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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 Djona M. Gaballah I.

Selective chlorination of unroasted and roasted spent hydrorefming catalysts was studied between 300 and 600°C using the following gas mixtures : C12+CO, C12+N2 and CI2+air. Such materials contain Co, Ni and Mo compounds supported by alumina and/ or silica. They also contain variable amounts of V compounds, C, S, etc., accumulated during the life time of the catalyst. Direct oxychlorination of the C+S rich sample allows higher extraction rates than those obtained by the carbochlorination of the same roasted one. It seems that the roasting step doesn't favor the economic metals' recovery. Results of the chlorination of C+S poor spent catalysts, in the presence of CO, in the chlorinating gas mixture, or of carbon added to the sample, were comparable. Cobalt and nickel chlorides were .extracted from the chlorination residues by their dissolution with acidified water, whereas molybdenum and vanadium chlorinated compounds were recovered by selective condensation from the vapor phase. The recovery rates of valuable metals as well as the selectivity were higher for the chlorination of spent catalysts than results obtained by the hydrometallurgical processing of the same sample. Results of the scale-up of the oxychlorination of the unroasted sample confirmed those of the laboratory scale. The global recovery rates were about 88 pct of cobalt, 93 pct of molybdenum and 76 pct of vanadium. The carbochlorination was applied to the recovery of W and Ti from Denox catalyst that is a carbon and sulfur free one. Recovery rates higher than 99 pct at temperatures lower than 500 °C could be obtained. This may indicate that the chlorination process can be applied to the treatment of various industrial wastes or by-product containing transition and/or refractory metal compounds A flow - sheet for the pretreatment of these materials is proposed.

Jan 1, 1995

By Fang-Qui Zu

Understanding the nature of liquid structures and properties remains an open problem for many fundamental and applied fields such as materials sciences and processing. And as well known, there is no other defined phase line above liquidus (TL ) in phase diagrams of ordinary binary systems. However, via different experimental resorts, our research results on over 30 metallic melts including alloys and elements show a novel physical image: temperature induced liquid-liquid structure transition (TI-LLST) can occur hundreds of degrees over TL. On the other hand, the solidification behaviors and structures out of the melts experienced TI-LLST are distinct from those out of the melts before TI-LLST. In this presentation, some characteristic aspects of the TI-LLST and the effects on solidification behaviors and structures are briefly summarized, and the pertinent rules and mechanism are also analyzed.

Jan 1, 2009

By L. Lü, M. O. Lai

"Mechanical alloying is a dry, high energy ball milling process which has been used to synthesize metallic powders in the solid state. The present study use this technique to synthesize Cu-base shape memory alloy powder from commercial Cu70Zn30, Cu86Zn14 and element AI powders. The evolution and formation of shape memory alloy powder were monitored using X-ray diffraction and microscopy. It was observed that shape memory alloy powder started to form after 1.8 ks of mechanical alloying. ? phase was clearly detected after 3.6 ks of mechanical alloying. The intensity of X-ray diffraction of the y phase increased when mechanical alloying duration was prolonged indicating an increase in the amount of y phase. Microstructure observation showed different stages of formation of alloyed powders: welding between powders and formation of layered structure, deformation and fracturing of layered structure, and finally the formation of alloyed powders.IntroductionMechanical alloying (MA) is a process used for producing powders with controlled and extremely fine microstructure. It was original developed in 1966 (1) to produce aNi-based superalloy combining oxide dispersion strengthening with gamma prime precipitation hardening. In recent years this technique has been used in producing a wide range of materials including intermetallic compounds (2, 3), amorphous materials (4-6) and other materials (7-9). In MA, a blend of powders is subjected to highly energetic compressive collision. The powder panicles are welded and fractured during ball milling. Therefore, it is essential that at least one of powders should be ductile to act as combiner. It has however been found that brittle components without soft element can also be mechanically alloyed (10), even ceramic powders (11).The present work aims to study the mechanism of formation of shape memory alloy powder during MA."

Jan 1, 1994

By Kafui Nyavor

The indirect, and the direct contact mechanisms of bacteria oxidation of sulfides were studied using Thiobacillus ferrooxidans and pyrite. The aim was to determine which of the two generally aeeepted mechanisms played a dominant role, if any, during acid mine drainage (AMD) formation from the oxidation of sulfide minerals. The results show that at a pH of 4.5 where T. ferrooxidans are quite active, but where initial chemical oxidation of pyrite to Fe2+ is limited, the bacteria were unable to directly oxidize pyrite to any significant extent. Whereas, in the presence of Fe2+, T. ferrooxidallS assisted oxidation of pyrite by the indirect mechanism was observed and sustained over the pH and Eb range where the bacteria is active. The results lead to the conclusion that the direct contactmechanism of pyrite oxidition by T. ferrooxidans is insignificant. The predominant, and possibly the only, pathway involves the indirect bacteria oxidation of available Fe2+ to Fe3+, which in turn oxidizes FeS2 to generate additional Fe2+ and acidity in a cyclic process.

Jan 1, 1996

By T. J. White

Each year, thousands of tons of toxic concentrates are produced as the unwanted byproducts of industrial operations and smelting activities. The fate of these materials remains open, as in general their consumption is limited and potential markets contracting. Xtaltite (pronounced crystal-tight) is a Synthetic Mineral Immobilization Technology (SMITE) optimized for the concentration, detoxification and consolidation of toxic metal wastes. In this approach, we seek to mimic nature to produce durable synthetic minerals that survive for aeons in well characterized geological settings. This approach has high public acceptability because the concept is easily understood by the layperson and the long term stability of the waste form may be predicted with confidence. In addition, where Xtaltite is used for mine backfill, a system of ecologically sustainable mining development is established. This paper details the design and fabrication of Xtaltite under oxidizing and reducing conditions. To illustrate and contrast these stabilization regimes, specific reference will be made to the treatment of thallium, chrom~um and arsenic wastes. Waste form performance under TCLP, dynamic boiling water tests and in other leaching media will be compared and discussed with respect to their relevance to different disposal options.

Jan 1, 1995

By Tom Lewis

The metal finishing and electronic industries are searching for ways to recycle materials · and reduce costs. The areas of heavy metal waste and water recycling has gained new interests with the potential of impacting the operation's bottom line. Lewis Environmental Services, Inc. has completed numerous heavy metal recovery and effluent recycling projects with its ENVIRO-CLEAN PROCESS for government and private sector clients. This patented process utilizes a proprietary chemically treated granular activated carbon with enhanced heavy metal adsorption capabilities combined with electrolytic metal recovery to produce a saleable metallic product. The process generates no sludge or hazardous waste and the effluent meets EPA .limits. This paper covers several heavy metal removal projects, two fullcscale commercial installations, and one treatability case study.

Jan 1, 2000

By O. Forsén

A new cell construction was designed for the study of the electrochemical behaviour of additives in conditions that simulate real copper, electrorefining. The behaviour of gelatine and thiourea was studied by applying different electrochemical methods, i.e. polarization resistance and voltametric measurements. In this study, individual galvanostatic electrolysis experiments were carried out for 120 hours. The organic additives were introduced to the electrolyte at certain intervals and their concentration was varied in the range &om zero to four ppm. An optical microscope was applied for the examination of copper cathode deposit microstructures. The results show that gelatine has a polarizing effect on the deposition potential of copper whereas even small amounts of thiourea depolarize the electrodeposition of copper. The maximum inhibitor efficiency of gelatine was obtained at a gelatine concentration of slightly lower than two ppm. When both gelatine and thiourea were present in the electrolyte, the depolarizing effect of thiourea exceeded completely the polarizing effect of gelatine. If chloride ions were added to gelatine and thiourea containing electrolyte, the electrochemical behaviour of the system was altered drastically. Chloride ions resulted in the prevailing of polarization effect caused by gelatine while the depolarizing effect of thiourea disappeared in this system. The polarizing effect of gelatine increased until chloride ion concentration of 30 ppm was reached. Also, the above electrochemical phenomena could be detected in the optical examination of copper deposit microstructure.

Jan 1, 1995

Al2O3,-WC Composite powder for cutting tools was synthesized by self-propagating high-temperature synthesis using A1 powder as a reducing agent. WC, W2C and Al2O3 were concurrently formed in WO3Al-C system. It was found that the complete reaction was achieved with excessive addition of carbon and appropriate processing parameters such as degree of dilution, particle size of aluminum, compaction pressures of green pellets and carbon source. The final product which was leached by 50% HN03+HF diluted solution was consisted of Al2O3-55wt% WC having 2-3um of mean particle size.

Jan 1, 1999

By Mikko Loponen

Outotec has developed an operator training simulator (OTS) platformsuitable for various hydrometallurgical processes. The complete solution is run in the cloud, where virtual client instances can be managed on-demand. The aim is to build a generalizable model that produces coherent results even when operating outside of ideal parameters, allowing the operator to train in unsteady state conditions such as start-up and shutdown. Complex software products are commonly associated with significant development time and cost. Utilizing modular software architecture, only the control system and processmodel are tailored for theOTS,whereas modules such as user administration and cloud-based client machine spawning can be imported, shortening development time. A generic acidic pressure oxidation process (POX) operator training simulation consisting of feed preparation, autoclave, dual-stage flash evaporation and off-gas scrubbing is described. Process is simulated using Outotec HSC Sim 9 process simulator and controlled by Siemens Simatic PCS7 control system.

By B. Erik Ydstie, Dimitrios I. Gerogiorgis, Sridhar S. Seetharaman

"Carbothermic production of aluminium is an important alternative to electrolytic processes and has in fact been identified several decades ago as a potentially feasible and profitable process. The cornerstone principle is to take advantage of the endothermic reduction reaction between carbon and alumina instead of resorting to extreme amounts of electric energy to ionize and reduce aluminium oxide to aluminium. Electric energy is necessary only for heating purposes.The present study focuses on constructing and solving a steady-state electrothermic model for obtaining the spatial distributions for electric potential, electric field intensity and temperature. The complex issues of reaction kinetics and multiphase flow are handled by an approximation and are not addressed at the present stage, due to the lack of complete validated models. Because of its inherent complexity, the reaction slag is considered a pseudohomogeneous layer.An electrothermic simulation encompasses important research challenges, due to the limited knowledge of thermophysical properties for high-temperature multi component molten slags. Therefore, thermophysical property modeling and a systematic compilation of published data is a necessary and major first step towards enhancing understanding of the process fundamentals. Models are obtained by analyzing measurement data from numerous literature references for the density, viscosity, thermal and electrical conductivity and specific heat capacity of the slag.The electric potential, field intensity and temperature distributions obtained reveal interesting maxima which indicate localized superheating and lead to important engineering conclusions. The temperature profile calculated will serve as the foundation for the flow problem solution. This computational study will form a basis for future research towards combining the scopes of microscale CFD modeling and mesoscale process modeling into a unified modeling approach."

Jan 1, 2001

By P. Henry

A novel electrochemical cell has been developed for the recovery of MnO2 from residue of pyrolusite ore leading loaded with Fe, Al Ni, Co and Si impurities, This new process can be considered as an alternative to the traditional methods : S02, H2O2 or bioleaching. It has been observed to proceed fairly rapidly and could prove to be a more economically viable process, as well as being more environmentally acceptable. Electrochemical characterization and kinetic studies have shown that MnO2 is effectively leached by electrogenerated ferrous ions at high current density from a pulp containing less than 5 g8 Fe. The chemical reactions are : Cathode (inox) : 2F23+ + 2e ? 2 Fe2+ Bulk: MnO2 + 2 fe2+ 4H+ ? Mn2+ + 2 Fe3+ + 2 H2O Anode (Pb-Ag) : H2O ? ½ O2 + 2H+ + 2e Global: MnO2 +2H+ Fe2+ = Mn2+ + H2O + 1/2 O2 The catholyte (MnO2 pulp) circulates upward in the expanded mesh cathode separated from the sulfuric acid solution anolyte by a separator which shows high mechanical resistance, low porosity, low potential drop, and reasonable cost. Laboratory and mini-pilot tests have led to the construction of an OT crating pilot plant (100 kg/hr) able to leach more than 95% of Mn, Ni, Co at 1000-1200 A/m2, 50°C with high faradic yield (> 95 %) and low power consumption (3.2 kWh/kg kWh/kg &4D). New applications like the treatment of spent Zn-Mn batteries, polluted soils, spent catalysts and oxide ore (cobalt, nickel) with electrogenerated redox species are now investigated at a laboratory and mini-pilot scale.

Jan 1, 2000

By Y. K. Rao

In the carbonyl process for the refining of crude nickel CO(g) reacts with nickel in the 310-370K range producing nickel tetracarbonyl, Ni(C0)4(g). Iron and cobalt impurities also form gaseous carbonyls but their partial pressures are low. The carbonyl is led to a decomposer plant wherein the gas disproportionates in the 500-600K range depositing pure metal on nickel pellets that move countercurrent to the gas-flow. This system serves to illustrate the fundamental principles involved in the vapor phase mass transport of elements, against temperature-gradient, under the influence of chemical potential gradient. Unlike in the crystal growth, the source is at a lower temperature (say 350K) whereas the seed is in the hot-zone (say 550K) of the closed ampoule-type reactor. By assuming virtual gas-solid equilibria in the end zones, with diffusion of gaseous species between them acting as a slight perturbation, the quasi-steady- state mass-transport rates are computed for a range of CO-pressures and temperatures.

Jan 1, 1993

By Maija-Leena Metsärinta

The behaviour of copper and lead in zinc roasting has been studied in laboratory scale roasting experiments as well as in large scale trials in an industrial fluidized bed, with the background of Outokumpu Kokkola Zinc smelter. Commercial zinc concentrates with a low and high ( up to 3 wt % ) copper content and with a low and high (up to 3.5 wt % ) lead content were oxidized to various desulphurisation degrees in the fluidized bed to establish the reaction mechanisms and the paths for copper and lead oxidation in the roasting. Influences of the agglomerate size on the roasting kinetics and micro-scale phenomena were also determined. Optical microscopy was used on the calcine and the findings are presented as numerous photographs of the polished cross sections. SEMIEDS techniques were used for analyzing chemically the phases and particle morphologies present in the samples. Computational thermodynamics was applied to the complex phase equilibria occurring during roasting in the agglomerating calcine. A complete oxidation of zinc concentrate with a high copper and lead content requires a careful control of oxygen coefficient in the roasting in order to maintain a stable operation of the fluidized bed. Oxygen coefficient thus seems to have a significant impact on the hydrodynamic stability of the fluidized bed with fine raw materials.

Jan 1, 2003

By Maija-Leena Metsiirinta

The behaviour of copper and lead in zinc roasting has been studied in laboratory scale roasting experiments as well as in large scale trials in an industrial fluidized bed, with the background of Outokumpu Kokkola Zinc smelter. Commercial zinc concentrates with a low and high ( up to 3 wt % ) copper content and with a low and high ( up to 3.5 wt % ) lead content were oxidized to various desulphurisation degrees in the fluidized bed to establish the reaction mechanisms and the paths for copper and lead oxidation in the roasting. Influences of the agglomerate size on the roasting kinetics and micro- scale phenomena were also determined. Optical microscopy was used on the calcine and the findings are presented as numerous photographs of the polished cross sections. SEM/EDS techniques were used for analyzing chemically the phases and particle morphologies present in the samples. Computational thermodynamics was applied to the complex phase equilibria occurring during roasting in the agglomerating calcine. A complete oxidation of zinc concentrate with a high copper and lead content requires a careful control of oxygen coefficient in the roasting in order to maintain a stable operation of the fluidized bed. Oxygen coefficient thus seems to have a significant impact on the hydrodynamic stability of the fluidized bed with fine raw materials.

Jan 1, 2003

By Zhang Yongzhu

Developments on bioleaching of low grade ores and refractory gold ores by T. Ferrooxidans in China are summarized. Effect of the ions on bacterial growth, bioelectrochemical reaction mechanism of sulfide minerals and bacterial reaction mechanism are also discussed.

Jan 1, 1992

By E. J. Peuraniemi

Primary copper production using suspension smelting techniques like Outokumpu Flash Smelting always causes some dust formation. Flue dust particles are formed when sulphide feed material reacts violently with oxygen inducing particle disintegration and total desulphurisation of fragments. In the process, flue dust follows the off-gases to the heat recovery boiler (HRB) where its sulphation takes place because of prevailing conditions. Sulphation releases heat and causes also a drop in particle melting temperature and, further, particle sticking to the walls and heat exchange tube banks. Sulphation of synthetic CU20 particles were examined using a laboratory scale fluid-bed reactor. This study aims to a better understanding of flue dust behaviour in a HRB and, thus, to a better operational practise and design of a HRB. The effect of PSO/PO2 -ratio and temperature on the sulphation kinetics were tested. Standard chemical analysis, light optical and scanning electron microscopy with energy dispersive spectroscopy were used to examine the samples.

Jan 1, 2001

By Luiz A. Teixeira

A process is described whereby worn, deffective or crystallized photoconductive Se-As layers can be stripped off from aluminium photocopier drums, using hydrogen peroxide solutions in conditions such that the aluminium substrate is preserved from chemical attack. The process allows the stripped drum to be recoated with a new photoconductive layer, and to be put again in use.

Jan 1, 1990

By R. Steven Izatt

Green chemistry principles will be discussed, and examples will be given of the use of Molecular Recognition Technology (MRT) to selectively separate specialty metals such as cobalt, nickel, bismuth, rhenium, molybdenum, indium and germanium from various primary and secondary feed streams. Recovery of these metals has numerous advantages including (i) conservation of valuable resources, (ii) prevention of environmental damage, and (iii) elimination of capital and operating expenses due to re-processing or disposal of metal-bearing streams.

By William Petruk, J. H. Gilles Laflamme, Jean Robitaille, Louis J. Cabri

"A quantitative mineralogical study using ore microscopy, electron microscopy, proton-microprobe, image analysis, and material balances was done on samples from the circuit of a concentrator in Quebec, with particular emphasis on the Cu concentrate. The ore contains many different minerals, of which the principal ones, in decreasing order of abundance, are pyrite, sphalerite, chalcopyrite, bornite, galena, tennantite, and pyrrhotite. Minor to trace amounts of covellite, chalcocite, stannoidite, mawsonite, colusite, wittichenite, miharaite, hessite, petzite, electrum, and an unidentified Cu-Pb-Bi-sulfide also occur.Liberation of pyrite is very high in all size fractions for all samples (ranging from 80-91 %). Liberation of chalcopyrite, bomite, sphalerite, and tennantite is relatively high, on average, in the head .sample and Cu concentrate (55-78% and 66-88%, respectively). Most of the chalcopyrite in the flotation tails is not liberated, whereas about one half of the tennantite and sphalerite are liberated in both the flotation and :final tails. Recoveries calculated for the Cu concentrate (on the basis of assays, mineralogy, and image analysis) are chalcopyrite 72. 5%, bornite 73. 7%, sphalerite 41.0%, tennantite 70.9 %, and galena (together with some trace minerals) 34.2%. It was also calculated that the Cu concentrate contains 10.0 % of the pyrrhotite and i.4 % of the pyrite.Materials balance calculations were done on the five major sulfide minerals to determine the mineralogical distribution of 13 major, minor, and trace elements (as determined by protonmicroprobe analyses). It was determined that tennantite is the principal carrier of Bi (67%), As (90%), and Te (86%) in the Cu concentrate. Therefore, removal oftennantite, which is mostly liberated in the Cu concentrate would significantly reduce these three contaminant elements, but at a loss of9% of the Cu, 2.0% of the Zn, and 0.7% of the Ag. The precious metals (Au, Ag) occur as discrete minerals (electrum, petzite, hessite). Some of the Ag also occurs in solid solution in bornite (23.1% of Ag in Cu concentrate), tennantite, and sphalerite. Four of the major sulfides (chalcopyrite, bomite, sphalerite, tennantite) in the ore also contain measurable concentrations of the following trace elements: Se, Cd, In, Sn, and Sb, occurring mostly as solid solutions. Some of these elements are also concentrated (up to about 18%) in minor and trace minerals such as colusite, stannoidite, and mawsonite."

Jan 1, 1999