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By Michael E. Stout

M.A. Industries, Inc. has developed and is now offering on a commercially available basis, complete systems to recover and recycle lead from spent SLI batteries. The system begins with the breaking and separation of the component parts of the batteries and subsequent treatment of the effluent water produced by this operation. The recyclable materials recovered from this process are metallic lead, lead paste and polypropylene. The lead paste is introduced into a process to convert it from a lead sulfate to a lead carbonate. The process also regenerates the salt solutions into reusable carbonate. The lead carbonate is then leached into an acid bath where it is later recovered by a proprietary electrolytic process. The metallic lead is recovered in a short rotary furnace producing metal for further refining and alloying. The polypropylene is further washed and then introduced to a reclaim extruder along with the proper modifiers and additives. The resulting resin can then be sold on the open market to injection molding processors. This complete system greatly reduces the amount of waste to be disposed of and completely complies with all applicable EPA guidelines.

Jan 1, 1993

By Gabriel Riveros

Fire refining of copper consists of two stages copper oxidation and copper reduction. Very frequently the capacity of the anode furnace is determined by the rate of copper reduction. The analysis of factors affecting the rate of the oxygen reduction from a liquid copper with solid carbon or injected hydrocarbons pointed out the role of the mass transfer in a liquid copper in final stage of the reduction. Experimental results of copper reduction with graphite and injected natural gas in laboratory- scale crucibles showed two stages of the reduction process with a sharp change of the controlling mechanism. The estimated dynamic surface area of gas bubbles based on the measured bubble frequency and the gas flowrate allowed for the detennination of the reaction constant as a degree of the partial pre-combustion of the air/natural gas mix. The variation of the used reductant as a function of the oxygen concentration and temperature has been evaluated based on the detennined kinetic model. The intensification of copper reduction in fire refining has been discusses on the basis of obtained kinetic data and analysis of various factors detennining the time of reduction.

Jan 1, 2003

By Bo Björkman

A controlled dust generation whereby the dust generated would be enriched with specific metals would considerably facilitate the possibilities of recovering metals from such dusts. A basic understanding of the dust forming mechanisms is of fundamental importance to achieve a controlled dust generation. The present study deals with dust formation in a copper converting process. Dust samples collected from various places in the gas cleaning system were characterised for chemical and mineralogical composition using chemical analysis as well as microprobe analysis. Thermodynamic calculations were used to predict the formation of chemically formed dust at various temperatures and amounts of leakage air to the gas system. The results show that a separation of mechanically formed dust. e.g . Si0:2. Cu and chemically formed dust. e.g .? Ph, Zn, As, Bi. could, to some extent, be obtained due to their different particle sizes. A selective condensation of Pb, Zn and As at various temperatures could. according to thermodynamic calculations, he possible at high temperature. A selective condensation of metals requires an airtight gas cleaning system or a gas cleaning system with a limited amount of leakage air in order to maintain the desired temperature level.

Jan 1, 1996

By John Dasher

One of our War Plants processed Bolivian concentrates as low as 17% Sn by the Arnhem process (pressure leach with HCL) and sent the waste acid down a ditch to Galveston Bay where the chlorides, mostly iron, hydrolyzed. Oyster men, and Texas, demandedimpoundment until a disposal process could be developed. A recycle process found by lab work was recommended, piloted and a plant built. This involved cementation of As Sb, Cu, Bi and Ag on light moving scrap iron and of Sn & Pb on Al turnings (then not recyclable), evaporation and crystallization of hydrous FeCl2, roasting crystals in a muffle furnace and absorbing HCI for reuse. The residue from leaching the low grade concentrates was floated to remove undissolved sulfides, classified and passed over sand and slimes tables to get a smeltable concentrate, a discardable sand tail and a slimes tail worth treating After desliming at 2 micro meters cassiterite, oxide flotation gave good, lab results; but commercial equipment wasn't adequate then. Chloride volatilization, with or without smelting gave high recoveries of Sn as SnCl2, whose marketing was questionable. I have heard this was finally fluxed and smelted.

Jan 1, 1992

Cospidie (3CaO*2SiO2*CaFe2) is one of the most important compounds crystallized in mold flux films during casting in the continuous casting process of steel, The primary crystallization field of cuspidine has been experimentally developed in the CaO-SiO2-CaF2-SiF4 system. The cuspidine-NaF binary and cuspidine-CaF2-NaF ternary systems have been also experimentally determined to study effects of addition of NaF on the primary field of cuspidine. In order to discuss its thermodynamic stability the standard Gibbs energy of formation of cuspidine has been deterimed by an electromotive force methods using CaF2 as solid electrolyte and a transpiration method as follows: ^fG° (cuspidine) /kjmol-1 = 5198 + 0.825T (+12) (1313<T/K<1329): EMF method ^fG° (cuspidine) /kjmol-1 = 5178 + 0.813T (+8) (1221<T/K<1469): Transpiration method The chemical potential diagram and constituent activities for the CaO-SiO2-CaF2 System have been evaluated based on the obtained thermodynamic data.

Jan 1, 2003

By C. Lupi

Zinc impure solutions as spent electrolytes, leach liquors coming from aqueous treatment of both minerals and solid waste, need to be purified before undergoing the treatment to obtain the final product. Solvent extraction is one of the most selective operations particularly when many metallic ions are present in solution. Zinc pure solutions are frequently obtained using DZEHPA as extractant. In this work an investigation on zinc extraction effectiveness of naftenic acid was carried out. After determining the best diluent and the optimal extractant concentration, the partition coefficient was determined as a function of temperature, equilibrium pH and zinc concentration. Finally same batch tests to determine the equilibrium curves at room temperature on exhausted electrolyte coming from zinc cell were carried out by using naftenic acid, D2EHPA and TBP. The pH giving, for each extractant, the best extraction yield was selected in order to compare the equilibrium curves. Experimental results show that all the examined extractants are very effective in zinc extraction if the process conditions are appropriately selected. In order to avoid an impure solution pre- treatment and to obtain the maximum ertraction yield the appropriate solvent can be chosen.

Jan 1, 1998

By Chen Zhang

Polycrystalline Ti-rich NiTi thin films have been deposited from a single NiTi target using a DC magnetron sputtering system. Free standing film was obtained by using a single crystal silicon substrate. Thickness ofthe thin films is controlled at around 12 pm. In this investigation, the effect of deposition temperature on the microstructure and transformation temperatures of the thin films is studied. Influence of post heat treatment temperatures on the properties of the thin films is also investigated. Transformation temperatures of the thin films are determined by differential scanning calorimetry (DSC). The surface microstructure of the thin films is studied using a scanning electron microscope (SEM), and the crystallinity is determined using x-ray diffractometry. It is found that the thin film deposited on a hot substrate is crystalline even when the substrate temperature is as low as 300°C, while the normal crystallization temperature for an amorphous thin film is around 500°C. The microstructure of the film deposited on a hot substrate shows a very fine grain size. The grain size increases with increasing substrate temperature during deposition. The effect of post deposition heat treatment on grain size is minimal.

Jan 1, 1999

By C. Lupi

Electric arc furnace dust generated during the production of steels is regarded as hazardous waste because of the presence of leachable elements such as Cr, Pb, Cd .... Different processes are available according to the management policy chosen by the steelmaker: disposal. recycle and/or recovery. The feasibility of an hydrometallurgical Zn recovery process on fumes generated during the pyrometallurgical treatment of EAF dust has been investigated. The recovery of metallic iron, chromium and nickel as molten metal provides fumes very rich in zinc oxide ( 63.1% ) and poor in zinc ferrite. This secondary dust is still an hazardous waste and represents the raw material for the recovery of Zn and Pb. The waste material is first leached in 1.5 M sulphuric acid at 30°C to provide a Zn, Fe and Mn rich aqueous solution and a Pb and Ca sulphate rich sludge. The iron is eliminated by precipitation because is harmful to the following electrowinning process. The ftltered and purified leached solution is acidified in order to obtain good electrowinning conditions. A pure cathodic deposit of zinc is then produced in an electrolytic cell at laboratory scale.

Jan 1, 1996

By Roger Altman

The solubility of copper in primary spinel crystals encountered in reverberatory slag samples has been determined by electron microprobe analysis. These spinels, which ranged in composition from 22% A12O3 to pure magnetite, contained small quantities of dissolved copper (0-0.4%). Based on literature data it was estimated that the solubility limit of copper in solid magnetite is no greater than about 1% at 1200°C and about 2% at 1250°C. However, it was found that practically every spinel crystal examined contained significant amounts of matte inclusions. Further examination of converter slag revealed large quantities of irregularly shaped precipitated magnetite crystals which contained a large proportion of copper inclusions. Additional experimentation showed that the total copper content in reverberatory slag samples was greater than the sum of the estimated en- trained plus dissolved matte in the slag. This difference is believed to be significant and is due to the presence of matte inclusions in the spinel crystals. In the present reverberatory slag samples these inclusions accounted for about 1/2 of the amount of sulfide directly entrained in the slag.

Jan 1, 1976

By Maria K. Kojo

The interaction between various slags and a nickel concentrate containing pyrite, pentlandite, and violarite were investigated by submerging concentrate pellets in molten slags. The slags were contained in MgO-A12O3 spinel crucibles. The slag oxidizes the iron sulfides in the concentrate, resulting in a nickel matte. The amount of S02 gas formed during reaction was measured to determine the oxidation reactivity of the slags. The experimental variables included temperature, the ferric/ferrous ratio of slag, and other slag properties such as the FeO/SiO2 ratio and the MgO and NiO contents. The reactivity of the slag depended in a complex manner on its oxidizing power, viscosity, and interfacial tension. The slag composition for the greatest reactivity was determined to be Fe3+/Fe2+ = 0.3, Fe/SiO2 = 1.3, and % MgO = 2. This slag, however, caused substantial foaming. Increasing the MgO content to 10% or replacing it by 5% MgO + 8% NiO eliminated at a slight decrease in reactivity. The implications of the findings from this work in the bath smelting of nickel sulfide concentrates are discussed.

Jan 1, 1995

By Zhuo Sheng

We have designed a high-temperature Raman micro-furnace and cell that is suited for the electrochemical process study of the NO3 − in molten NaNO3– KNO3 (fraction of NaNO3 50 wt%) salt. During the cycle voltammetry and constant potential electrolysis process, the Raman laser beam was focused near the electrode; subsequently, the Raman spectra are obtained and the reduction process of NO3 − is analyzed. In the CV cathodic scan process, the new peak attributed to the ν1 mode of NO2 − emerges, and the peaks assigned to superoxide ions (O2 −) and peroxide ions (O2 2−) are not found. In the constant electrolysis process, the peaks at 1130 and 800 cm−1 appear when the potentials are between −2.0 V and −3.2 V (vs. Pt). The results show that when the NO3 − is reduced in molten the NaNO3–KNO3 mixtures, the reduction product O2− cannot stably exist, and O2− will react with NO3 − to form of superoxide ions (O2 −) and peroxide ions (O2 2−).

By Minji Jun

Leaching of the surface-coated metals from waste acrylonitrile butadiene styrene plastics (WABSP) has been investigated in the ammoniacal solution. The ammoniacal leaching of WABSP (typically containing 4.1 wt% Cu, 1.3 wt% Ni, 0.03 wt% Cr) efficiently dissolved copper and nickel, leaving unleached chromium as fine particles. The results indicate that the anions of different buffer media for metals leaching follow the order: CO3 2− > Cl− > SO4 2−. A declined leaching with high NH4OH–(NH4)2CO3 ratio (8:1) and a steep rise in extraction with high pulp in solution revealed the influence of anion (CO3 2−) and cation (Cu2+) present in the system. The leaching performed in carbonate solution by maintaining 5.0 M total NH3 concentration as NH4OH–(NH4)2CO3 ratio, 4:1; pulp density, 200 g/L; agitation speed, 400 rpm; temperature, 20 °C and time, 120 min yielded the maximum extraction (>99%) of copper and nickel. The study reveals a plausible recovery of the surface-coated metals from the WABSP without altering the properties of polymer material that can be recycled separatel

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 Roger Agnew

Sulphide ores mined by Inco Limited in the Sudbury District contain small quantities of cobalt. During beneficiation, cobalt distribution to various streams is similar to nickel. After smelting, nickel is selectively extracted by carbonyl refining and the cobalt remains in the carbonylation residue. This residue is processed in a specialized hydrometallurgical plant to produce precious metal residues, copper cathodes, and a nickel- cobalt carbonate intermediate product. The nickel-cobalt is shipped to Port Colborne where the cobalt is separated as cobaltic hydroxide and refined to metallic cobalt. This paper deals specifically with the recently constructed Electro Cobalt Refinery. The cobaltic hydroxide is dissolved and residual zinc, copper and nickel are removed by ion exchange and organics by a carbon column. The purified cobalt solution is fed to the electrowinning circuit where cobalt rounds are produced on stainless steel mandrels. In the design and construction of the refinery, special attention was directed to materials of construction both for the process equipment and the physical plant, operating control and flexibility, and the quality of the working environment. The end result is an efficient and clean operation which yields a product of excellent quality.

Jan 1, 1988

By Andrzej Warczok

Intensive smelting of copper concentrate in Teniente Converter (CT) leads to the production of high grade matte and highly oxidized slag. Smelting slag is processed in Teniente vascular slag cleaning furnace. The slag composition and forms of copper affect the slag cleaning process and final copper content. Converting of high grade matte in Pierce-Smith converter faces some difficulties in proper slagging of iron oxides. Overblowing in copper making stage allows for slag liquidation but leads to high content of copper oxide in converter slag. Converter slag recycling into CT results in the increase of the participation of oxidic copper. Separate treatment of converter slag and its impact on the forms of copper in CT slag has been analyzed. Thermodynamic properties of a system and kinetic limitations pointed out the negative effect of converter slag recycling on the forms of copper and copper recovery in slag cleaning stage. Experimental results of slag cleaning tests in a crucible scale as well as microscopic examination of laboratory and industrial slag samples supported the above analysis and permitted to formulate recommendations of separate processing of converter slag. Keywords: copper, losses, slag, recycling

Jan 1, 2001

By Yong Hack Lee

Nonferrous smelting processes have been through a rapid transformation since the beginning of 1980. The copper smelting technology has changed from the conventional Blast Furnace process to the Flash Smelting and MIB process. In the field of lead smelting, the technology has changed from the Blast Furnace Smelting to the Direct Smelting such as QSL and KIVCET. In 1992, Onsan Refinery successfully commissioned Direct Smelting QSL technology for lead. The QSL could produce more than 160,000 ton per year of lead bullion from lead concentrate and various residues. Moreover, since the year 2000, the TSL (Top Submerged Lance) Technology utilizing the same Direct Smelting process has been successfully commissioned to treat lead concentrate as well as lead sulfate residue produced from a hydrometallurgical zinc plant. This paper presents and compares the energy flows of lead smelting processes such as a conventional process and the Direct Smelting Processes plotted on the Pb-O-S phase diagram. The oxygen potential diagram suggests how to control the oxygen potential in the fum ace. Also, it describes the recent operational experience in the TSL plant of Onsan Refinery with necessary mass balance of key elements.

Jan 1, 2003

By Yong Hack Lee

Nonferrous smelting processes have been through a rapid transformation since the beginning of 1980. The copper smelting technology has changed from the conventional Blast Furnace process to the Flash Smelting and MIB process. In the field of lead smelting, the technology has changed from the Blast Furnace Smelting to the Direct Smelting such as QSL and KIVCET. In 1992, Onsan Refinery successfully commissioned Direct Smelting QSL technology for lead. The QSL could produce more than 160,000 ton per year of lead bullion from lead concentrate and various residues. Moreover, since the year 2000, the TSL (Top Submerged Lance) Technology utilizing the same Direct Smelting process has been successfully commissioned to treat lead concentrate as well as lead sulfate residue produced from a hydrometallurgical zinc plant. This paper presents and compares the energy flows of lead smelting processes such as a conventional process and the Direct Smelting Processes plotted on the Pb-O-S phase diagram. The oxygen potential diagram suggests how to control the oxygen potential in the furnace. Also, it describes the recent operational experience in the TSL plant of Onsan Refinery with necessary mass balance of key elements.

Jan 1, 2003

By Gabriel Riveros

The stags from the Teniente Converter (TC) have high copper and magnetite contents. The reduction and copper impoverishment of these slags in an electric furnace was simulated in the laboratory, as part of a conceptual study for the Ventanas smelter of ENAMI. The effect of power input, electrode immersion, temperature of the slag, coke and solid revert additions on the rate of magnetite reduction and copper recovery was investigated. It was found that the addition of solid reverts, containing copper matte, enhanced the recovery of copper. Magnetite stratification and a corresponding gradient of the copper content occurred in the slag. Microscopic examination of slag samples showed the presence of copper in the form of matte and metallic copper inclusions. The results of the experimental work combined with an analysis of the phenomena that take place in an electric furnace led to a better understanding of the slag cleaning mechanism. The successful start-up of the slag cleaning electric furnace at the Ventanas smelter resulted in good copper recovery and confirmed the beneficial effect of solid reverts addition. Electrode consumption is lower than anticipated. No bottom build-up problems have been experienced. Keywords: copper, slag, magnetite.

Jan 1, 2001

By Pan Gu, Zhen Zhang, Jiang Diao, Bing Xie, Hongyi Li

Viscosities of FeO-SiO2-V2O3-CaO-P2O5 slags have been measured at the temperature range of 1673 K to 1773 K (1400°C to 1500°C). This investigated system represents the major components of basic vanadium slag that is an important intermediate product of a novel vanadium extracting process, in which removal of phosphorus and extraction of vanadium can be achieved from the vanadium-containing hot metal simultaneously. It was found that higher CaO/SiO2 ratio resulted in lower viscosity in the composition range of interest. Also, the viscosities increase with the increasing P2O5 concentration. The varying viscosities can be attributed to the modification in complexity and polymerization of the slag network. The variation of apparent activation energies are in tune with the viscosity measurements. The results of this work revealed the effect of CaO/SiO2 and P2O5 on the viscous properties of FeO-SiO2- V2O3-CaO-P2O5 slags and therefore provide the theoretical foundation for the control of the coupling de-P and V-extraction process.

Jan 1, 2016

By Dengfu Chen, Mujun Long, Youguang Ma, Xin Xie, Xing Zhang, Leilei Zhang

"Processing parameters of a submerged entry nozzle (SEN) affect significantly on the patterns of fluid flow and temperature distribution in beam blank continuous casting mold with double SEN s. Effect of the geometry structure and immersion depth of double SEN s on the fluid flow in beam blank continuous casting mold was studied by water modeling. Results showed that, the optimal nozzle inner diameter was 40mm, and immersion depth was 70-90mm. The mold surface fluctuation, slag distribution, impact depth and removing rate of inclusion particles were discussed under different processing parameters of double SENs. As the results indicated, slag distribution was more non-homogeneous with a higher casting speed. The results provided basic data for the design and optimization of SENs used in beam blank continuous casting mold.IntroductionNear-net-shape casting has the distinct advantages of less rolling procedures, higher metal recovery and lower energy cost. Therefore, in the recent decades, one of the recent trends in the steel making process is moving toward near net shape casting. in which beam blank casting is a typical technology. The schematic section of beam blank is shown in Fig 1."

Jan 1, 2014