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By Filippos Patsiogiannis

Laboratory size (5 kg) aluminum killed low carbon steel melts were desulfurized with synthetic fluxes in zirconia crucibles. The sulfur, oxygen, aluminum, silicon, and manganese contents in the melt were determined as a function of refining time and temperature. With a good argon shield and synthetic flux cover, melt reoxidation was not observed. Sulfur removal followed first order reaction kinetics. The effectiveness of calcia saturated calcium-aluminate (12CaO.7Al2O3) based fluxes in desulfurizing the steel melts was evaluated. The effects of initial sulfur level of the melt, weight of the flux (slag), and additions of tellurium, fluorspar, and barium oxide to the melt on the kinetics of desulfurization were also studied.

Jan 1, 1993

By Joon H. Jang

At a selected pH, hydrothermal oxidation of chalcopyrite was carried out under controlled F+,, at elevated pressures and temperatures (172-200°C) by balancing the rate of oxygen injection against the rate of consumption. Chalcopyrite was converted to covellite (CuS) and digenite (CU1.8S) with rejection of iron and sulfur to the solution. Covellite forms in the first stage, followed by nucleation and growth of digenite in the second stage. The effects of rapid and slow injection of stoichiometric quantities of oxygen are compared. Both the covellite and digenite form a porous layer occupying the same volume as the original chalcopyrite grain. An electrochemical kinetic model is presented to correlate the observed results.

Jan 1, 1993

By I. M. Ritchie

Cyanide owes its great success as a lixivant for gold to the great strength of the Au-CN bond. A replacement for cyanide must similarly be a strong complexant for gold (I) or gold (III). The various alternatives are briefly considered and it is concluded that only thiosulfate has a reasonable chance of replacing cyanide as a relatively non-toxic lixivant at the present time. However, there are considerable technical problems to be overcome before thiosulfate can be considered to be a realistic alternative to cyanide. Firstly, the leaching of gold using aerated ammoniacal thiosulfate with copper as a catalyst is a complex process which needs to be understood and controlled carefully in order to achieve maximum recoveries with minimum reagent losses. Secondly, there needs to be an option similar to the CIP process for recovering and concentrating the dissolved gold thiosulfate complex from pulps produced in the processing of low grade gold ores. The prospects for overcoming these technical' challenges are evaluated and discussed.

Jan 1, 1998

By J. V. Atwood

The U.S. Bureau of Mines has developed a novel Double Membrane Electrolytic Cell (DMEC) that exhibits unique features for recycling contaminated metals and metal alloys. The DMEC incorporates two anionic ion exchange membranes, separating anodic and cathodic regions of the cell. The ion exchange membranes prevent significant transport of unwanted cationic impurities to the catholyte from the impure anolyte while the anion/cation balance in cell compartments is maintained through the free movement of anions between compartments. The membrane barrier makes it possible to electro refine highly contaminated materials or to electrowin from solution while utilizing alternate anode reactions. Sinceanolyte and catholyte cross contamination has been eliminated, premium cathode products are produced. The DMEC has been tested at bench, pilot, and commercial scales. Configuration of the DMEC, cell operation, scale, up efforts, and significant design factors are discussed. Two separate recycling investigations utilizing DMEC technology are presented. The first investigation examines recovery of high purity cobalt and nickel from severely contaminated super aIloy scrap. The second involves? upgrading contaminated cobalt in the U.S. Government's National Defense Stockpile. Capital and operating costs for both potential applications are presented.

Jan 1, 1995

"EAF dust is categorized as a hazardous solid waste. EPA approves only two treatment methods: either sending the dust to zinc recycling facility, or stabilizing it first and then disposing it to a specially-lined landfill. Both treatment methods are costly to EAF steelmakers. In order to reduce the cost and even better to make profit from the dust, EAF steelmakers need to find a costeffective technology to separate zinc from EAF dust. This paper is dedicated to discussion of a novel recycling strategy: in-process separation of zinc from EAF dust. The concept of in-process separation of zinc from EAF dust is first defined, and then a simple Zn concentration model is developed. From this model, two approaches of in-process separation of zinc from EAF dust are derived: (1) prematurely capturing dust at very high temperature when zinc is still in vapor status, (2) prematurely collecting dust immediately after quickly cooling EAF off-gas from high temperature to low temperature. Next, thermodynamic analysis is conducted to understand zinc behavior in EAF off-gas. It is demonstrated in theory that zinc is in vapor status while it exits from electric arc furnaces. At last, recycling routes and economics of in-process separation of zinc from EAF dust are discussed.IntroductionElectric arc furnace (EAF) plays an increasingly important role in steel production. According to USGS, steel production from electric arc furnaces has long exceeded that from basic oxygen furnaces [JJ. In 2009, electric arc furnaces produced 64% of total steel in the United States.Along with the fast growth of EAF steel production, generation of EAF dust is also rapidly increasing. A survey by AIM Market Research showed that 10 - 20 kg EAF dust was generated for every ton of EAF steel produced [2] In 1999, the United States alone produced 770,000 metric tons of EAF dust [3] In Europe, annual generation rate of EAF dust is more than one million tons [4-5]. In Japan, about 450,000 tons of EAF dust is produced each year [6] Globally, total generation of EAF dust was estimated to be more than 5 million tons per year [5] EAF dust is categorized as a hazardous solid waste since it often contains heavy metals, such as lead, chromium and cadmium. US Environmental Protection Agency (EPA) approves only two methods for treating EAF dust: (1) recycling the dust by EAF-dust recyclers, and (2) specially landfilling the dust for disposal after it is chemically stabilized. These two methods of treating EAF dust are both very costly to EAF steelmakers. It was estimated that a fee of $150 to $200 per ton of EAF dust was paid for various treatment options, which added approximately $2 - 3 cost for every ton of liquid steel produced by electric arc furnaces [?J."

Jan 1, 2011

By Daniel K. Kim

The charge for the copper refinery is a mixture of anodes produced at San Manuel from BHP source concentrate and copper purchased from external sources. Control of unwanted impurities in the tankhouse - is very important and beneficial. Currently available removal/recovery technologies were reviewed for the control of bismuth and antimony levels in the electrolyte. Recent studies have focused on solvent extraction (SX) technology and generated successful results for the removal and subsequent recovery of bismuth and antimony. The SX system employs the reagent, ACORGA SBX-50, in conjunction with a patented high chloride stripping system. The latter enables recycle of the eluant, avoiding the high costs associated with conventional systems, such as regeneration of resin. Concerns over potential transfer of organics and chloride ion to the electrolyte were readily addressed, solved and demonstrated using conventional, established technology. This paper describes the benefits of electrolyte purification, the flexibility afforded by the SX system, the operational practices necessary for maintaining adequate control of bismuth and antimony impurities in the electrorefining environment and possibilities for future development /exploitation of the Zeneca SX system at the San Manuel refinery.

Jan 1, 1998

By J. B. W. Bailey

The Noranda Horne smelter in Quebec, Canada has change considerably during the last two decades to accommodate varying custom concentrate receipts, closure of the Horne mine, better working conditions, environmental programmes, new technology and increased energy and labour costs. This paper highlights the reasons for changing the smelter from two calcine charged and one wet charge reverberatory furnaces fired by coal to a smelter using. tonnage oxygen oil, natural gas and coal in a single wet charged reverberatory furnace and a Noranda Process continuous Reactor. The current operation 1 described, including three major topics; the use of oxygen/fuel burners on the charge banks of the reverberatory furnace which has increase the smelting rate from 680 to 1100 tonnes of concentrate per day; the oxygen enrichment of the Noranda Process converting air to achieve smelting rates of over 1800 tonnes of concentrate per day; the converting of the mixture of 73 percent copper matte produced from the Noranda Process and the 33 percent copper matte produced from the reverberatory furnace.

Jan 1, 1983

By J. L. Johnson

Remediation of small-arms firing ranges is being investigated by the Naval Civil Engineering Laboratory and the U.S. Bureau of Mines. Scheduled closures of military installations, as well as the management of active ranges, require the development of methodologies for heavy metals removal to prevent their entering the surrounding environment. The impact berms contain high concentrations of metals, and the soil and vegetation surrounding the berms were found to have slightly elevated levels. The heavy metals characterized are in the form of whole bullets, a wide size distribution of free fragments, smeared lead on the surface of the soil grains, and very finely attached particles. Gravity beneficiation can remove liberated metal contamination effectively. Weak acetic acid leaching shows promise in lowering the final metal contamination to allow the soil to pass the Environmental Protection Agency's (EPA) Toxicity Characteristic Leaching Procedure (TCLP) criteria.

Jan 1, 1991

By Kirsi M. Riihilahti

The oxidation characteristics of solid copper matte particles under simulated Kennecott-Outokumpu Flash Converting conditions are presented. The effects of feed matte grade, matte particle size, oxygen-to-matte mass ratio, oxygen content of the process gas and temperature on the particle oxidation rate, quality of conversion, particle size change and particle morphology were determined. The converting quality was highest (~68) with the 58% copper matte at 1100°C. At similar conditions, the 72% copper matte was more likely to produce copper oxides and leave unoxidized particles rather than directly produce sulfur dioxide at 1100°C, resulting in an average converting quality of 55. The quality of conversion was poorest for the 72% matte at 920°C (~45); the sulfur removal was extremely low even with a relatively high degree of oxidation. Fragmentation of the particles was significant in all cases with the 72% matte. A higher O2/matte .ratio and higher temperature, in general, resulted in increased fragmentation while oxygen enrichment had no significant effect. With the 58% matte, particle size was found to increase for the finest fractions rather than to decrease due to particle expansion.

Jan 1, 1998

By D. J. Droppert

This paper describes the precipitation-production of crystalline scorodite (FeAs04.2H20) from arsenic-rich sulphate-based metallurgical solutions at ambient pressure (95°C). Arsenic is precipitated by means of a controlled precipitation technique in which the supersaturation of the solution is carefully controlled. By controlling the supersaturation in the presence of seed material. the formation of amorphous ferric arsenate is prevented. Scorodite is known to be the most stable As(V) compound and is therefore preferred as host mineral for arsenic immobilization. The effect of the following parameters on the preCipitation behaviour and kinetics of scorodite are discussed: Type of base seed concentration initial [As]. sulphate concentration. neutralization rate. seed recycling and method of Fe(ll!) addition to Fe-deficient arsenic solutions.

Jan 1, 1996

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

By J. L. Watson

The composite nature of titanomagnetites found on the west coast of the north island of New Zealand is an important parameter in the beneficiation of the black beach sands for export to Japan. To investigate this composite nature, borehole and plant samples from the Waipipi Ironsands Ltd property were subjected to a series of separations in heated Clerici solutions at densities varying from 3.2 to 4.6 g/cc. The resulting density fractons were analyzed magnetically and a set of distribution curves for composite grains proposed. In addition the experi¬mental data was plotted to produce titanomagnetite sand 'washability curves" which illustrate the possible problem areas in beneficiation that may arise due to composite titanomagnetite grains. From this data a set of guidelines are suggested for interpreting the curves in terms of ease of gravity concentration. The composite nature or liberation of titanomagnetite grains is shown to favor high and low grade composites with few intermediate compositions being isolated. The relationships between grain size, borehole depth and liberation are examined and related to beneficiation procedures for the black sand deposit.

Jan 1, 1982

The effect of change in slag composition upon metal losses to the slag and the relationship between slag composition and slag matte separation was investigated at 1400°C. The synthetic slags containing CaO, MgO, SiO2,, A1,0, and FeO were similar to those employed in the electric furnace smelting of sulphide Cu-Ni concentrates containing PGM (Precious Group Metals) from the Merensky Reef of South Africa. The matte with a grade of 9.3% Cu and 16.0% Ni was a typical electric furnace product. The results indicated that the Cu and Ni solubility in the slag increases with the increase of the basicity ratio and CaO and MgO contents of the slag. At constant CaO/MgO ratios the rise in basicity decreases the metal losses. When FeO and SiO2 contents of the slag are kept constant, the substitution of MgO with CaO decreases the metal losses. The relationship between slag composition and matte-slag separation was found to depend primarily on the basicity ratio and the FeO content of the slag. The net effect comes from a strong interaction of the two in such a way that increasing basicity and decreasing FeO contents deteriorate the clean separation of the two phases.

Jan 1, 1994

By T. K. Mukherjee

The importance of the processing of secondary resources such as solid industrial wastes and liquid effuents as well as byroducts for the recovery of the associated metal values hardly needs any elaboration. Such processing contributes in no small measure.towards the augmentation of the availability and the supply position of resources. As an added benefit, it leads to a reduction in environmental pollution caused by the undesirable waste materials. As some typical examples of secondary resources in the Indian scenario, mention' can be made of spent catalysts, metal/alloy scrap, ash, consumed batteries, flue dust, slag, sludge and slime, pickling solutions, spent acids; plating rinse solutions, spent etchants, waste water from synthetic fibre manufacture and from tanneries etc. These wastes constitute a source of a variety of non ferrous metals. In the processing of secondary resources like these, the techniques of hydrometallurgy such as solvent extraction play a pivotal role. This paper outlines the efforts made to use solvent extraction to recover (1) base metals such as copper, zinc, nickel and cobalt from a number of secondary resources like cake, and sludge(2) refractory metals like molybdenum and vanadium from sulphidic, byproducts and spent catalyst and (3:) nuclear metal like uranium from phosphoric acid. In the case of base metals, process flowsheet involving the use of acidic extractants such as DEHPA and PC88A have been optimised. The problem of iron removal from the leach liquor, "which influences the metal recovery process significantly, has drawn a special emphasis. hi the case of refractory metals, basic extractants .like Alamine 336 has been pressed into service to produce kilogramme. quantities of pure salts of molybdenum and vanadium, Finally, the paper gives a brief account of plant experience in recovering uranium from phosphoric acid, using 'a solvent system comosed of DEHPA and TOPO.

Jan 1, 1996

By T. K. Mukherjee, C. K. Gupta

"The importance of the processing of secondary resources such as solid industrial wastes and liquid effluents as well as byroducts for the recovery of the associated metal values hardly needs any elaboration. Such processing contributes in no small measure towards the augmentation of the availability and the supply position of resources. As an added benefit, it leads to a reduction in environmental pollution caused by the undesirable waste materials. As some typical examples of secondary resources in the Indian scenario, mention can be made of spent catalysts, metal/alloy scrap, ash, consumed batteries, flue dust, slag, sludge and slime, pickling solutions, spent acids, plating rinse solutions, spent etchants, waste water from synthetic fibre manufacture and from tanneries etc .. These wastes constitute a source of a variety of non ferrous metals. In the processing of secondary resources like these, the techniques of hydrometallurgy such as solvent extraction playa pivotal role.This paper outlines the efforts made to use solvent extraction to recover (1) base metals such as copper, zinc, nickel and cobalt from a number of secondary resources like cake, and sludge (2) refractory metals like molybdenum and vanadium from sulphidic byproducts and spent catalyst and (3) nuclear metal like uranium from phosphoric acid. In the case of base metals, process flowsheet involving the use of acidic extractants such as DEHPA and PC88A have been optimised. The problem of iron removal from the leach liquor, which influences the metal recovery process significantly, has drawn a special emphasis. In the case of refractory metals, basic extractants like Alarnine 336 has been pressed into service to produce kilogramme quantities of pure salts of molybdenum and vanadium. Finally, the paper gives a brief account of plant experience in recovering uranium from phosphoric acid, using a solvent system comosed of DEHPA and TOPO."

Jan 1, 1996

By Senlin Xie, Wanlin Wang, Lejun Zhou

"The innovative development of multiphase slag in hot-metal treatment has attracted considerable attention due to the reduction of CaO consumption and minimal environmental emission. In order to improve the efficiency of dephosphorization and to reutilize the waste-slag as an alternative source of phosphate ores, it is important to increase the distribution ratio of P2Os between the solid solution (2CaO· SiO2-3CaO· P2O 5) and liquid slag. An investigation was carried out to study the effects ofNa2O and B2O3 on the distribution ratio of P2Os, the results indicated that the increase ofNa2O would enhance the distribution ratio of P2Os with the formation of solid solution (2CaO·SiO2-Na2O·2CaO·P2Os), while B2O3 has the opposite function, and changes the morphology of solid solution. The study would provide an instructive way for the design of multiphase slag and re-utilization of waste-slag.IntroductionIn order to meet the increasing demand for high quality low-phosphorus steel, it requires a high efficient hot metal dephosphorization process. The current slag system for hot metal treatment contains large amount of solid CaO dispersed in liquid slag, which introduced a large amount of CaO consumption due to its low solubility, especially when CaF2 was restricted due to the environmental concerns. Therefore, new refming method to improve the utilization efficiency of CaO by using a solid/liquid coexisting multiphase slag was proposed, and the studies regarding to solid solution formation mechanism, mass transfer behavior of phosphorus and the phase relationship for multi-phase slag have been conducted. [1-6]Normally, hot metal dephosphorization slag consists of CaO--SiOz-FeO--P2O 5, and it has been approved that 2CaO·SiO2 forms a solid solution with 3CaO·P2Os at the hot metal treatment temperature over a wide range of compositions. [7] Kitamura et al [8] pointed out that the (2CaO·SiO2-3CaO·P2O 5) solid solution plays an important role in dephosphorization, and it has been regarded as an absorbents for phosphorus to lower the phosphorus content in liquid phase, which makes it more capable for future dephosphorization. l Besides, the multiphase slag has the potential to be recycled as a source of phosphorus, if the (2CaO· SiO2-3CaO· P2O 5) solid solution could contain high phosphorus content, and it can be separated from FeiO matrix 8hase due to the large difference of their magnetic properties under the strong magnetic field. [10, 11]"

Jan 1, 2014

By J. L. Holman

The Bureau of Mines is investigating recovery of Ni, Co, Cr, and other metals from mixed contaminated supera110y scrap. The scrap is melt-refined and cast into anodes for electrodeposition of recyclable Ni-Co alloy. Melt oxidation using roasted superalloy grinding sludge as oxygen source can divert the Cr to the slag but with excessive Ni-Co loss. Melt oxidation-carburization or direct melt carburization retains -95 pct of the Ni-Co in the anode alloy. With direct carburization, -90 pct or more of the Cr and other refractory metals report to the anode alloy, largely as carbide phases insoluble in electrolysis. Electrorefining data relate parameters such as controlled cathode potential, Fe and Cr impurities, pH, and compartmented cell use, to current efficiency and Ni-Co deposit quality. Recovery of -90 pct of the Ni-Co in the scrap can be achieved. Preliminary experiments to recover Cr, W, and other metals from the anode sludge and other byproducts are discussed. 347

Jan 1, 1987

By Michael Zinigrad

The quality of metallic materials depends on their composition and structure and these are determined by various physico-chemical and technological factors. To effectively prepare materials with required composition, structure and properties it is necessary to carry out a research in two parallel directions: Comprehensive analysis of thennodynamics, kineties and mechanisms of the processes taking place at the solid-liquid-gaseous phase interface during welding processes and development of mathematical models of the specific welding technologies. We have developed unique method of mathematical modeling of phase interaction at high temperatures. This method allows us to build models taking into account the thennodynamic characteristics of the processes, the influence of the initial composition and temperature on the equilibrium state of the reactions, the kinetics of heterogeneous processes, the influence of the temperature, composition, hydrodynamic and thennal factors on the velocity of the chemical and diffusion processes. The model can be implemented in the optimization of various technological processes in welding, surfacing, casting as well as in manufacturing of steels and non-ferrous alloys, materials refining, alloying with special additives, removing of non-metallic inclusions.

Jan 1, 2003

By J. T. I. Poijärvi

Outokumpu Harjavalta Metals Oy operates copper and nickel smelters, three sulphuric acid plants and nickel refinery at Harjavalta and copper refinery and precious metal plant at Pori. The by-products of these plants are presented in this paper. The by-products of the smelters include products from slag cleaning of flash smelting furnaces and converters, flue dusts and smelter off-gases. Weak acid and sludges from cleaning of smelter off-gases and acids are the by-products of the acid plants. The by-products out of the copper refinery are crystallized metal sulphates and sludges from electrolyte purification, on which a co-production process of the copper tankhouse is based. The main by-products of the precious metals plant are products from anode slime treatment and platinum metal group concentrates in the recovery of precious metals. Sludges from nickel matte leaching and precipitates from solution purification are the by-products of the nickel refinery. The formation, treatment and processing as well as the research work done for the utilization instead of dumping of the by-products in the production of copper and nickel will also be discussed in this paper.

Jan 1, 1995

By Kotaro Ogura

"The electrolysis process in which CO2 is selectively reduced to C2H4 at a three-phase(gas/solution/metal) interface on a copper-mesh electrode has been developed in a concentrated solution of potassium halide. At open-circuit potential, CO2 is captured on the electrode by being inserted into the double-layer consisting of halide anions specifically adsorbed and potassium cations which are located in the Helmholtz inner and outer layers, respectively. CO2 thus activated is subjected to the electrochemical reduction. In the early stage of reduction, CO2 is converted to formate radicals that are adsorbed on the electrode by taking the place of halide anions. The reductive coupling of these radicals results in the formation of intermediates such as -CH2C(O)- and CH2=CH-, and C2H4 is finally produced. The catalytic activity of the electrode process involving the insertion of CO2 into the double layer is not deteriorated at all during the electrolysis, and the continuous reduction of CO2 to C2H4 is possible with the addition of inorganic acid under the assistance of natural energy.Carbon dioxide is a serious pollutant released from fossil fuel power station, internal combustion and many industrial operations. The easy release of CO2 to the air has caused the global warming, and the technique which intends to curtail CO2 by pushing it back into the ground has been suggested. However, this problem should be greatly mitigated if CO2 can be converted to innocuous substances. Especially, the reuse of CO2 as fuels and chemicals is extremely effective not only for the mitigation of the global warming but also against the depletion of the fossil fuel reserves. Several processes for converting CO2 to valuable compounds have been proposed including hydrogenation over heterogeneous catalyst at high temperature and electrochemical and photochemical reduction. In the conversion and cutback processes of CO2, however, it is of importance that the process is feasible under mild conditions, because the secondary generation of CO2 is feared if high energy is required and supplied with a fossil fuel. In this meaning, the electrochemical reduction of CO2 taking place at room temperature, which is similar to photosynthesis, is promising. From the practical point of view, it is further necessary that the conversion rate is high enough and the product is satisfactorily valuable."

Jan 1, 2008