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By A. Schönecker, P. Y. Pichon, B. Kraaijveld, Y. Meteleva-Fischer

"Ribbon-growth-on-substrate is a casting method, which offers a possibility to control heat flow, nucleation and subsequent crystal growth at the liquid-substrate interface. This technology allows for low-cost and high throughput shaping of silicon sheets with controlled crystal grain size and orientation for use in solar cells. In this work, sheets of silicon- metal silicide composite materials were produced and their microstructure was studied. It was shown that depending on the relevant phase diagram and casting conditions, a micro/nano-sized eutectic structure of the casted sheet can be formed. Such composite materials possess properties promising for various applications in energy generation, storage and conservation. The advantages, potential and challenges of the ribbon-growth-on-substrate technique for production of composite sheet materials as well as novel areas of application for such materials are discussed.IntroductionThe Ribbon Growth on Substrates (RGS) process is well known in the solar industry as a process to produce multicrystalline silicon wafers. An industrial size pilot production line for continuous casting of silicon wafer was developed by RGS Development B.V. in the Netherlands (Figure 1). A comprehensive review of this technology and properties of the produced silicon wafers were reported by Schönecker et al [1]. The principle of the RGS process is explained in Figure 2. The relatively cold substrate extracts the crystallization heat from the liquid silicon in the casting frame. This results in the growth of a silicon ribbon (Vc) in contact with the substrate. When the substrate (Vp) is transported from the casting zone into the cooling section, the crystal growth stops, the wafer can be removed and the substrate can be re-used. Last few years large work was done on the industrialization and market development of RGS wafers for the solar industry. Part of this work was discussed by Schönecker et al [2]. Although there is still a good perspective on the middle and long term solar market for the RGS wafers, the current market situation was found to be unfavorable for new entrants."

Jan 1, 2014

By Nural Kuyucak

Acid mine drainage (AMD) occurs at operating and abandoned mine sites as a result of oxidation of sulphide minerals, and is characterized by low pH and heavy metal contamination (e.g. Fe, Zn, Cu, Cd, Al, Mn). It usually requires treatment before release in order to meet regulatory requirements. Chemical methods, such as lime neutralization and sulphide precipitation, are commonly used to treat AMD. However, the conventional processes require high capital and operating costs, and constant attention for many years into the future. In addition, the amount of sludge produced by conventional lime treatment processes poses an increasingly significant disposal problems at decommissioned mining operations. There is, therefore, an urgent need to develop passive, cost-effective processes for mitigating AMD and seepages originating from tailings and waste rock areas. Noranda Technology Centre (NTC) has been evaluating various methods being developed by other institutions, and exploring new ideas, to achieve passive in situ processes for treating AMD. These methods include anoxic limestone (ALS), lime-organic mixture (LOM), biosorbents (BIOS) and biotrench (BT). Current investigations at NTC involve preliminary bench-scale testing. Based on the outcome of the bench tests, a field test will be performed at a selected site. Details of the bench tests are discussed in the paper. Key Words: Acid mine drainage, treatment, metals removal, passive treatment, anoxic lime, limestone, biological treatment, sulphate reducing bacteria, biosorption, biosorbent

Jan 1, 1993

By Denise C. R. Espinosa

Rechargeable lithium batteries are one of the most promISIng technology in battery development. Although Li ion batteries have been used as an alternative to the more polluting and less performing Ni-Cd batteries, Li ion batteries have limited life and their disposal is uncertain. It is imperative that valuables from wastes, such as lithium, should be recovered. The main objective of the present work was to characterize secondary lithium batteries for cellular phones. This was done using unit operations of mining processing, x-ray diffraction (XRD), chemical analyses and the rmogravimetric analysis (TG). The unit operations were hammer mill grinding, knife mill grinding, size separation and magnetic separation. After the hammer grinding process, the plastic cases were almost intact, however, they have released the cylindrical lithium batteries themselves and these parts correspond to 70% of the total battery weight.

Jan 1, 2001

By Gaballah Djona M.

Spent hydrorefining catalysts contain about 5 % of CoO and/or NiO, 12 % of MoO3 and up to 10 % of V205. They are generally supported by alumina and contain up to 25 percent of C, S and hydrocarbons. Such materials are potentially hazardous to the soil and to water resources. Selective chlorination of raw unroasted samples with Cl2 + air gas mixture had been investigated. At temperatures lower than 600 °C, it was possible to recover more than 90 % of nickel and cobalt chlorides, about 99 % of the molybdenum and up to 75 % of vanadium chlorinated compounds. CoCl2 and Ni/Cl2 were extracted from the chlorination residues by their dissolution with acidified water. Molybdenum and vanadium chlorinated compounds were recovered by selective condensation from the vapor phase. The chlorination of Al2O3 could be limited to less than 6 %. The scale up of this treatment was successful and a flow-sheet is proposed.

Jan 1, 1995

By Shenghui Guo, Jianbo Lan, Hongying Xia, Jinhui Peng, Lihua Zhang, Libo Zhang

Spent Hawaii nut shell was converted into a high-quality activated carbon via steam physical activation. Analysis of the experiment including activation temperature, activation duration, steam flow rate on the adsorption capability and yield of activated carbon were identified. Response surface methodology showed that the activation temperature was identified as 866 , an activation duration of 36 min and a steam flow rate of 2.5mL/min with the methylene blue adsorption number of 195 mg/g and yield of 77.75%. The key parameters that characterize quality of the activated carbon such as the BET surface area, total pore volume and average pore diameter were estimated to be 1125m2 /g, 0.94mL/g and 5.21 nm, respectively. Additionally, by the SEM analyses of char and activated carbon, the surface of activated carbon has large number of pores of irregular and heterogeneous morphology.

Jan 1, 2016

By Joseph Hamuyuni, Pekka Taskinen

We present experimental results for the liquidus in the system Cu2O - CaO -Al2O3 at 1250 oC. In this study, we quantified the liquidus by the equilibration/quench/analysis technique, with Cu2O, Al2O3, and CaO as primary materials exclusively. Experiments were conducted in air at an at oxygen pressure (p) = 21.3 kPa). Equilibrated specimens were quenched in brine solution of 10 wt% NaCl. We then quantified the liquid chemical compositions by means of Energy-Dispersive X-Ray Spectroscopy (EDS) and Electron probe micro-analyzer (EPMA). This study reveals inconsistences in liquidus surface of the present ternary diagram of the system here in mentioned. Differences of up to 10 wt % compositions of the species have been observed.

Jan 1, 2015

By R. Boom, Y. V. Meteleva-Fischer, B. Kraaijveld, H. Kuntzel

"Segregation of impurities during refining of metallurgical grade silicon (MG-Si) is an option to produce solar grade silicon (SG-Si). Directional solidification is a last step in production of SG-Si effective for removal of metallic impurities. The possibility is investigated to use metallic impurities originally present in MG-Si for removing boron and phosphorus. MG-Si has been treated using two methods: 1) alloying with calcium and 2) refining with Na2O-CaO-SiO2 slag, both by controlled cooling. The microstructure of silicon and the impurities distribution have been studied before and after the treatments. Using EPMA phosphorus and boron have been detected in 1-2 wt% concentration range in several intermetallic compounds in grain boundaries after both treatments. This observation points to a different possible mechanism of silicon refining from boron and phosphorus. Controlled cooling improves migration of phosphorus and boron to the silicide phases in grain boundaries, which can be removed by acid leaching treatment.2. IntroductionStandards for silicon solar cells and growing demand on “green” energy require economical and efficient route to the production of solar grade silicon. Refining of cheap metallurgical grade silicon is one of the promising options, where application of existing metallurgical approaches can result in cost-efficient production on industrial scale. Focus in refining is on impurities, which are most difficult to remove: B, P, Al, Ti, due to their large segregation coefficient in silicon and low vapour pressure [1]. Moreover, more environmentally friendly technology in comparison to the traditional Siemens process [2] will be in accordance with societal needs. Based on properties of common impurities in metallurgical grade silicon, alloying refining and slag refining are suggested as competitive techniques having potential effect on removal of impurities harmful for conversion of solar energy [3, 4]. Alloying with Ca followed by acid leaching was found to be effective for removal of Fe and Ti from silicon [5] and to enhance also removal of boron [6] and phosphorus [7, 8]. In the work of Inoue et al. [8] drastically increasing removal of phosphorus from silicon has been observed with an increase of Ca content and a thermodynamics-based explanation was provided. Since phosphorus has been found to condense in the secondary precipitate mainly composed of CaSi2, it can be removed together with iron and titanium by consecutive acid leaching treatment. Slag refining is one of the metallurgical methods proposed to be effective for refining of metallurgical grade silicon from boron [9, 10]. Slags with additions of the following oxides to silica have shown positive effect on removal of boron: CaO [11-13], Na2O [11,14]. Mechanism of slag refining from boron is based on oxidation of boron followed by its incorporation in the slag network [9,11]; the same mechanism is suggested for refining from phosphorus taking into account that oxides of boron and phosphorus are known as network-formers [15]."

Jan 1, 2012

By Derk G. E. Kerfoot

The extractive metallurgy of nickel and cobalt has proved to be a particularly fruitful area for innovation in hydrometallurgy and electrometallurgy ever since the development of the Hybinette process for nickel in the early 1900's. In current practice, nickel concentrates are generally smelted to high grade mattes which are then refined to metal by a combination of hydrometallurgy and electrometallurgy, although low grade copper-nickel concentrates are refined directly by the ammonia pressure leach process. Matte refining processes in commercial operation include the direct electrolysis of matte, the ammonia pressure leach, sulphuric acid leaching using air or oxygen at elevated pressure, or at ambient pressure, and chlorine or chloride leaching. Refined nickel is recovered either as electrolytic cathode, or as metal powder by hydrogen, reduction. Hydrometallurgy has also found application in the treatment of nickel laterite ores, both in the reduction roast ammonia-ammonium carbonate leach process, pioneered by Caron and in the Moa Bay acid leach process. Cobalt is recovered as a co-product of copper in central Africa, and as a byproduct of hydrometallurgical nickel refining elsewhere. In the African plants, the copper-cobalt concentrates are roasted and leached in sulphuric acid solution, and copper and cobalt are recovered separately from the leach solution by direct electrowinning. A variety of hydrometallurgical techniques are used for the separation of cobalt from nickel, including selective precipitation and crystallization, solvent extraction, and ion exchange. Like nickel, refined cobalt is recovered either as electrolytic cathode or as metal powder by hydrogen reduction.

Jan 1, 1988

Equilibrium calculational software programs can be effectively utilized to illustrate the importance of activity or concentration, solubility, temperature, solution pH, solution potential, and ligand complexation to students studying hydrometallurgy. The calculational program STABCAL will be demonstrated. illustrative examples for the creation of diagrams such as EH-pH, activity or concentration-pH and activity or concentration-EH will be presented to demonstrate the fundamentals of real hydrometallurgical systems. Speciation, titration and mixing will be used to simulate or predict operational processes. Applications will include treatment of Acid Mine Drainage (Berkeley Pitlake water and sediments), mass balance potential/pH diagrams, leaching and selective separation of metals from electroplating sludge, metal adsorption at femhydrite surfaces, and flowsheet development for treating mercury sulfide K106 sludge.

Jan 1, 2002

By M. I. Kalashnikova

Results of investigations concerning precipitation of heavy non-ferrous metals from solutions using precipitators based on elemental sulphur and lime with gypsum transfer to a separate product are given.

Jan 1, 2003

By P. Lussiez

Precipitates consisting of amorphous ferrihydrite and crystalline goethite have been prepared by aging hydrolyzed Fe (III) solutions at room temperature. The precipitates have been characterized by x-ray diffraction and differential thermal analysis. The amorphous ferrihydrite transforms to goethite with time. The ferrihydrite to goethite transformation is affected by the presence of small amounts of copper or nickel coprecipitated with the iron. .The addition of copper decreases the amount of goethite at a given aging time and increases the amount of coprecipitate which is initially dissolved in sulfuric acid, but it does not seem to affect the dissolution of the crystalline part'. It is proposed that adsorption of copper hydroxo species on goethite nuclei delays the ferrihydrite to goethite transformation. The effect of nickel is less dramatic than that of copper. Apparently a portion of the added nickel is adsorbed on the goethite crystallite surface rather than incorporated into the goethite lattice.

Jan 1, 1981

By Pesic. Batric

A novel chitosan-pyridoxal-epichlorohydrin was synthesized and evaluated in our laboratories. The evaluation was achieved by performing kinetic and equilibrium studies of copper sorption. The parameters examined were pH, temperature, concentration of copper, particle size and selectivity of copper sorption against iron, zinc, cadmium and cobalt. It was found that pH was the most important parameter, and sorption of copper increased with pH increase in the range pH 2.5-6.0. The low activation energy of the sorption reaction, 1 1.13 kJ/mole (2.66 Kcal/mole), showed that temperature was not an important parameter. The synthesized chitosan was selective against iron, zinc, cadmium and cobalt. The selectivity with respect to last three metals was achieved by the kinetic difference of sorption, as sorption of copper was much faster than for other metals. Iron (Fe2+) does not adsorb on chitosan. The mechanism governing the sorption of copper is intraparticle diffusion. This finding was supported by the dependance of copper sorption on the square root of time, the low activation energy, and the fit of experimental data in the diffusion through the product layer equation.

Jan 1, 1994

By Hiroyuki Sano, Chikabumi Yamauchi, Mitsuru Tanahashi, Toshiharu Fujisawa, Shin-ya Iwahori

"Pyrometallurgical process using Cu2O-based slag was proposed as a recycling process for copper scrap. However, it is difficult to remove nickel from copper by oxidative refining. Therefore, it is necessary to reduce the concentration of nickel in copper before the oxidative refining. In the present work, the copper enrichment stage in this recycling process, where copper scrap melt is separated into the Fe-C-Cu melt and the molten copper, was taken up and the compositions of both melts were measured. Based on the above results, the distribution ratios of nickel between the Fe-C-Cu melt and the molten copper were calculated. Furthermore, the optimum condition of copper enrichment stage was discussed from the viewpoint of nickel removal and copper recovery. The possibility of recovering 4N-purity copper by using this recycling process was confirmed.IntroductionRecycling is well known as a method for saving resources and reducing environmental damage. More than 99% of copper is used in metallic form - as metal or copper alloys[l]. High-grade copper scrap is directly re-melted and reused, while low-grade copper scrap is transported to copper smelters to be pyrorefined and electrorefined. Nevertheless, a great amount of copper is being stockpiled in the cities and should be recycled in the near future. At that time, the current recycling process will face new problems due to the increases in the recycling rate to the smelters. This includes insufficient combustion heat to melt copper scrap and ·almost no benefit in electrorefining because the scrap does not contain gold and silver. Thus, an alternative pyrometallurgical method for copper scrap refining will be required."

Jan 1, 2000

By T. H. Jeffers

The U.S. Bureau of Mines' Salt Lake City Research Center. has developed porous polymeric beads containing immobilized non-living biological materials for extracting metal contaminants? from wastewater&. Immobilized biological materials include peat moss, algae, biological polymers, and other materials that demonstrate high .affinities for heavy metals. The beads, designated as BIO-FIX beads, have distinct advantages over traditional methods of utilizing biological materials in that they have excellent handling characteristics . and can be used in conventional processing equipment or low-maintenance systems.. Toxic metals such as copper, cadmium, zinc, lead, and mercury are several of the many heavy metals effectively removed from mine wastewater& using B'IO"FIX beads. Continuous cyclic testing indicated that the beads continued to produce treated effluents which met National Drinking Water Standards (NDIJS) after 175 loading-elution cycles, Adsorbed metals were removed from the beads using dilute ?mineral .acids. In many cases" the extracted metals were further concentrated to enable processors to reclaim the metals, thus minimizing the generation of a hazardous sludge. Tests indicated that use of the beads in a low-maintenance system was particularly effective for treating remote acid mine drainage waters? and small toxic seeps from hardrock mining districts ..

Jan 1, 1991

By K. L. Money, R. R. Bleakney, R. H. Hanewald

The processing of EAF baghouse dusts, rolling mill scales, and belt grinding swarfs from the specialty steel industry will be reviewed. In addition, the INMETCO process has been modified so as to recover nickel, chromium and iron from many other waste materials such as pickling solutions, filter cakes, spent nickel and chromium plating baths, super alloy wastes, and nickel-cadmium batteries. INMETCO is the only North American company presently capable of recycling nickel-cadmium batteries by high temperature metals recovery.

Jan 1, 2000

By Chang-Young Choi

Korea Zinc commenced zinc production in 1978 with a capacity of 50,000 tpa. Since then, continuous investments have been made and resulted in Korea Zinc now being the biggest zinc and lead producer in the world. In the course of increasing zinc production capacity, the company management realized that the company needed a lead smelter to prevent the solid waste disposal problems by treating the lead containing solid waste. This paper begins by briefly stating the objectives and the roles of the lead smelter at Onsan. It describes the QSL process and the TSL process, and further extends the description of the TSL process, through which harmless inert solid waste could be produced for secure final disposal. It is also mentioned that the TSL process plays an important role in the integration of zinc and lead production. Throughout the paper, a positive attitude in handling the environmental issues in the non-ferrous smelting industry is emphasized. Finally, a solution for the solid waste disposal problem in the zinc and lead industry is proposed, with which the environmental issues can be an opportunity rather than a crisis. The current operation at Ousan suggests the future direction of the non-ferrous smelting technology that all of the zinc and lead producers should pursue.

Jan 1, 2003

By Dong Joon Min, Joo Hyun Park, Mi Sun Choi, Jae Hong Shin

Sublimation of ZrCl4 is important for the production of nuclear grade metallic Zr in Kroll’s process. The sublimation kinetics of ZrCl4 was investigated by TGA under both isothermal and non-isothermal conditions. The sublimation rate of ZrCl4 increased with increasing temperature under isothermal conditions. ZrCl4 sublimation was confirmed to be a zero-order process under isothermal conditions, whereas it was first-order kinetics under non-isothermal conditions. The activation energy of ZrCl4 sublimation under isothermal conditions was 21.7 kJ/mol. The activation energy for non-isothermal sublimation was 101.4 kJ/mol and 108.1 kJ/mol with the Kissinger method and Flynn- Wall-Ozawa method, respectively. These non-isothermal activation energies were very close to the heat of sublimation (103.3 kJ/mol). Sublimation occurs by two elementary steps: surface reaction and desorption. Therefore, the overall activation energy of ZrCl4 sublimation is 104.8(±3.4) kJ/mol. The activation energy of the surface reaction and desorption steps are proposed to be 83.1 kJ/mol and 21.7 kJ/mol, respectively.

Jan 1, 2014

By Ann M. Hagni

The mineralogical, chemical, microtextural, and particle size character of electric arc furnace (EAF) dusts are being studied by reflected light microscopy, scanning electron microscope-energy dispersive spectroscopic analysis (SEM-EDS) and electron probe microanalysis (EPMA). The dusts consist predominantly of metallic iron, iron oxide, and calcium-iron-manganese silicate phases, together with smaller amounts of iron-manganese-zinc-calcium, iron-calcium-zinc-manganese, and calcium-iron-manganese silicates. The samples vary in their zinc contents. Chlorine occurs in phases containing iron, lead, zinc, manganese, and calcium. The dust particles range greatly in size from 1 to more than 300 ~m, but most particles are about 1 to 6 ~m. Larger particles. about 20-50 um across. also are present. They are predominantly spherical in shape, but some are cenospheres, and others are more angular particles, some of which are broken spheres and cenospheres. Their internal microtextures exhibit evidence of liquid immiscibility, exsolution, skeletal crystal growth, and oxidation react i on rims. Because EAF dusts have been classified by EPA as hazardous wastes, there is heightened interest in the treatment of these dusts to render them non-hazardous. The mineralogy of products of pyrometallurgical treatment of EAF dusts by flash furnace and pyrohydrolysis are currently under study.

Jan 1, 1991

By Kimio Itagaki

"As a contribution to understand the smelting of copper or nickel matte by blowing oxygen or oxygen-enriched air, the phase equilibrium and the distribution of minor elements between the iron-silicate based slag and the Cu2S-FeS or Ni3S2-FeS matte at 1573K were investigated in a magnesia crucible under controlled partial pressures of SO2 at 0.1, 0.5 and 1.atm. At a given matte grade, the solubility of copper in the slag was found to be independent of p5O2 while that of nickel was dependent on pSO2 and these behaviors were analysed thermodynainically based on a concept of oxidic and sulfidic dissolution of the components in the slag. When the matte grade was specified, the distribution ratios of X, defined as (wt pct X in slag)/(wt pct X in matte}, for As, Sb and Bi increased with increasing p5O2 while that for Ag was constant against p5O2.IntroductionA combination of intensive reactors with the use of oxygen or oxygen-.enriched air as the blowing gas has provided a number of improved copper and nickel smelting processes such as INCO-Flash, Outokumpu-Flash, Mitsubishi-Continuous and IBRC (top blown rotary converter) processes. Phase equilibrium and thermodynamic studies for the slag and the copper matte or the nickel matte under high partial pressure of SO2 are of practical importance for evaluating the behaviours of the related components in the oxygen-smelting.A series of experimental studies have been already conducted in a limited range of conditions for Pso2 around 0.1 atm, which corresponds to the smelting with air-Stowing [1-5]. However, there remain very few data on the phase equilibrium in the matteslag systems under higher partial pressures of SO2. Tavera and Davenport studied the phase equilibrium between the copper matte and fayalite slag phases under the partial pressure of SO2 controlled at 0.1 - 1 atrn but without controlling the partial pressures of sulfur and oxygen [6]. A potential diagram for the Cu-Fe-S-O-SiO2 system at 1523 - 1573K suggests that the partial pressure of S2 equilibrated with the matte and the fayalite slag with saturated SiO2 under the high SO2 pressure is considerably high at 10-4 - 10-2 atrn [7]. This condition must require controlling of p52 as well as Pso2, in the equilibrium experiments, otherwise, the equilibrium condition may be hardly attained due to the continuous flushing of sulfur from the system."

Jan 1, 2000

By D. L. Yopps

Platinum-group metal (PGM) flotation .. concentrate from the Stillwater Complex, MT, was subjected to biooxidation using Thiobacillus ferrooxidans in an effort to break down the sulfide minerals and liberate the ? associated PGM's for subsequent chemical leaching. Bacterial treatment oxidized up to 94 pct of the sulfide present, destroyed the PGM-bearing pentlandite [ (Ni,Fe),9Ss) mineralization, and dissolved most of the nickel in the concentrate. Results showed that increased sulfide oxidation during the biological stage led to improved PGH recovery in the subsequent. chemical leaching stage. cyanidation at 80° c proved to be the best chemical leachant tested. It removed 7.6 pct of the palladium, 94 pct of the rhodium, 97 pct of the gold, but only 34 pct of the platinum from the biooxidized concentrate.

Jan 1, 1991