dissolving more than 90% of the metals of interest contained in batteries. The subsequent separation of metals by solvent extraction, using organophosphorous extractants like DEHPA and Cyanex 272, allowed the production of pure solutions of rare earths, cadmium/manganese, cobalt, nickel and lithium, enabling their further recovering.IntroductionRecycling is the best approach for end-of-life management of spent batteries mainly by environmental reasons but also motivated by resources conservation and, in some cases, by economic profits. Most relevant electrochemical systems of portable cells are Zn-Mn02 (ZMB, alkaline and saline), nickel-cadmium (NiCd), nickel-metal hydride (NiMH) and lithium-ion (LIB). These batteries are collected, sorted and usually treated separately, applying for pyrometallurgical or hydrometallurgical technologies, the former being the most common.Several processes have been developed and some of them industrially applied, as described in some available review papers [l, 2]. In Europe for ZMB systems the oldest processes are Batrec [3] and Citron [4]. Although having differences in details, both are based on pyrometallurgical recovery of zinc by distillation, in metallic or oxide forms, being manganese retained in the slag together with iron. Hydrometallurgical alternatives are also available, like Zincex [5] and Recupyl [ 6] processes, both using sulfuric acid solutions as leachant. The application of the existing technologies to battery recycling, instead of using dedicated processes, is other alternative already tested, being the Waeltz furnace or the Imperial Smelting some examples."

Jan 1, 2012

By William R. Opie

Considerable effort by extractive metallurgical research organizations has been devoted recently to developing pollution-free processes for treating copper sulfide concentrates. A number of hydrometallurgical processes are in various stages of development and have been subjected to economic evaluation. Although the hydrometallurgical approaches eliminate SO2 emission problems, they create objectionable effluents and residues, make precious metals recovery complex, and are not very efficient for treating chalcopyrite. Furthermore, they are consumers of considerably more energy than pyrometallurgical processes which produce blister copper that can be electrorefined to commercial grade cathodes. This paper discusses a pyrometallurgical process under development by AMAX Base Metals Research & Development, Inc. (1) The original objectives set for the process development were: 1. Sulfur control of at least 95% with elimination of fugitive emissions. 2. Copper and precious metal recoveries as good as or better than conventional processes. 3. Low capital cost. 4. Competitive operating costs 5. Use of known proven technology where applicable.

Jan 1, 1976

Physical and chemical properties of the salt flux phase play a significant role in the recycling of UBC in Aluminum melting processes. Particularly knowledge of several properties such as salt vapor pressure, melting temperature, loss of aluminum, corrosion of refractories are useful for the process control decisions in order to attain a good quality of aluminum produced. A literature review and analysis of several salt flux systems for the selection of a flux for the Aluminum melter (low temperature natural gas bath melting) process were made. Based on these analysis two salt flux systems are recommended for further studies. These are NaCl?KCl?LiF system and NaF?LiF?KCl system with small amounts of other salt additives. Application of these fluxes to Al industrial processes are discussed.

Jan 1, 1996

By S. R. Reddy

Thennodynamic properties of several quaternary systems are calculated using our recently modified Margules equations. The modified Margules equations are expressed up to infinite order in the vicinity of solvent. Quaternary system of one solvent and three,solute partials are derived. First order interaction coefficients of binary, ternary and cross -interaction parameters of quaternary system are used to'evaluate the partial functions. In the original fonn of Margules equations,derived partial functions are convergent and same 'as Unified ,Interaction Parameter Fonnalism. But considering up to infinite order of the Margules coefficients, the functions are divergent, in order to overcome this restriction, Margules equations are modified to get consistent equations. Derived partial functions are thennodynamica Hy consistent with Maxwell and Gibbs Duhem relations. The derived logarithmic activity coefficient of the solvent and solutes are consistent with the ternary systems. The calculated data, ie., activity coefficient values of nitrogen and interaction coefficients are in good agreement with the data of Fe-Cr-V -N. Fe-Ni-V -N, Fe-Cr-Ta-N and Fe-Ni-Ta-N systems.

Jan 1, 1999

By G. R. Palmer

The success of future electric vehicles will depend greatly upon the power supply choices made today. Research is presently being conducted by automotive engineers and electrochemists to determine what battery type may be the most promising. Not only are product production and application efficiencies being evaluated but also environmental concerns of reclamation and recycling. Rechargeable batteries using nickel-metal hydride electrodes are strong candidates for these electric vehicle applications. The U.S. Bureau of Mines is investigating hydrometallurgical technology that separates and recovers purified metallic components present in nickel-metal hydride battery scrap. Sulfuric, hydrochloric, and nitric acids are all capable of dissolving the battery electrode alloys given the proper operating conditions. Solvent extraction of the leach solutions using D2EHPA removes iron, and selective precipitation shows promise of recovering the other metals in the H2SO4 and HNO, systems.

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 Zhang Libo, Li Wei, Peng Jinhui, Guo Shenghui, L. Jing

Partially stabilized zirconia ceramics (PSZ) were prepared by microwave sintering using natural baddeleyite which was obtained by flotation of baddeleyite ore as starting materials. Because of using natural baddeleyite as raw and the process producing no waste, it realized shorter process, energy savmg, environmentally-friendly and non-damage processing. In this work natural baddeleyite stabilized with 3.8wt.% CaO were sintered at 1300°C for 60min in a multi-mode 2.45GHz microwave furnace. Microwave sintering could fast heating and sintering. Besides that, microwave sintering could heat materials wholly, low the sintering temperature, improve the materials properties and save energy. X-ray spectrum displayed the product composed by the tetragonal phase and monoclinic phase that also showed the product was PSZ. Fine and uniform microstructures were observed in the product through scanning electron microscopy. PSZ which was with high density was confirmed by the method of the Archimedes technique.

Jan 1, 2011

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 Robert D. Rogers

The demand for phosphate will continue into the future, because phosphate is currently irreplaceable as a plant nutrient and in many chemical applications. Phosphate is not recycled, so the supply must be replenished through a process of mining and purification. Numerous microbial isolates. obtained from the environment were screened find those which demonstrated the greatest promise of solubilizing PO4 from the ore of interest. Screening was accomplished in a step wise manner an agar plate bioassay, shake flask studies, and semi continuous growth conditions. It was found that with the proper conditions of nutrient supply and solution pH; the bacteria and. fungus used in the semicontinuous process were able to solubilize in excess of 80% of an Idaho rock phosphate ore (RP) within nine days. A significant amount of solubilization occurred within the first six days. There was a 'reasonable correlation between the occurrence of soluble Ca and PO.4 during the processing of the RP thus providing evidence that the RP was being disintegrated by the organisms. In all cases, HPLC analysis of the solutions in which PO4 had been. extracted from RP showed that organic acids, which have been implicated as the mechanism of solubilization, were present.

Jan 1, 1991

By Baozhong Zhao

The direct smelting of copper concentrates to copper metal in a single furnace offers environmental and energy advantages over conventional two-stage copper smelting processes. However, the direct copper making results in unacceptably high level impurities (As, Sb and Bi) in the anode copper. Experimental studies have shown that it is possible to remove these impurities from molten copper by injection of sulfur-hexafluoride. This paper discusses the experimental findings on the influence of various factors on the rate of removal of impurities, such as the impurity inter-effects, initial oxygen content in the metal and injection rate of SF6.

Jan 1, 1995

By A. E. Isaacson

Bureau of Mines researchers developed and tested equipment to measure corrosion rates on a commercial-scale mill as an aid in predicting the effect of corrosion on minerals and how this effect relates to downstream processing. Bench-scale experiments were designed for duplicating ore grinding conditions closely enough that realistic rate determinations can be made in laboratory tests. Rates measured in a laboratory system compared favorably with those measured in the field. Cast steel was found to have corrosion rates in a copper mill and laboratory test cell of 22 and 21 mpy, respectively. Corrosion was found to account for less than 5% of the total grinding media wear in the operations studied.

Jan 1, 1987

By Jun Sugiyama, Hiroyuki Sano, Toshiharu Fujisawa, Hideki Takeuchi, Chikabiuni Yamauchi

"The solid .state electrotransport (SSE) is one of the most promising methods for the elimination of gaseous impurities from chemically active metals, such as rare earth metals. . In the present work, the SSE process was applied for the oxygen removal from praseodymium. The SSE factors, such as effective valence, were measured under the various temperatures, electric field intensities and initial oxygen contents, and the effects of those conditions on the SSE process were discussed. Furthermore, the solubility of oxygen in .solid praseodyillium was also measured·, by using the SSE method and metal-oxide equilibrium method.IntroductionWhen a direct current is passed through a solid alloy, not only electrons but also solute atoms are transported as charge carriers toward the anode or cathode. This phenomenon is referred to as an electrotransport or electromigration. The solid state electrotransport (SSE) is the application technique, based on this principle, to the pUrification of the solid metallic materials.Rare earth metals are used for various functional materials, such as magnetic, optical or electronic materials, therefore their high purity metals are required [l ,2]. However, rare earth metals are chemically active and have a strong affinity with gaseous elements (e.g. oxygen, nitrogen, hydrogen and carbon). In many cases, eliminating operations of gaseous elements have not been always made commercially, because these impurity elements could not be eliminated by usual treatments applied to the purification of ·common metals. As an alternative method, authors have proposed the· application of the SSE process to the elimination of gaseous impurities from rare earth metals. Investigations have been carried out on the yttrium-oxygen and neodymium-oxygen systems and the results were already reported[3,4]."

Jan 1, 2000

By D. M. Jones

Dust generation data have been obtained from 19 industrial Outokumpu flash furnaces. Statistical analyses of the data have been carried out and the most significant factors affecting dust generation evaluated. The results indicate that dust production may most effectively be minimized by: 1) Minimizing the distance between the molten slag and the furnace roof 2) Optimizing burner design and combustion parameters.

Jan 1, 1996

By I. Gaballah

Spent hydrorefining catalysts may contain 4 to 6 % of COO and/or NiO, 8 to 16 % of Moo3 and up to 10 % V205 generally supported by alumina. Raw samples are roasted in order to eliminate carbon, sulfur and hydrocarbons contained in the spent catalysts. The roasting optimum temperature and time are 500 "C and 7 hours. Selective chlorination of roasted samples with Cl2 + air, Cl2 + N2 and Cl2 + CO is investigated in order to recover the valuable metals. Depending on the chlorination it is possible to recover more than 80 % of the Ni and Co about 95 % of the Mo and up to 80 % of vanadium compounds. Cobalt and nickel chlorides are obtained by leaching the chlorination residues' by acidified water. Molybdenum and vanadium chlorides and/or oxychlorides are obtained by selective condensation from the vapor phase. The chlorination of the catalyst support, Al2O3, can be limited to less than about 5 %. Besides the reaction temperature and time, the oxygen partial pressure of the chlorinating gas mixture appears to be the key factor for the reactions' selectivity.

Jan 1, 1993

By Onuralp Yucel, Ahmet Turan, Murat Alkan, Hasan Ozer

SHS (Self-propagating High-temperature Synthesis) is one of the important methods to synthesize B4C powders. The process contains the reaction of boron oxide powders (B2O3) with magnesium reducing agent and carbon black carburizer. SHS products are leached in HCl media to purify synthesized B4C powders in the following step. In the present study, effects of various functional additives (KClO3, KHSO4, MgSO4.7H2O, NaCl, MgO and Na2SO4) in the SHS stage were carried out. Various proportions of the additives were mixed with the initial SHS charge mixtures. Two different molar ratios were employed in the initial SHS mixtures as 1:3:0.8 B2O3:Mg:C and 1:2.5:0.8 B2O3:Mg:C. After the SHS step, HCl leaching process was applied to the SHS products. Filter cakes were dried and characterized by using X-Ray Diffraction Spectroscopy, BET and chemical analysis techniques.

Jan 1, 2015

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 Junbiao Liu

Rutile is mostly produced from placer sands. Its beneficiation from primary deposits has rarely been investigated. However, there is interest in primary deposit because of the depletion of sand deposits. The Zaoyang deposit in China is the only rutile primary deposit currently mined. The plant employs a Tabling-Magnetic process which recovers only 20% Ti02 at a grade of 87%. This study shows that significant improvement on the recovery (52% at the same grade) can be achieved. This study includes a detailed mineralogical examination and the development of a processing flowsheet of the ore. The gangues are primarily amphiboles, garnets, zoisites, and chlorites. The liberation of rutile occurs at about 200 mesh. Gravitational, flotation, and magnetic separations are all employed in the process developed, depending on the mineral characteristics and experimental results. The flotations circuit utilizes benzyl arsonic acid to float rutile and sodium fluosilicate to depress the gangues. This is a new reagent scheme for rutile flotation.

Jan 1, 1989

By H. Soto, J. Jara, F. Nava

A method has been developed to recover cyanide and copper from solutions containing copper complexes and thiocyanate. Copper is precipitated as copper thiocyanate or as copper cyanide depending on pH and the concentrations of thiocyanate and cyanide in the effluent. The copper precipitate assays over 50% copper and presents good dewatering characteristics. After settling it can be separated from the effluent by filtration. The solution containing the bulk of the cyanide is then oxidized with ozone to transform the remaining thiocyanate into cyanide. This results in a regenerated solution rich in free cyanide that can be recycled to the cyanidation process. Careful control of the pH of the solution is required. First, pH of the effluent is lowered to optimize the precipitation and oxidation stages, then the pH is restored to an alkaline value to regenerate the cyanide solution. Recoveries of over 96% copper and cyanide were obtained in laboratory tests using industrial solutions. With this procedure, cyanocidic gold/copper ores could be treated economically by heap leaching, since the cyanide consumed by the copper impurities could be regenerated at very low cost (most of the cost of cyanide regeneration would be compensated by the copper credits). In order to achieve this, a bleed of the barren solution could be treated by the proposed method, and then recycled to the leaching step. The volume of solution to be treated should be large enough to keep a cyanide/copper molar ratio higher than 3:1. This would assure that copper does not cause undue interferences in the leaching or the carbon adsorption stages. If the thiocyanate content is low, the oxidation stage can be avoided, and the solution can be recycled to the leaching stage directly after the solid-liquid separation stage.

Jan 1, 1997

By R. E. Moore

The lining systems currently in use in BOF furnaces, certain steel ladles, and the slag line of electric are furnaces were developed during the late seventies through the mid-eighties using a trial and error method of combining aggregate, carbon sources, additives and binders. They are currently based on magnesia, graphite, metal additives and resin binders, the selections of each being tied to the anticipated intensity of the use conditions. The general functions of the respective constituents are well appreciated, however, there is still a great deal that is not known about how the socalled antioxidants protect the graphite nor how impurities from the graphite and the aggregate enter into the wear processes. In a simplified assessment of wear processes, it appears that if the deoxidized layer can be kept very thin, less than 810 mm in depth, and if the viscosity and quantity of the matrix glassy phases can be controlled to resist erosion of the deoxidized layer, lining life can be maximized for the various applications. This paper will discuss the characteristics of the starting materials systems currently being employed for applications requiring a deoxidation function to realize extended wear. It will not attempt to explain all the complex interrelationships between the respective constituents but will point to the potential for improvements through the use of improved constituents.

Jan 1, 1991

By Knut H. Bech, Stein Tore Johansen

"The collision efficiency for small particles relative to 2D spherical bubbles in a developed turbulent flow field were calculated applying an adopted version of the CPD program FLUENT. The turbulence field was related to bubble size and fluid properties. The results were compared with analytical theory. The turbulence intensity was found to be the most important single parameter for collision efficiency. Effects of boundary layer thickness and particle diameter were discussed. IntroductionRemoval of inclusion particles from melted aluminium can be facilitated by means of a rotor system that supplies kinetic energy and gas bubbles to the floating metal. At the surface the inclusions adhere to the surface dross or slagg which is removed at regular intervals by the operators. When applying computational fluid dynamics (CFD) to model such a system, one experiences difficulties with the large range of turbulent length-scales encountered, from the large geometrical scales of the rotor and container, through the bubble size and down to the particle diameter. A mathematical model for the complete system will be both complex and require an extreme spatial resolution. Another way of dealing with the problem is to model the micro-scale phenomena separately and apply the results to create a model for the macroscopic system. In a previous work [12] we addressed these problems and developed a procedure for calculating turbulence enhanced flotation to bubbles. It was found that turbulence may have a profound effect on the collision rate of particles to idealized bubbles. In this study we recognize that only a fraction of the total turbulent kinetic energy generated by the rotor's work on the liquid metal may contribute to enhanced flotation. By using a model spectrum for the turbulence, the fraction of turbulent energy in eddies smaller than the bubble diameter is calculated. A twodimensional CFD model was then constructed to calculate the collision efficiency between particles and bubbles of various sizes."

Jan 1, 1999