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By Vitalij K. Pecharsky

Recent interest in complex aluminohydrides as potential near ambient, ultra-high capacity, solid-state sources of hydrogen (e.g., for fuel cells) calls for an improved understanding of the processes occumng in these hydrogen-containing materials during both the release and the uptake of hydrogen. Lithium aluminohydride (LiAlH4) rapidly releases 5.2 wt. % of hydrogen (i.e., nearly four times more than LaNis-based alloys) during mechanochemical processing at ambient conditions in the presence of transition metal catalysts. Using a variety of solid-state characterization techniques, the mechanochemical transformations in a series of LiAlH4 - metal catalyst systems have been examined and preliminary insights on the mechanism have been obtained. Surprisingly, the well-known hydrogenating-dehydrogenating catalysts, such as Ni and Pt, are practically inactive in the mechanochemical dehydrogenation of LiAlH4.

Jan 1, 2002

By Farhang Hedjazi

Anglo Asian Mining have recently installed an industrial-scale UF/RO plant to treat process liquors from the integrated heap leach/agitation leach/ resin-in-pulp gold ore treatment facilities at their Gedabek gold-copper mine in Azerbaijan. The UF/RO plant is designed to treat 60 m3/h of leach solution to produce discharge quality water. The RO concentrate, which contains elevated concentrations of copper, silver and cyanide, is sent to the company’s SART plant for the recovery of the metal values as a precipitated sulphide concentrate and the cyanide, which is recycled to leaching. The new water treatment plant improves the sustainability of the operations at Gedabek by enabling replacement of fresh water input with RO permeate and safe discharge of permeate to the environment, during periods of excess water balance. The paper includes pilot plant data and early results from the full-scale plant.

By C. Kathryn Sole

The close proximity of cobalt and nickel on the Periodic Table and their frequent occurrence together in nature means that their separation in primary hydrometallurgical flowsheets is not only often necessary, but requires the use of innovative chemistry to achieve high selectivity. Today, increasingly stringent demands for the high-purity cobalt and nickel salts required for battery applications in consumer electronics, electric vehicles, and solar applications are again challenging the state of the art. The evolution of cobalt–nickel separations is traced from the basic precipitation technologies employed in 1960s, through commissioning of the first cobalt solvent-extraction plant in South Africa in 1974, to the commercialisation of organophosphinic-acid extractants (which provided a step-change improvement in selectivity) and their eventual widespread use in the 1980s and ’90s. This was followed later by their sulphur analogue, which enabled different possibilities for laterite processing in the new millennium. Separations in chloride media, which take advantage of the different speciation chemistries, and nickel extraction by oximes in ammoniacal systems are also discussed. More recently, chelating and solvent-impregnated resins have added further dimensions to the possibilities for flowsheet design and enabled higher purity products to be attained from both primary and secondary sources. Selected case studies and flowsheets are described.

By M. Okido, O. Takai, Z. Zhao, M. Ishikawa, R. Ichino, K. Kuroda

"Electrolytic method was applied to calcium phosphate coating on titanium plates as an excellent technique for high density and intensive contact of coated films on biomaterials. The effect of H2O 2 as oxidation reagent on coating characteristics was examined to obtain biomineral films. Solution was containing 7.0 X 10·3 mol/dm3 ofCaC12 and 3.0 X 10·2 of Ca(H2PO4)z, kept at 55 ""C. All deposits were hydroxyapatite (HAp) in this study, independent of H2O 2 concentration, applied cathodic potential and solution pH. In the case of H2O 2 addition, an increase in cathode current started at the low potential, namely, ca. -0.2 V (vs. SCE). In contrast, the current increased at more than ca. -1.4 V in the solution without H2O 2 addition. H2O 2 appeared to be an effective reagent for increasing nucleation density and improving adhesion of deposits on titanium plates.IntroductionIn recent years, many researches have been undertaken to develop the techniques of calcium phosphate coating on titanium or bioglass for medical implantation. High density and intensive adhesion of coating are necessary for adding bioaffinity to these materials and for inducing bone morphogenesis on them when implanted in human body.1) Electrolytic deposition has been a newly developed method as high-speed deposition process. By this method, the supersaturation of calcium phosphate can be increased just in the vicinity of metal substrates and the heterogeneous nucleation is promoted on them. In this process, H2O is reduced according to eq. (1) on the cathodically polarized electrode"

Jan 1, 2000

By Arpad E. Tonna

Recycling of materials from lithium-oxyhalide batteries is a complex task, since the dismantling of batteries is associated with many hazards. The electrolyte and the lithium anode metal are extremely reactive in the presence of water or water vapor. Therefore, the dismantling process is a complex task. In this process, the lithium battery is electrically discharged, then frozen in liquid argon, and cut into small size pieces. These are fed into an incinerator, where the unreacted portion of lithium metal, thionyl chloride, plastic separators and carbon paste are decomposed and burned to gaseous products. The aluminum, iron (steel) and nickel pieces are recovered as saleable scrap metals. The off-gases are scrubbed with an alkaline sodium carbonate containing solution. The clean gases are released to the environment. The particulate mater recovered from the scrub-suspension would be available as additive to the cement industry . The recycling of battery decomposition products improves the economic viability of the disposal processes. Work is in progress to develop safe handling, processing and recycling large size lithium batteries.

Jan 1, 1995

By E. Charles Abbey

Manganese in electrolyte has both beneficial and detrimental effects in Zn electrowinning. Mn oxidizes to form MnO2 on Pb–Ag anodes, cell walls and pipes. MnO2 reduces anode corrosion but also leads to short circuiting and maintenance issues. MnO2 is thought to interact with chloride ions and produce oxidized chlorine species. The interactions between Mn and Cl are not well understood. Therefore, two sets of 45+ day bench scale experiments were conducted to investigate the effects of the manganese to chloride ratio on anode corrosion rate and electrolyte chemistry using rolled Pb–Ag anodes. Daily manganese and chloride losses from the electrolyte appeared to be correlated. Increasing the average Mn/Cl− ratio from ∼7:1 to ∼11:1 reduced the anode corrosion rate. Increasing the ratio above 11 did not reduce the corrosion rate further. Anode scales produced with Mn/Cl− ratios at and above 11:1 contained some γ–MnO2 while scales formed with ratios less than 11:1 did not.

By R. Kola

Since more than 15 years the Waelz process at "Berzelius" in Duisburg has proved suitable for reprocessing the zinc and lead containing dust and .sludge which inevitably occur in making steel in EAF-plants. The produced Waelz-oxide is agglomerated in a hot-briquetting plant and charged to an Imperial Smelting Shaft Furnace to recover the valuable elements in form of metallic zinc and lead. In view of the actual importance of the dumping problems of the EAF wastes a description of the "Berzelius" treatment route is given but also the situation in Western Europe is illustrated. Dust from stainless steel production is successfully treated in the Scan Dust Plasma Process in order to recycle Chromium and Nickel, while the resulting Zinc-Dust is treated via the Waelz-ISF-Route. For treatment of low Zinc-containing dust, sludge and fines from integrated steelworks, pilot scale tests have been carried out successfully in the Circulating Fluid Bed in order to recover metalized iron and .zinc/lead fume. A 30,000 tpy Demonstration Plant is planned?.

Jan 1, 1990

By Shoukun Wei, Cong Wang, Lin Cheng, Zhiyu Qiao, Jingkui Liang, Weidong Zhuang

"The subsolidus phase relations in the Sm2O3-CeO2-CuO ternary system sintered at 1000°C in air have been investigated by X-ray powder diffraction. The system can be divided into two ternary phase regions and three binary phase regions. Solid solution Sm2-xCexCuO4-y is the only ternary phase in the system. The maximum solid solubility was confirmed to be x = 0.2. The crystal structure, oxygen content and superconductivity of the solid solution Sm2-xCexCuO4-y have been investigated.I. INTRODUCTIONAfter the first discovery of the superconducting ceramic system La-Ba -Cu-O[l] with Tc = 30 to 40K, other families of cuprate-based ceramics have been synthesized with higher critical temperature. These oxides include the R-Ba-Cu-O (R: rare earth) systems (Tc=90K or so)[2,3], the Pb-Sr-(R,Ca)-Cu-O systems (T c = 50 to 100K), the Bi-Sr-Ca-Cu-O systems (Tc=80 to 105K)[4], the T1-Ba-Ca-Cu-O systems (Tc=85 to 125K)[5], the Hg-Ba-Ca-Cu-O systems (Tc=90 to 150K)[6,7], and some others. The improvement of Tc is very rapid. The measurement of the Hall and Seebeck coefficients shows that they all are p-type superconductors. In 1989, Tokura et al.[8] discovered the superconductors R2_XCexCU04_y(R = Nd, Pr, Sm) with Tc=20 to 24K (onset) and found that the charge carrier is electron in contrast to their hole doped counterparts. This discovery increases the fundamental understanding of the cuprate-based superconductors by comparing their characteristics and mechanisms to those of the p-type superconductors.One of the outstanding features of these n-type superconductors is the difficulty in obtaining samples in good charactors, such as the difficulty in obtaining zero resistivity state in single crystal or bulk samples; the semi-conductivity of bulk samples in ordinary state (opposite to the superconducting state) and a reducing reaction involved before the superconductivity has been found[9]. Therefore, it is necessary to optimize the sample preparation of the n-type superconductors. All the n-type superconductors have been found· considerable solid solubility. The compositional variations play a governing role in the carrier doping of the superconducting phases. Also, it is vital to the ceramic processing of superconductors to identify the compatible phases in the phase diagram. Finally, there is always the possibility of finding additional compounds, both superconducting and non-superconducting, in an unexplored system."

Jan 1, 1996

By Zhang Chuanfu, Tan Pengfu

"A thermodynamic model is developed to predict the distribution behaviors of Ni, Co, Sn, Pb, Zn, As, Sb, Bi, Au and Ag in copper pyrometallurgical process. In this model, as more as 21 elements (Cu, S, Fe, Ni, Co, Sn, As, Sb, Bi, Pb, Zn, Au, Ag, 0, N, C, H, Ca, Mg, Al, and Si) and 72 compounds (in fayalite-slag-making system) or 74 compounds (in ferrite-slag-making system) are considered. Accessory-element behavior is studied for two types of slag , fayalite and ferrite, and two levels of oxidation. The allowance is also made to account for physical entrainment in the melts.-Model simulations are carried out to study the effects of controllable process parameters such as feed composition, smelting temperature, degree of oxygen enrichment and volume of oxygen enriched air. The model can be used in copper flash process, Mitsubishi process and Noranda process. The predictions by the present computer model are compared with the known industrial data from Gui Xi Smelter in China, Home Smelter in Canada and Naoshima Smelter in Japan and excellent agreement between calculations and industrial data is obtained. In this paper, the effects of oxygen enrichment, matte grade, smelting temperature, and types of slag on accessory-element behavior among matte, slag and gaseous phase have been elucidated.I . IntroductionThe presence of trace quantities of minor elements such as As, Sb and Bi in copper significantly reduces its ductility, electrical conductivity, and lowers its thermal conductivity. Embrittlement of copper also occurs due to impurity-phase precipitates at the copper grain boundary interfaces. They deteriorate not only the electrical conductivity of copper but its workability in hot working."

Jan 1, 1998

By Omid Marzoughi

Chromium has a wide range of applications, including as an alloy addition in various steels and also as a corrosion resistance coating. Carbothermal reduction of chromite ore (FeCr2O4) in a submerged arc furnace is an important industrial process for extracting chromium, but the energy consumption is excessive. It is suggested that one area for future research is the low temperature carbothermic solid state reduction of chromite to produce an intermediate product, which can subsequently be upgraded to ferrochromium. In this regard, a thermodynamic model has been developed to investigate this process and the effects of temperature, carbon additions and ore composition on the recovery of chromium and the grade of the ferrochromium, have been studied. Further development of the model may allow it to be applied to the simulation of other processes for the recovery of chromium from chromite ores.

By Leiting Shen

The thermodynamics of tungsten ore decomposition in mineral acid and alkaline solutions were studied. The published thermodynamic data of tungsten minerals were collected and assessed. The Gibbs energies of CaWO4 (−1538.43 kJ/mol), FeWO4 (−1053.91 kJ/mol), MnWO4 (−1206.08 kJ/mol), H2WO4 (−1003.92 kJ/ mol), and Na2WO4 (−1455.58 kJ/mol, aq) at 25 °C were adopted in the calculation using HSC software. The results show that CaWO4 is decomposed more readily in Na2CO3 solution than in NaOH,while FeWO4 andMnWO4 aremore reactive inNaOH solutions. Froma thermodynamic point of view, tungsten ore decomposes easily in acid solutions despite most ΔGo T increasing slightly with temperature. Oxidizing Fe2+ to Fe3+ in acidic solutions facilitates decomposition of FeWO4, and the reaction of CaWO4 in H2SO4 solution occurs more easily than in other mineral acids, due to the formation of sparsely soluble CaSO4. The results fit well with the experimental data and industrial experience previously reported in the literature.

By Bradford C. Wesstrom

The extraction of metals from Copper Refinery Slimes may involve many different processes. This paper describes the use of pressure leaching for decopperizing of copper refinery slimes at the El Paso Refinery. Process equipment will be described, along with the process chemistry, unit operations and unit processes associated with the decopperizing process. Copper contained in the raw slimes ranges from 15-35%. After autoclaving less than 1 % copper remains.

Jan 1, 2000

By A. Jakobsson

Studies of the rate of interdissolution in oxide systems in the solid state are of importance in materials processing through the powder-metallurgical route. As there is a need for following the rate of the such reactions continuously, a new method based on high temperature X-ray diffraction was developed. Mechanical mixtures of the oxides were placed in a high-temperature X-ray diffraction unit and the changes in the intensity and position of the peaks with highest intensity for both the components were followed as functions of time. A suitable theoretical model has been developed in order to interpret the experimental data and evaluate the diffusion coefficients. The method was applied in the case of the system MgO-NiO. The results obtained are compared with those obtained by another new method, based on solid-state galvanic cell technique with calcia stabilized zirconia electrolyte, developed in the Department of Theoretical Metallurgy. The advantage of the present techniques to monitor the progress of the reaction continuously make them suitable for computer control of such processes.

Jan 1, 1995

By Jürgen Antrekowitsch, Thomas Griessacher

"Heavy metal containing residues are typically hazardous wastes because on the one hand, a deposition gets more and more complicated and on the other hand, the large amounts of metals like Zn, Cu, Fe and Pb represent a significant value. Thus, a post-treatment of these materials with the recovery/recycling of the metals and stabilization of the waste is not only ecological but often also economical. The therefore typically applied recycling processes utilize pyrometallurgical steps, where carbon or carbon monoxide from fossil coal and coke is used as a reducing agent, which results in large amounts of CO2 emissions. An alternative option is the application of a hydrogen-rich gas emitted in biomass utilization processes as a carbon-neutral reducing agent. Investigations in a retort process which were done at different temperatures and times showed excellent results concerning the achievable reduction rates and final contents of the heavy metals for various residues.IntroductionNowadays heavy metal containing residues like electric arc furnace dust (EAFD), dust from cupola furnaces, waelz slag, etc. are declared as hazardous wastes in a growing number of countries due to the leachability of the heavy metals in these residues. For that reason it is no longer possible to landfill these materials or use them for road construction or disposal works. Some land filling activities, carried out until now, have only been realizable because of some process modifications or cost intensive post-treatment steps of these residues. But the disposal capacities for such materials are decreasing, therefore increasing the prices. The second point for the growing disposal limitations is the stringent environmental legislations and regulations, which restrict the number and amounts of materials which can be dumped [1 – 5].From the other point of view these heavy metal containing residues usually have high contents of zinc, lead, iron, etc., which represent a significant value and therefore a big potential to recover these metals. This is why in recent years the number of recycling processes and the amount of recycled heavy metal containing residues have continuously increased. These recycling processes have the target to recover the valuable metals from the residual materials in the form of a saleable product as well as the stabilization of the slag produced in these processes [5, 6]."

Jan 1, 2011

By Yury Kapelyushin

Formation of cementite in the reduction of hematite by CO–CO2 gas was studied in situ using high temperature XRD (HT XRD) analysis. Reduction of hematite was examined in the temperature range 873–1173 K by CO–CO2 gas mixture with high carbon activity. When carbon activity in the system was 1.5, cementite was formed only at 1023 K; it was not observed in experiments at 973, 1073 and 1123 K. Formation of cementite was observed at 923–1073 K when carbon activity increased to 3–5; and at 873 K when carbon activity was 10. Formation of cementite at 973–1073 K proceeded through metallic iron; however, in the reduction of hematite at 873 and 923 K, iron was not observed; cementite apparently was formed directly from wüstite. XRD spectra were used to estimate concentration of carbon in austenite in the process of cementite fromation.

By Peter G. Cooper

"During 1987, the feasibility of modernising the ER&S smelter at Port Kembla, NSW, Australia was studied. The selection of appropriate technologies to carry the smelter into the 21st century considered issues such as capital cost, existing infrastructure, feed mix, capacity, product quality, flexibility and potential for further development. Both hydrometallurgical and pyrometallurgical process schemes were considered. Some novel combinations were assessed but ultimately rejected. Final technology selections included proven smelting and anode furnace processes, pyrometallurgical slag cleaning and modifications to existing equipment. This process scheme balanced risk against development potential within the constraints imposed by the existing plant.BackgroundThe Electrolytic Refining and Smelting Company of Australia (ER&S) has operated a custom copper smelter at Port Kembla since 1908. Existing technology includes a sinter plant/blast furnace, three small Peirce Smith converters, two reverberatory anode furnaces and a conventional tankhouse. These process units were all installed prior to 1960 and have proven to be flexible enough to process the wide variety of domestic feed materials purchased by ER&S.However, by the early 1980s, threats to domestic concentrate supplies highlighted the need for major changes to reduce operating costs to world competitive levels. Various studies in the ensuing years failed to identify an economically attractive solution. Furthermore, pressures were increasing to improve the environmental performance of the smelter.During 1986 the options for redevelopment were again considered and by the end of 1987 technologies for the retrofit had been selected and a full feasibility study was completed."

Jan 1, 1988

By John W. Ahlrichs

Microscope, electron microprobe and x-ray diffraction have been used to provide quantitative evaluation of products from the mill, smelter, refinery and other metallurgical processes. Phase compositions and their quantities are necessary for an adequate understanding of the various products obtained throughout an operation and in laboratory testing. By careful evaluation, important information can be gained in improving recoveries and increasing grades at various stages of processing. Four case histories are discussed in this paper. Quantitative microscopic counting techniques are applied to mill products to determine degrees of locking and liberation of the economic minerals. Rapid, but accurate evaluation aids the metallurgist to develop or improve the grinding and flotation circuits. In the smelter, the identification and quantification of the phases are important for predicting reaction mechanisms and kinetic trends. Mineralogic techniques have been applied to conventional smelter products, and to those obtained in laboratory tests for newly developed innovations to smelting. Small, but important, values of gold occurrences in ore are difficult to determine. Evaluation of gold usually requires special separations into various mineral concentrates, followed by assays and mineralogic determinations of the products. Numerous occurrences of solid solution constituents can be treated as by-products, but often they are deleterious to metallurgical treatment. Most solid solution problems can be unraveled by the mineralogist's tools.

Jan 1, 1981

By David A. Neudorf

Known resources of nickel laterites considerably exceed nickel sulfide resources and there is a growing consensus that most new nickel production will be sourced from laterites. The development of nickel laterite projects is very capital intensive due to inherently low grades, inability to concentrate ore prior to processing, complex processing technology and typically large infrastructure requirements. This has resulted in most recently proposed projects being "mega-projects," to achieve economics of scale. However, this may result in unacceptable project risk in many cases. Furthermore, many known laterite resources are not large enough to support a mega-project. This paper describes an alternative model for nickel laterite project development that allows, smaller scale and reduces capital exposure. The requirements of this model in terms of process technology, infrastructure and commercial innovation are described. Keywords: Nickel, Laterite, Project, Economics

Jan 1, 2004

By Hsing Kuang Lin

Ferric chloride leaching w.as applied to a complex sulfide ore from Tok, Alaska to dissolve zinc, lead, silver and copper. Gold in the leaching residue, as well as in the ore, is found to be refractory to the conventional cyanidation process. Roasting, pressure oxidation and elemental sulfur removal followed by cyanidation were tested to improve gold dissolution. Also tested were thiourea leaching and high-pressure cyanidation. The readsorption of dissolved gold by carbonaceous matter in the chloride leaching residue was analyzed. Based on the experimental results, factors causing difficulty of gold dissolution from the leaching residue are discussed.

Jan 1, 1989

By Marion Dattilo

The search for an improved anode for the electrowinning of lead from fluosi1icic acid medium has led the U.S. Bureau of Mines to investigate composites. Polymer bonded metal oxide powders which may contain catalyst additions were prepared by pressing. These composites display an improved activity toward the oxygen evolution reaction over electrodeposited lead dioxide on titanium, carbon, and nickel substrates. These composite electrodes contain 5 to 10 wt. " binding polymer, with the balance being metal oxides. Lowered anodic potentials achieved using the compnsite anodes resulted in lower levels of lead dioxide deposition during electrowinning.

Jan 1, 1995