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By Marco Olper

After two years of extensive research a new and innovative modification to the CX-EW process has been exploited. This process, called CX-EWS, avoids completely all the critical aspects of the previous process which affected the cost of the energy, of the chemicals and of The maintenance of the insoluble anodes. All these benefits reflect a saving of about 30% of The operating costs compared to the present traditional production and allow for a total operating costs of less than 6.5 cts/lb. lead (net of raw material cost). With this new technology it is allowed for the first time the treatment in the same plant facilities of both primary lead sulphide concentrate and spent batteries. The paper describes the technical and economical aspect of the new process with a feasibility study for 150,000 t/y spent battery facility throughput.

Jan 1, 1995

By Jean Goldschmidt

Recycling of fine oxidized particles of non-ferrous metals usually cannot be carried out by pyrometallurgical methods. 'Hydrometallurgy provides an alternative technology to reintroduce? the resulting products as secondary raw materials into the industrial cycle, thereby saving resources and energy while keeping the environment a little cleaner. The paper summarizes the methods employed by Hydrometal to achieve these objectives and? stigmatizes the latest counterproductive international regulations which create ever more obstacles to environmentally sound recycling.

Jan 1, 1995

By V. L. Stolyarova

As part of an effort to develop the fluoride electrolysis route for the production of rare earth metals and alloys, a study of the thermodynamic properties of DyF3 has been carried out by Knudsen cell mass spectrometry. A quadrupole mass spectrometer QMS 420 was used in conjunction with the Knudsen cell arrangement. The experiments were carried out in the temperature range 1280-1440 K. Vaporization was carried out from platinum, molybdenum and tantalum cells. The Dy*, DyF+, DyF2+ fragment ions and the DyF3 parent ion were identified in the mass spectrum of the DyF3 vapour. The DyF, vapour pressure was obtained by the complete isothermal vaporizadon method as well as the ion current comparison method, and the enthalpy of sublimation of DyF3 was evaluated. From the DyF3 vapour pressure data obtained at different temperatures, the enthalpies of formation of DyF3 in the gaseous as well as condensed phases have been evaluated. The experimental data are compared with the thermodynamic information available in literature.

Jan 1, 1995

By M. H. Staia

A Venezuelan ilmenite concentrate has been chlorinated at a temperature of 700" C by carbon tetrachloride. In the experimental rig, built at laboratory level, the direct chlorination process yielded a TiCI, recovery of approximately 85% after 280 minutes processing. The partial pressure of carbon tetrachloride was nearly atmospheric (0.94 atm). Product vapors from the reactor were fractionally condensed in a condenser which was maintained at a temperature of 250°C meanwhile TiCl, vapors were condensed in refrigerated coils at a temperature of -20°C. The concentrate used in this investigation was obtained by applying gravitational and magnetic concentration methods to the black sands. The experimental results have shown the need to asses the influence of the weight ratio of ilmenite to carbon tetrachloride on the resultant products. The equilibrium of the heterogeneous system has been calculated taking into account the initial experimental conditions.

Jan 1, 1995

By G. Diáz

A basic technology coping with a wide range of secondary zinc sources has been developed. The process combines an electrowinning stage, a solvent-extraction unit and a leaching procedure. The acidity generated in zinc electrowinning, transferred by the organic solvent to the aqueous raffinate, is reused to leach the zinc secondary materials. The basic process recovering zinc is described in detail. The route recovering other valuable metals such as copper, cadmium and lead associated with zinc is also described. This non-ferrous metals recovery route is advisable for either ecological and/or economical reasons. Main results of an experimental program aiming at the demonstration of the suitability of the process for several feed materials are summarized. Waelz oxides, galvanizing ashes and EAFD coming from different sources were tested in laboratory and continuous pilot plant campaigns. High zinc recovery, low reagents and utilities consumption, and effluents meeting environmental regulation were confirmed. The paper also includes the main results of a feasibility study of an industrial "base case". A mixed raw material and Spanish EAFD and 20,000 ta of zinc ingots production were chosen. The SGH zinc recovery from secondary raw material by means of the clean, safe and profitable Modified Zincex Process has been demonstrated. This reliable technology is ready for industrial application.

Jan 1, 1995

By Marion Dattilo

The search for an improved anode for the electrowinning of lead from fluosi1icic acid medium has led the U.S. Bureau of Mines to investigate composites. Polymer bonded metal oxide powders which may contain catalyst additions were prepared by pressing. These composites display an improved activity toward the oxygen evolution reaction over electrodeposited lead dioxide on titanium, carbon, and nickel substrates. These composite electrodes contain 5 to 10 wt. " binding polymer, with the balance being metal oxides. Lowered anodic potentials achieved using the compnsite anodes resulted in lower levels of lead dioxide deposition during electrowinning.

Jan 1, 1995

By Andrew B. Suttie

The lead-acid battery recycling industry was seriously affected during the 1980s by increasing environmental protection costs and poor lead prices. The process is now being repeated in the 1990s causing further difficulties, for recyclers. In Europe, many lead-acid battery recycling plants use rotary furnaces. The Darley Dale smelter, redeveloped between 1984-87, uses only rotary furnaces. A review of options for this plant has been completed and 'concluded in favour of further investment to exploit more fully the benefits of rotary furnace technology.

Jan 1, 1995

By W. L. Dalmijn

The processing of scrap and scrap cars starts with size reduction by a hammermill, or shredder. After the liberation the magnetic fraction is removed. The remaining non¬magnetic fraction mixed with other materials is screened and each fraction is processed separately. The increased use of plastic has a negative effect on the recovery of metals and waste production. At Huron Valley, Belleville Michigen, USA, the non-ferrous fraction from 5 million obsolete cars per year, containing 200,000 tons of non-ferrous metal, is processed. Aluminium Is recovered with a heavy medium separation process and concentrated with eddy current separators. The remaining heavy non-ferrous fraction is concentrated by a new combination of eddy current separation and image processing. After this separation process the zinc fraction is melted and refined and the copper, brass, stainless steel and other high-quality concentrates are sold to the secondary industries. The recycling of car scrap has become an important source of metals and materials for the secondary. materials processing industry.

Jan 1, 1995

By Andreas Weber

Batrec operates a plant for the recycling of used dry batteries with a capacity of 3000 tons per year. The plant Is situated In a tourist area of Switzerland and has complied with all the strict emission restrictions. The process yields four products: FeMn. Zn, Hg and slag. No hazardous waste Is produced. All types of batteries can be treated.

Jan 1, 1995

By Y. K. Rao

Relatively pure crystalline lead sulfate (PbSO4) can be produced by chemical vapor transport from an impure source such as the lead-acid battery paste or the roast-ore-leach-residue from a hy¬drometallurgical process-route. In a closed-reactor, transport of matter is induced by a tempera¬ture-gradient and the steady-state transfer rate can be calculated using the data on the standard free energies of formation for the species present and the pertinent binary diffusion coefficients. The present work focusses on chemical vapor transport in a tubular reactor (1.4-cm inner diameter x 10-cm long) with the source- and deposition-ends held at 850°C (T,) and 750°C (Td), respectively; PbC12(g) is the 'solvent' or 'transport agent' and NiSO4(s) placed in the source-zone -serves to maintain a sufficiently high S0,-potential such that the stability of the lead sulfate species is ensured. For the purposes of analysis, the gas-phase in the reactor is assumed to consist of eight species: H2O, PbC12, SO3, SO2. O2 HO, C12, and PbC14. The reaction between C12(g) and PbSO4(s) in the high-temperature source-zone produces PbCl2, SO2, and 02; four more reaction-equilibria in the same zone yield other species. In the low-temperature deposition-zone, reaction equilibrium involving PbC12, H2O, and SO, leads to the nucleation and growth of PbSO4 crystals; three other reaction-equilibria occur in this zone. By employing the virtual equilibrium state for the end-zones and coupling it to the Stefan-Maxwell diffusion equations for each of the gas species, the respective partial pressures for these, in the source- and deposition-zones, are computed at steady-state. From these data, the molar fluxes of PbCl2. PbCl4, and so forth, are determined. Allowing for the transport-enhancing effects of thermal convection, the net transport rate of lead (or PbSO4) is duly calculated for specified initial conditions. The predicted rates show very good agreement with measured rate data reported in the literature [ V. Plies, T. Kohlmann and R. Gruehn: Z. anorg. allg. Chem, 568, 62 (1989)

Jan 1, 1995

By James T. Skoch

With the ongoing pressure on the secondary aluminum business to limit the amount of waste generated from processing aluminum dross, it becomes very advantageous to preprocess the dross to reduce waste. The advantage of preprocessing is that it significantly reduces the oxides and salt cake generated when melted. Various products can be produced from the oxides for the steel industry. The following paper will demonstrate that removal of oxide fines before melting will result in large volumes of material not being landfilled. We will show that the end result of this technology is to significantly reduce the amount of salt cake sent to a landfill while maximizing the recyclability of the aluminum dross.

Jan 1, 1995

By Philippe Charlier

Recycling of aluminium contained in used aseptic beverage cartons is a difficult task which has nevertheless to be tackled by our modern societies. Techniques have earlier been developed by the paper and pulp industry for the recycling of the board fibres from collected post-consumer beverage cartons. A joint technical feasibility study by Granges and a leading beverage carton producer has dealt with different techniques for handling residues from repulping facilities. The aluminium obtained can be used as raw material for the production of thin gauge foil, thus closing the recycling loop.

Jan 1, 1995

By P. L. Sibrell

The U.S. Bureau of Mines has tested cyanide leaching for recovery of palladium (Pd) from spent petroleum processing catalysts. Three different catalyst samples were supplied by a spent-catalyst processor. These catalysts consisted of a zeolite base and contained 0.4 to 0.7 pct Pd. During alkaline cyanide leaching, the catalysts exhibited ion-exchange properties due to their zeolite matrices. Hydrogen ions were released from the zeolite in exchange for sodium ions in solution, resulting in a significant decrease in solution pH. This could present a safety hazard because of the potential for release of toxic hydrogen cyanide gas. A pretreatment .step where the catalysts were contacted with a 1.0M sodium hydroxide solution was found to prevent the pH shift from occurring. Following the sodium hydroxide pretreatment, two stages of leaching at 160 °C with solution containing 1 pct sodium cyanide and 0.1M sodium hydroxide gave at least 75 and up to 95 pct Pd recovery. The Pd was quantitatively recovered from the leach solution by thermal decomposition in an autoclave at 250 °C for 1 h. The Pd content of the precipitate was over 50 pct. Thermal decomposition also decreased the total cyanide content of the barren solution to less than 0.2 mg/L. The catalyst leach residues passed the Federal Toxicity Characteristic Leaching Procedure and the California Waste Extraction Test, indicating that landfill disposal of the leach residues would be acceptable.

Jan 1, 1995

By J. N. Hryn

This paper describes some of the work done in Phase 1 of a multi-year, five-phase program aimed at demonstrating the economic feasibility of producing commercial-scale quantities of commodity materials derived from salt cake residue-oxide. The amount of salt cake generated annually in the U. S. is estimated to be 510,000 tons, including 340,000 tons of residue-oxide. Used beverage can (UBC) processing accounts for the majority of residue-oxiae that could be made available for further processing into commercial products. To characterize the composition of residue-oxide. eight residue-oxide samples from various secondary processors were obtained and analyzed. Surprisingly, the composition of residue-oxide was found to be independent of source or alloy family being processed, with? the exception of slightly elevated silicon levels in 3XXand UBC residue-oxide samples. Major phases detected in the residue- oxide were? alumina, spinel, and aluminum hydroxides. Preliminary economic analyses indicated that the refractory market appears to be the best choice for high value-added products produced from residue-oxide with minimum processing. Bench-scale tests indicated that low silicon containing residue-oxide is ready to enter this market, but the elevated silicon content of UBC and 3XX residue-oxide preclude this possibility. A separation technology should 'be developed to remove silicon-containing . species from the alumina and spinel values Present in residue-oxide. This technology would then allow UBC and 3XX residue-oxides to be converted to significantly higher value-added products.

Jan 1, 1995

By A. D. Zunkel

The zinc in electric arc furnace dust (EAFD) arises from the fuming and oxidation of the zinc present, mainly as galvanizing, in automotive scrap. The dust is collected from the electric furnace offgases in bag filters and is classified by the EPA as a hazardous waste (K061). As more zinc is used in galvanized sheet on automobiles and more automobile scrap is recycled via the EAF, the more zinc will be available for recovery and recycling. EAFD will become a more prevalent and important source of zinc compared to the traditional zinc sulfide concentrates ifit can be cost effectively processed.

Jan 1, 1995

By Katsutoshi Inoue

The sulfuric acid leaching of spent hydrodesulfurization catalysts yields an acidic solution rich in rare metals such as molybdenum, vanadium, cobalt, and nickel in addition to aluminum. For the purpose of separating and recovering the rare metals from the solution, basic solvent extraction characteristics of the metals involved with commercially available acidic organophosphorus reagents like TR-83, PC-88A, PIA-8 and CYANEX 272 as well as aliphatic alpha-hydroxyoxime LIX 63 from sulfuric acid media were investigated in the present work. It was demonstrated that CYANEX 272, PIA-8 and LIX 63 possessed excellent selectivity for molybdenum and vanadium over the other metals at comparatively low pH. Further, recovery of molybdenum and vanadium from the total leach liquor by the selected extractants was discussed. Additionally, in order to achieve preferential separation and recovery of cobalt and nickel over an appreciable amount of aluminum from the raffinate obtained after recovering molybdenum and vanadium, a systematic investigation was conducted on synergistic extraction behaviors of the mixed solvents of LIX 63 in combination with a series of acidic extractants such as CYANEX 272, PIA-8, PC-88A, D2EHPA, TR-83 and OPEHPA for cobalt, nickel and aluminum. It was elucidated that all of these mixtures could exhibit a good synergistic effect for extraction of cobalt and nickel, and that the lower the pKa of the acidic extractants, the greater the synergism. Contrarily, the extraction of aluminum, was considerably suppressed by LIX 63. Effective extraction of cobalt and nickel away from aluminum was accomplished from the sulfate solution at low pH (1.0 - 2.5) with the mixtures. In particular, the mixtures consisting of LIX 63 and CYANEX 272 or PIA-8 appeared to be the most feasible and economic from an industrial point of view, yielding acceptable separation efficiency for cobalt and nickel over aluminum and .a low acidity requirement for stripping cobalt and nickel as well as negligible degradation of LIX 63. Aluminum can be readily recovered as sulfate salt from the raffinate obtained after recovering molybdenum, vanadium, cobalt and nickel as outlined above by conventional crystallization method.

Jan 1, 1995

By Bernd Kos

The management of waste materials in the aluminum industry is as important as in other basic industries. Due to the high value of the-by products of the melting process and their toxic properties we took the challenge to develop a process technology to reduce the environmental impact and to help industry to get a better yield of their by products/raw materials. In melting operations metal losses due to oxidation are nearly unavoidable, the amount of such losses, however, can be controlled. Aluminum dross actually is a by product and any shop would like to get rid of it in the most economic way. This by product still contains up to 70% valuable metal! In the present work we describe possibilities to separate metal and residues for further processing. Recycling of metal concentrates, selling of dross and dumping of the residues have been the typical solutions up to now. But there are technologies available which are designed to reduce the waste to a minimum or even avoid it altogether. Such alternatives are processing of the dross into materials which can be reused in other industrial processes in order to avoid any dumping. This can be done by separating the metal and the residues by centrifuging and further use of the residues in the chemical or refractory industry. ECOCENT means economical and ecological recovery of aluminum by centrifuging of hot dross. This process, developed by FOCON Austria, is based on the idea of treating the hot dross as quick as possible in a single operation to avoid exothermic losses, intermediate storage and unnecessary handling as well as to save energy. In the ECOCENT process the hot dross is fed without any fluxing salt additions into a converter where the relevant parameters for separation, like temperature and viscosity, will be adjusted. Further big lumps of dross are ground into smaller pieces in order to improve the later separation of the metal. After homogenizing and adjusting the temperature, the hot dross is poured as quickly as possible into a centrifuge. In the ladle or alternatively the mould of the centrifuge the centrifugal forces are used for the separation of aluminum from aluminum oxide, the major constituents of dross. The separated pure metal can either be discharged liquid or as solidified aluminum ring. The design of the device for the production of liquid or solid metal is almost identical. As soon as the centrifuging is finished the liquid aluminum can be poured back into the furnace or can be used for ingot pouring. After the pouring of the metal the "dry" residues are removed just by turning the ladle. Alternatively the aluminum solidifies in the mould and is discharged as a compact ring. The separation of the residues from the aluminum ring is automatic. Due to the batchwise operation the composition of the metal is the same as in the skimmed furnace of origin. The complete treatment cycle needs about 40 minutes. The recovery rate of aluminum is better than 90% of pure metal. This technology is highly flexible by its nature and can easily accomodate various operational requirements. The consumption of energy is more than 50% lower compared to conventional dross processing as the ECOCENT process is using the inherent energy of the hot dross. These extremely good results are not dependent on the aluminum content of the dross even from very dry dross most of the metal can be recovered. The main advantages compared to conventional dross processing are the high recovery rate, the known analysis of the metal and the immediate reuse of the recovered aluminum. The high recovery rate and the pure metal result in a short amortization period. The compact ECOCENT unit needs a minimum of space since extensive handling can be avoided. The electronically controlled process needs no cooling water and is simple, safe and environmentally sound. The residues are free of fluxing salts, their content of metallic aluminum is low and the environmental problems are thus greatly reduced.

Jan 1, 1995

By H. M. . van der Donk

In this work an overview is given about the techniques available for the removal of metallic impurities from molten aluminium. The overview is focused on the removal of iron. Also, some experimental results are given about the creation of iron-rich intermetallic compounds in an aluminium system, which are subsequently removed by gravity segregation and filtration techniques. This work is part of an ongoing research project of three major European aluminium companies who are co-operating on the subject of recycling of aluminium packaging materials recovered from household waste by means of Eddy-Current techniques. Using this technique the pick-up of some contaminating metals, particularly iron, is almost unavoidable.

Jan 1, 1995

By Vince Newberry

Alcan Rolled Products at Oswego, New York, commissioned Recycle II during May of 1995. Recycle II is an advanced technology UBC recycling facility designed to meet the most stringent environmental standards enforced to date in the United States, particularly with respect to NO, and particulate emissions. This paper addresses the exacting requirements and strategies of Alcan's Recycle II project andThorpe Technologies' design considerations and solutions for the supply of environmentally favorable melting furnace and delacquering systems. The furnaces are equipped with low NOx regenerative burners and furnace pressure and hearth gas flow controls designed specifically for processing the hearth gases through baghouses. The delacquering system is a new generation Apros concurrent flow unit designed for low NOx emissions.

Jan 1, 1995

By LeRoy C. Prichard

The scrap based steel producers in the United States generate an estimated 650,000 tons of electric arc furnace (EAF) dust annually which is classified as hazardous waste, K061. These scrap based producers commonly referred to as mini-mills represented 39% of the steel produced in 1994. Based upon the EAF plants being installed or planned today, it is a reasonable projection to anticipate 50% of the steel produced in the United States will be by EAF's. Using a straight line projection of percent of steel produced to tonnage of EAF dust generated, this will result in 833,000 tons of dust being generated upon the completion of these new EAF producing plants, presumably by the year 2000. Because the United States is a capitalistic economy, a steel producer is in business to make a profit therefore dust management becomes a very important variable in the cost of making steel. An EAF mini-mill dust management program must consider at least three components. First the handling of the dust must be in accordance with the law; i.e., the Environmental Protection Agency rules and state and local municipalities guidelines governing K061. Second, it must be an economical solution that allows a company to manage its dust processing costs, a component of its total steel production costs while producing steel at a profit. Third, the dust management program should be one that is environmentally responsible; viz., the program should reclaim or recycle the dust constituents, as feedstock materials or saleable products. The first component, obedience of the law seems to be a relatively straight forward, common sense objective; however, as nearly every mini-mill operation will testify it has been a area of changing laws with confusing variations when it comes to K061. Even more frustrating is the fact that obedience or compliance today does not mean that the company will be considered law abiding in the future.The liabilities associated with

Jan 1, 1995