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By W. K. Collins

Engineered Scavenger Compounds (ESCs), developed by the U.S. Bureau of Mines, are a novel class of compounds that can selectively recover a desired element from a solid or molten alloy. Lithium titanate (Li2Ti3O7 or L'20-3T'02) is being used as an ESC to recover lithium (Li) from Aluminum-Lithium (Al-Li) alloys. X-ray diffraction measurements have shown that lithium titanate undergoes a phase change from an orthorhombic structure to a hexagonal structure. This change is due to the incorporation of Li in the matrix of the material and the effect of temperature. Although both are metastable, the hexagonal phase that forms during the scavenging of Li from Al-Li alloys appears to be the more stable phase. Recovering Li from the ESC by electrodeposition does not cause the structure to revert to the orthorhombic phase. Both the orthorhombic and the hexagonal structures of Li2Ti3O7 have similar scavenging capacities for Li. This paper proposes a new mechanism for the phase transformation.

Jan 1, 1993

By den Bulck A. Van

In Europe, 50% of the copper originates from recycling. High-Cu containing scraps are regularly rich in impurities like Fe, Ni, Sn and Pb. Many high-Cu containing scraps are fed directly into anode-furnace casting installations or furnaces with limited refining capability. The impurities levels of the anodes produced in these processes should however remain acceptable for further electro-refining. The distribution of Sn between copper and slag has been investigated for conditions relevant to copper converting. Unlike previous studies, this work focuses on the behavior of Sn relevant to fire refining conditions, which are essential for anode refineries.In this study, liquid Cu–1Sn and CuOx–FeOy–SiO2 slag, with CaO additions, were equilibrated at 1300 °C in vacuum sealed SiO2 ampoules. After metal–slag equilibration, the samples were quenched in water. The composition of the slag and Cu metal was investigated with Electron Probe X-ray Microanalysis. The distribution coefficients of Sn between slag and Cu metal were determined as a function of slag composition.

By W. D. Riley

Engineered Scavenger Compounds (ESCs), developed by the U. S. Bureau of Mines I are a novel class of compounds that can selectively recover a desired element from 'a solid or molten alloy. Lithium titanate (Li2Tip7 or Li20' 3TiO.) is being used as an ESC to recover lithium (Li) from Aluminum-Lithium (AI-Li) alloys. X-ray diffraction measurements have shown that lithium titanate undergoes a phase change from an orthorhombic structure to a hexagonal structure. This change is due to the incorporation of Li in the matrix of the material and the effect of temperature. Although both of the structures are metastable, the hexagonal phase that forms during the scavenging of Li from AI-Li alloys appears to be the more stable phase. Recovering Li from the ESC by electtodeposition does not cause the structure to revert to the orthorhombic phase. Both the orthorhombic and the hexagonal structures of Li.Til07 have similar scavenging capacities for Li. This paper proposes a new mechanism for the phase transformation.

Jan 1, 1991

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 Konstantina Chalastara

Mixed phase titanium dioxide (TiO2) nanoparticles synthesized through hydrolysis of TiCl4 solution at different conditions, namely concentration, pH, and residence time are characterized and evaluated as photocatalysts. The process is operated in a continuous stirred-tank reactor, CSTR giving blends of anatase, brookite, and rutile nanoparticles that were further evaluated to find the optimum mixture for a photocatalytic sorption material. The titania nanoparticles are first characterized in terms of photocatalytic activity under UV light illumination using an organic model compound (methyl orange) and after that are tested for removal of toxic selenate and selenite species from simulated effluent waters.

By Marco Antônio Siqueira Rodrigues

The possibilities for treating rinse waters fiom chromating bath by electrodialysis are discussed together with the possibilities of optimizing the treatment process for waste reduction and reuse of water and chemical products. An industrial effluent with 4600 ppm of Cr(VI), besides other metallic contamination, was used as work solution. This solution has been recirculated on an electrodialysis cell of three compartments, using exchange membranes Selemiom AMT and CMT. A migration of dichromate ions into the anodic compartment was obtained, so that an extraction of circa 99.9 % of Cr(VI) present on the solution was observed, resulting in water with a Cr(V[) concentration of 4 rnd. These results show that electrodialysis can be used to treat these effluents, and this water could be reused as rinse water. The solution of the anodic compartment, consisting at the beginning of the experiment of H2S04, 0.1 N, reached 7200 mg/l of Cr(VI). This concentrate could be reused on the chromating bath itself.

Jan 1, 1999

By Geoffrey A. Brooks, M Akbar Rhamdhani, Md Saiful Islam

A novel electrically-enhanced metal purification using slag has been developed. This was achieved by applying DC potential between liquid metal and slag phases. The concept was demonstrated through small-scale experiments at temperatures of 1500-1600oC for the removal of boron from Si-B melt using CaO-SiO2-16wt%Al2O3. Silicon (containing B) and slag were reacted in an alumina crucible in a resistance tube furnace. A circuit was produced by immersing graphite rods into the silicon bath and the slag layer. Electrical potential differences of up to 3.5 V were applied during the reactions. The reaction rates, the opencircuit voltages and short-circuit currents (in the case when the potential was applied) were then measured and determined for various slag to silicon ratio. It has been shown from this study that both the apparent rate and the boron partition ratio were increased by a factor of approximately 1.6.

Jan 1, 2014

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 Metehan Erdogan, Ishak Karakaya, Fuat Erden, Emre Ergül

"The FFC Cambridge process was suggested as a promising Si production technique for the expanding solar energy industry. Direct electrochemical reduction of bulk SiO2 plates and porous SiO2 pellets in molten CaCl2-NaCl salt mixture were investigated at 750°C by applying 2.8 V potential difference. The produced Si powder was brown and found to be contaminated by the Ni and stainless steel plates used as the cathode contacting materials. The reduction rates of the bulk SiO2 plates and porous SiO2 pellets were compared from variations of current and accumulative electrical charge that passed through the cell during the electrochemical reduction. The amorphous bulk SiO2 plates were reduced slightly faster than porous pellets of crystalline SiO2. The overall reduction potential of SiO2 pellets against the graphite anode at 750°C in molten CaCl2-NaCl salt mixture was determined as 2.3 V by cyclic voltammetry. This potential was supported by calculations.IntroductionMetallurgical grade Si cannot be directly used in electronic industry and some intermediate steps are required to produce industrial solar grade silicon (SOG-Si). A promising alternative solar grade silicon production technique is the FFC Cambridge Process [1]. Production of Si by electrochemical reduction of SiO2 at 850oC in molten CaCl2 electrolyte was first studied by Nohira et.al. [2]. In their study; Si formation was observed on bulk SiO2 cathodes after 1 hour of electrolysis. Complete electrochemical reduction of porous SiO2 pellets was first reported by Jin and his coworkers [3]. The mechanism of electrochemical reduction of SiO2 to Si in molten CaCl2 was explained in another study [4]. Reduction rates of bulk SiO2 and porous SiO2 pellets were also compared previously and it was found that reduction rates for bulk plates were higher [5]. Furthermore, it was reported that mixing Si into porous SiO2 pellet increased the reduction rate [5]. Mo [2, 4-7], Ni [3, 8, 9] or Si [6] were used as cathode contacting materials in various studies. Yasuda et. al. [6] produced Si with 99.80 % purity using Si plates as cathode contacting material to reduce metal contamination."

Jan 1, 2012

By Merete Tangstad, Lars Klemet Jakobsson

"Slag refining is a promising refining method for boron removal from silicon as a part of a metallurgical route for production of silicon for solar cells. There is, however, limited data on the distribution of impurity elements between silicon and different types of slags. In the present study, the distribution of boron and calcium between silicon and slag were determined at 1600 °C for calcium silicate slags with a CaO/SiC>2 ratio between 0.65 and 1.3. An almost horizontal linear trend was found for the distribution of boron between silicon and slag, and the borate capacity was found to follow the relationln(CB0, ) = 30.8 + 2.96-V (1)where V\s the CaO/SiCh mass ratio within the range of the experiments.IntroductionSolar grade silicon feedstock contributes significantly to the total cost and energy required to make crystalline silicon solar cells. A less expensive and less energy requiring method of solar grade silicon production is therefore needed in order to make crystalline silicon solar cells more viable as an energy source. Silicon is an abundant element and the manufacturing cost of solar grade silicon is therefore mainly determined by costs related to purification of metallurgical grade silicon. The Siemens process is the most common process today, but it is an expensive and highly energy requiring process that gives silicon with a higher purity than is needed for crystalline silicon solar cells. A cheaper and less energy requiring method for production of solar grade silicon can either be achieved by modifying the Siemens process or by using a new production method. Purification of metallurgical grade silicon through a metallurgical route is a promising method that is already in use industrially. It has however proven to be hard to lower the boron content to 0.3 mg/kg or less, which is the requirement for most p-type crystalline silicon solar cell manufacturers. Slag refining is seen as one of the most promising approaches that can be used to bring down the boron content to the required level, but there is not much data on how boron is distributed between silicon and binary calcium silicate slags [1-4]. The distribution of boron between silicon and calcium silicate slags at 1600 °C has been studied in this work, and the obtained data has been used to calculate the borate capacity of binary calcium silicate slags."

Jan 1, 2012

By Antonio Luraschi

The constituents iron, oxygen, silica and cop- per are of principal interest in slags utilized in pyrornetallurgical processes for producing copper. Accordingly, phase relationships in the.Cu-Fe-0-SiO2 system are important when one considers the physico- chemical behavior of slags. These phase relation- ships for the quaternary and constituent ternary systems are developed from available information. Isothermal composition and composition-oxygen potential diagrams, and oxygen potential-temperature diagrams are utilized to describe the' important relationships.

Jan 1, 1976

By S. Mondon

Hibi Smelter which is a Copper Smelter lining a blast furnace, produces 2,700 metric tons of anode copper per month. Generally, in a copper refinery, arsenic and antimony are considerably troublesome impurities. With regard to the elimination of antimony, Hibi Smelter has two handicaps described as follows. (1) Smelting under the slightly oxidizing atmosphere in the blast furnace. (2) Recycling the converter slag to the blast furnace after cooling. Therefore antimony and arsenic, mainly antimony, elimination tests, in which the alkaline flux was injected through the two tuyeres in the blowing stage, were carried out in the rotary anode furnace. Antimony and arsenic were respectively removed more than 90 96 from the molten copper, and their high eliminations are discussed by application of the transitory and permanent reaction model with the flux injection, which was presented by T. Lehner.

Jan 1, 1983

By Dalene Joalet Steenkamp

Excavation of industrial-scale furnaces allows for the systematic study of reaction sequences by identifying the different reaction zones within the furnace. In 2013, Transalloys excavated a 48 MVA submerged arc furnace that was used for silicomanganese production using the ore-based route. The excavation method was reported elsewhere as was observations made in terms of refractory wear and modes of electrical energy dissipation prior to excavation. The paper presented here, reports on the process reaction zones observed during the excavation and subsequent phase chemical analyses of a number of process samples obtained during the excavation. The zones identified were a loose burden zone, a dry coke-bed zone, a wet coke-bed zone, a hard build-up zone, and an alloy zone. The results are compared to observations made in the excavation of an industrial-scale SAF and a pilot-scale SAF in Norway. The presence of the hard build-up zone below one of the electrodes and absence of a slag zone below all three electrodes are unique features of the SAF excavated at Transalloys.

By Ralph H. Nafziger

The feasibility of smelting a Ni-Co-Cr-bearing laterite ore from southern Oregon was evaluated by the Bureau of Mines. The objective was to prepare a master alloy for subsequent stainless steel production. A mixture of the ore with suitable reductants and fluxes was smelted in a 50-lb-capacity single-phase ac electric furnace under sub- merged arc conditions. The smelting tests produced a metal in which most of the nickel was concentrated. High-chromium recoveries required an excess of carbon. The resulting metal alloys contain sufficient nickel for some stainless steels. Ferrochromium additions would be required to attain suitable chromium levels. This research was conducted under the Oregon Metals Initiative in cooperation with Walter B. Freeman.

Jan 1, 1993

By M. D. Stephens

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

Jan 1, 2001

By J. G. Zafiratos

The leaching of a Greek low-grade manganese dioxide ore, not amenable to conventional mineral processing operations, was studied using a mixed culture of Thiobacillus sp. bacteria. The experiments were carried out in specially designed continuously aerated and stirred tank reactors arranged in two-tank series. The first tank of each series was loaded with an elemental sulfur culture suspension while the second was loaded with a manganese ore high density slurry. The bacterial culture had been previously adapted to grow on elemental sulfur and also in the presence of manganese ore and dissolved manganous ion. A two level full factorial design was constructed in order to study the effects of the ferric ion concentration in the leach solution, the "elemental sulfu weight to ore weight" ratio, the ore pulp density and the composition of the dispersed gas. The responses which were investigated included percentage manganese recovery, co-dissolution of iron and manganese dissolution rate. Parameters with constant values throughout the experiments were the leach solution pH, the nutrient medium composition, the dilution rate and the ore and sulfur grain sizes. It was found that the ferric ion concentration was the most significant factor and had a positive effect on the final percentage extraction of manganese from the ore and also on the rate of manganese solubilization from the ore. The effects of the other factors studied are discussed in detail.

Jan 1, 1997

By M. K. Mohan

During the processing of metals like Cu, Ni, Co, large quantities of solutions, which contain co- products such as Sb, Cd, Pb etc. are generated. These solutions if processed to recover the metals help in conservation of metals as well as environment preservation. The present study was taken up to recover antimony from process solutions using zeolites. The effect of pH of the solution, time and type of zeolite viz., chabazite, mordenite, erionite and clinoptilolite on the sorption of antimony was investigated. Rate of sorption increases with pH and about 77-pct. antimony sorption was observed with chabazite at a pH of 6. Optimal conditions were established for the maximum recovery of antimony fiom process solutions. The mechanism of sorption for Sb was proposed in terms of adsorption and intraparticle diffusion. The calculated adsorption constants from Langmuir and Freundlich equations indicated that the adsorption of antimony on chabazite was strong.

Jan 1, 1999

By Mike Trovant, Stavros A. Argyropoulos

"A fixed grid numerical model for phase change problems is proposed. The model solves for heat transfer and fluid flow, via the coupled solution of the energy, continuity and momentum equations. In addition, the numerical scheme accounts for temperature varying thermophysical properties and determines the shrinkage profile resulting from phase and density change. Simulations are run to determine the effect of varying model parameters and wall cooling rates on the location and shape of the shrinkage void formation in cylindrical casts. Results are shown for both aluminum and magnesium.IntroductionThe mathematical modeling of phase change processes (be they solidification or melting problems) entails solving for many interrelated phenomena. A comprehensive numerical simulation of the casting of a metal, for example, would have to account for: (a) heat transfer in both the solid and liquid portions of the metal and in the mold, (b) the release of latent heat during phase change, (c) fluid flow behavior in the liquid portion of the metal, (d) temperature induced shrinkage caused by liquid contraction and solidification contraction, and (e) the development of thermal stresses with accompanying shrinkage in the solid portion of the cast and mold. A schematic of the relationships that exist between the coupled equations which govern solidification is shown in Figure 1."

Jan 1, 1994

The oxidation of zinc vapour plays a very important part in the operation of the Imperial Smelting Process. The kinetics of the reoxidation of zinc vapour by carbon dioxide and water vapour onto quartz and zinc oxide substrates is qualitatively understood and this pertains to the conditions found as the gases are being transferred from the furnace to the splash condenser. However, re-oxidation also occurs in the shaft of the furnace where the solid substrates are sinter and metallurgical coke. It was found that there was a threefold increase in the rate of oxidation on sinter, compared to quartz and a 30 to 300 increase in rate on the coke. This was attributed to the high surface area offered by these materials.

Jan 1, 2003

The oxidation of zinc vapour plays a very important part in the operation of the Imperial Smelting Process. The kinetics of the reoxidation of zinc vapour by carbon dioxide and water vapour onto quartz and zinc oxide substrates is qualitatively understood and this pertains to the conditions found as the gases are being transferred from the furnace to the splash condenser. However, re-oxidation also occurs in the shaft of the furnace where the solid substrates are sinter and metallurgical coke. It was found that there was a threefold increase in the rate of oxidation on sinter, compared to quartz and a 30 to 300 increase in rate on the coke. This was attributed to the high surface area offered by these materials.

Jan 1, 2003