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By Luis W. Pommier

Large quantities of sea sludge containing halogenated organic compounds, such as PCB, oils and metals like arsenic and lead have accumulated throughout the years at the bottom of sea channels and harbors and are obstructing navigation and creating environmental problems which need to be resolved. A sludge from a California port would be dredged by suction pumps, it would be processed in a plant which would be built either on firm soil or on floating platforms. The sludge shows contents of up to 1 ppm of PCB, 15 % oil and 10 ppm of arsenic, which generates a very fetid odor. Bench scale work indicates that most of the contamination concentrates on the solid phase, in fact, only minor amounts of oil report to the sea water and can be readily removed by physical means. After separation of the sea water from the solids of the sludge by decantation, it is possible to solubilize the PCB, the oil and the metals into an organic solvent leaving a non-hazardous soil for disposal near the harbor. The PCB is dehalogenated during the solubilization process leaving a liquor solution containing the oil and metals. The oil is extracted leaving an aqueous solution containing the arsenic. Further process extracts the arsenic from this solution rendering the liquid non-hazardous. Transportation and disposal of the sludge is impractical. There are hundreds of thousands of tons of hazardous soils accumulated in each harbor, which would fill the hazardous waste disposal sites available and it would be, prohibitively expensive to do so. It is not possible to compare the costs of decontamination with a competitive method. If it were, the proposed process would be less expensive than transportation and disposal and it has the advantage of removing the liabilities from the Responsible party. After a full scale continuous pilot project is run to decontaminate a small, 500 cubic yards accumulation of this type of sludge in a California harbor, a full scale environmental project would be initiated. The decontamination of one million tons of sludge would be completed in five years.

Jan 1, 1995

By B. J. Jody

Each year, about 11 million tons of metals (ferrous and nonferrous) are recovered in the U.S. from about 10 million discarded automobiles. The recovered metals account for about 75% of the total weight of the discarded vehicles. The balance of the material or shredder residue, which amounts to about 3 million tons annually, is currently landfilled. The residue contains a diversity of potentially recyclable materials, including polyurethane foams, iron oxides, and certain thermoplastics. This paper discusses a process under development at Argonne National Laboratory to separate and recover the recyclable materials from this waste stream. The process consists essentially of two- stages. First, a physical separation is used to recover the foams and the metal oxides, followed by a chemical process to extract certain thermoplastics. The status of the technology is discussed, and the process economics are reviewed.

Jan 1, 1994

By A. R. Udupa

The reduction roasting behavior of chalcopyrite has been investigated using various combinations of a desulfurizing agent, i.e., CaO or Na2CO3, and a reductant, i.e., CO, H2 or C. Using these, combinations the sulfur is removed from the mineral as CaS or Na2S rather than SO2 as is the case with conventional copper smelting and converting. The laboratory reduction ex¬periments were conducted using thermogravimetric analysis (TGA) and boat tests of mixed combinations of fine particulate reactants subjected to a continuous gas stream. The degrees of metallization were determined by both weight loss and chemical analysis methods and the products examined using optical and scanning electron microscopy and electron probe microanalysis. The percent reduction after one hour at 900°C ranged from 60% to 94%. From these data It was possible to provide postulations as to the controlling reduction mechanisms.

Jan 1, 1983

By Ronald Erdmann

Today the BOF filter dusts and sludges are mainly dumped due to their zinc contents. By typically ranging from 2 to 5 % they prevent the filter dusts and sludges from beeing recycled via the blast furnace route. Based on the different discharge kinetics of Iron and zinc during the main blowing period In a bottom stirred BOF a simple and efficient system for recovery allow zinc fractions has been developed. The obtained material Is suitable for recycling without nsc of shell formation In the blast furnace. Different subsequent development steps have been performed. By starling with a very simple lime dependent model the sludge from the BOF off gas cleaning system was collected in two different sludge channel systems. This model based an the fact that most of the scrap based zinc Is discharged from the melt within the first eight to ten minutes of the BOF process. To Improve the system a spectroscope zinc sensor was Installed at the hot section of the off gas cleaning system to get more reliable informations on the actual zinc concentation of the BOF dust. By use of the system up to 50 % of the BOF sludge can be recycled.

Jan 1, 1995

By Peter R. Sanford

Cyanides are present as a dilute constituent of streams from a variety of metallurgical and mineral-processing operations. In addition, a cyanide concentration in excess of approximately 100ppb is toxic to aquatic life, and consequently these operations require a waste-treatment process to reduce the already dilute cyanide species by several orders of magnitude. Furthermore, the waste streams may have flowrates in excess of a million gallons per day. The paper reports on research conducted with a laboratory?scale electrochemical porous (graphite felt) electrode (anode) flow-reactor, which was conducted in conjunction with a computer-aided simulation of a mathematical model describing the intrinsic rate-phenomena associate with the electrode processes. The laboratory-scale cell, of rectilinear geometry, was found to be capable of reducing a feed-stream anolyte (KCN-KOH and supporting electrolyte of a single salt ? K2SO4) with a cyanide concentration of 10ppm, to less than 100ppb, at current efficiencies in the neighborhood of 50%. The computer simulation of the cell performance based on the mathematical model (and constraints imposed for tractability) was found to provide only for qualitative agreement.

Jan 1, 1998

By Kenneth L. Driggs

The 1988 shift in primary smelting facilities from low grade matte (35%) reverberatory furnaces to high grade matte (63%) flash smelting heavily impacted a very stable and successful converter operation. Low matte grade converter campaigns averaged 36,000 short tons of copper and revert production/consumption was in balance. The conversion to high matte grades necessitated oxygen enrichment of converter blast and revisions in operating practices. After two years of operational development, campaign life has risen to over 40,000 short tons and revert production/consumption is again in balance.

Jan 1, 1991

By Yuhsuke Mizukami

Crude high Cr containing steel such as tool steel, heat-resistant steel or stainless steel is produced by dissolution of high carbon ferro-chromium into molten crude steel. In the refining process, decarburization is performed at the first stage, and deoxidation is followed in the next stage. Therefore, the equilibrium relation between dissolved Cr and 0 in molten Fe-Cr alloy after decarburization is very important when yield of deoxidizer is considered for the ovemll control and optimization of the process. It is well known that the yield of deoxidizer does strongly depend on the kinds of refractories of furnace in the secondary refining process. In the present work, the equilibrium relation between dissolved Cr and O in molten Fe-Cr alloy has been measured in a Cr2O3, MgO or Al2O3 crucible at steelmaking temperature. O contents at given Fe-Cr components have been lower in order of Cr2O3, Al2O3 and MgO crucible. The present results have been discussed based on the activities of the constituents in pure solid Cr2O3, and FeO-Cr2O3, MgO Cr2O3 and (AI,Cr)2O3 solid solutions.

Jan 1, 2003

By G. Gao

Flyash from municipal solid waste (MSW) incinerators is frequently classified as a characteristic hazardous waste due to its lead and cadmium content. Extensive investigation has therefore been carried out to detoxity the flyash by leaching and to recover lead, cadmium and zinc. Detoxification can be accomplished by leaching in HCI/NaCI solutions. Optimization of leaching conditions for effective detoxification and subsequent metal recovery can be achieved by controlling the acidity of the lixiviant and flyash to lixivaint ratio. Lead and cadmium In the leaching solution is recovered by cementation with zinc dust. Leaching and cementation experiments have shown that zinc concentrations suitable for electrowinning, > 15 g/liter, can be achieved. Experiments have also been performed to determine the effects of pH, particle size of the zinc dust used, quantity of zinc added and dissolved impurities on the cementation kinetics. After recovery of lead and cadmium, electrowinning or electrowinning coupled with solvent extraction can be used to recover zinc. A process flowsheet is presented.

Jan 1, 1991

By M. Brian Maple

A rich variety of phenomena are produced by superconducting-magnetic interactions in rare earth and actinide compounds. These phenomena, and the materials in. which they have been observed, are described in this talk, with an emphasis on the new high superconducting transition temperature (Tc) copper oxides. The Materials The-materials in which these phenomena occur can' be divided into two classes. In the first group, there are two distinct interpenetrating systems of electrons, a set of localized 4f or 5f electrons and a set of itinerant electrons. The localized f electrons carry magnetic moments and interact with the spins and momenta of the the itinerant electrons, which are involved in the superconductivity, via exchange and electromagnetic interactions; respectively. This category includes materials containing rare earth (R) and actinide elements with partially-filled f electron shells which have been inroduced as substitutional impurities [e.g., La1-xCexA12, Th1-xUx] or form a sublattice in compounds [e.g., RRh4B4, RMo6S8, RMo6Se8, the high Tc. superconductors RBa2Cu3O7-d(d - 0.05)]. Materials of the second type are characterized by a single band of electrons that is responsible for both superconductivity and magnetic order. This group includes heavy electron rare earth and actinide compounds [e.g., CeCu2Si2, UBe13, UPt3, URu2Si2], and the high Tc copper oxide superconductors such as the hole-doped systems Lag- MxCuO4 (M = Ca, Sr, Ba, Na) and RBa2Cu3O7-d(0 =d= 1) and the electron-dope system Ln2-xMxCuO4-y (Ln = Pr, Nd, Sm, Eu; M = Ce, Th; x = 0.15; y - 0.02).

Jan 1, 1992

By Berger. P.

The accepted definition of the function of an edge protector fails to specify adequately the several tasks which it must perform to be functionally effective: detailed analysis of these tasks leads to the reasoned conclusion that they cannot satisfactorily be fulfilled by the conventional types of "edge-strips". The true cost of edge protector failure is cumulative: renewal costs are dwarfed by the increased operating expenses and production losses which result from but partial or incipient failure of the edge-strip; yet, the several supposedly improved types, for use with starter-blanks, generally were "built down to a price", prolonging the agony, as it were. Clearly, a fresh appraisal of the problem was overdue, and more especially so with the advent of "permanent" cathodes. As a result, new methods of edge .protection have been developed, including the so-called "EDGEWISE" system in which the present author as patentee *) has a vested interest-which he hereby declares. Due mention is made of recent progress in protecting the edges of aluminium "Jumbo" cathodes in zinc electrowinning operations, although the present Paper is more concerned with edge protection of starter-blanks and permanent cathodes in copper ER/EW processes, where most of the "old" problems now may justifiably be claimed to have been overcome, Mention is also made - albeit at this time necessarily only briefly, and confined to edge protection - of "rigidized" metal blanks and permanent cathodes: a most recent development**) which may prove to represent a "breakthrough": time will tell.

Jan 1, 1987

By Supachai Surapunl

The distribution behavior of VA minor elements (As, Sb and Bi) in the smelting stage of the Mitsubishi process were evaluated thermodynamically based on thermodynamic data and operating data. The fractional distributions between the gas, slag and matte phases considered as the degree of vapor saturation of l.0 are as follows: 53.8, 27.2 and 19% for As, 23.6, 56.6 and 19.8% for Sb, and 91.3, l.1 and 7.6% for Bi, respectively. Arsenic is mostly distributed to the gas and slag phases. It is effectively eliminated by volatilizing and slagging. Antimony is mainly in the slag phase, which is suitably removed by slagging. Bismuth is easily vaporized to gas phase. The degree of vapor saturation has a large effect on the distribution behaviors of the three elements between the three phases. The amount of a minor element in the charge has an effect on the distribution of As but no effect on the distributions of Sb and Bi. Increasing matte grade and temperature results in the change of distributions for As and Sb, significantly. The change in the distribution ratio between slag and matte phases also considerably affects the distributions of As and Sb. The distribution behavior of Bi is not significantly changed by the change in matte grade, temperature and distribution ratio.

Jan 1, 2003

By M. S. Moats

Galvanic stripping, in conjunction with solvent extraction, has been proposed as a technical option to the challenging problem of iron removal in certain hydrometallurgical processes. The galvanic stripping process is based on the ability of a solid metal to directly reduce ferric ion to the ferrous state in an organic media. Stripping the iron into the aqueous phase is then easily accomplished. Previous work has shown the reaction kinetics and efficiency are affected by such operating parameters as water and oxygen contents, temperature, time and metal reductant. In this study, the optimum operating range for some of these variables was determined. Both zinc and iron metal were used in the separate stripping of iron from D2EHP A. Reasons for the differences in the extent of the reaction obtained using the various conditions are discussed.

Jan 1, 1996

By M. Neises, M. Roeb, C. Sattler, S. Stenger

"A two-step thermo-chemical cycle process has been developed and investigated. It is based on metal oxide redox pair systems, which can split carbon dioxide as well as water molecules by extracting oxygen atoms and reversibly incorporating them into their lattice. If concentrated solar radiation is used as the heat source, a promising method exists to produce synthesis gas from water and CO2. An easy way of operation is gained by the combination of a ceramic substrate as the absorber structure, which can be heated to high temperatures with concentrated solar radiation, and of a metal oxide coating which is capable to carry out the redox reactions. The performance and kinetics of a ferrite based redox material coated on ceramic substrates were investigated in a laboratory set-up. CO2 could be reduced with significant conversions. In addition, several side reactions were observed like the formation of carbon and like the Boudouard reaction.IntroductionThe search for alternative energy carriers and for processes able to reuse carbon dioxide stimulates the research for sustainable routes of alternative fuel production. In the scope of this search thermo-chemical processes combined with sources of concentrated solar energy have become more and more attractive. Ideally, the only raw materials for such processes are water (H2O) and carbon dioxide (CO2) enabling not only a process free of emissions, but also allow to reduce emissions of other processes by reusing CO2 to provide synthesis gas, which itself can be applied to produce chemical commodities or even better synthetic fuels like methanol or petrol.In contrast to the direct splitting of those raw materials, thermochemical cycles split water and CO2 in several steps and enable hydrogen (H2) and carbon monoxide (CO) generation at temperatures controllable by today’s technical equipment. One of the most interesting thermochemical cycles is a two-step process using metal oxide based redox systems. During the first step of this cycle (the regeneration step) the metal oxide is reduced setting some of its lattice oxygen free according to reaction (1). In the next step (the splitting) the reduced and activated material is oxidised by withdrawing oxygen from water and CO2 and at the same time hydrogen and CO is set free according to reactions (2a) and (2b) respectively."

Jan 1, 2011

By László I. Kiss, Verena Mackowiak, Alexandre Perron, Dominic Toulouse, Alicia Liedtke, Sándor Poncsák

"Bubbles play a very important role in different metallurgical applications like for example in electrowinning. During heterogeneous nucleation, the maximal size of the bubbles growing at the nucleation sites as well as the nucleation frequency is determined by the so-called detachment condition. Detachment occurs when the external forces acting on the bubble exceed the retaining forces along the solid-gas-liquid triple interface line. The phenomenon depends strongly on the shape and orientation of the solid surface and on the nature and strength of the external buoyancy and drag forces. In the present study the detachment conditions of bubbles from downward facing horizontal and inclined plates were studied experimentally under the effect of gravitational and hydrodynamic forces. The results show the deformation of the bubbles under the effect of the external forces and the detachment conditions as function of the bubble volume.IntroductionIn heterogeneous nucleation bubbles are generated at the so-called nucleation sites along the solid-liquid interfaces. They continue to grow there and after they reached a certain size they detach from the solid surface and leave the nucleation site. This scenario is well known both in boiling and electrolysis. During the growth period a stable equilibrium exists between the forces that retain the bubble at the nucleation site and the forces that try to remove it. This equilibrium evolves with the increasing volume of the bubble to the point when the detachment forces overcome the retaining forces.The life of a single bubble generated by heterogeneous nucleation can be divided into two periods separated by the detachment - or in other words by the departure - of the bubble: first the growth at the nucleation site and then the movement away. The knowledge of the detachment conditions makes possible the determination of the maximal volume of the bubble at the nucleation site that, in tum, makes possible the determination of the nucleation frequency. This is why so many researches have been directed toward the clarification of the details of the bubble detachment in the past decades. The equilibrium between the attaching and separating forces depend on the presence of body, surface and flow induced forces in the liquid, on the geometry and orientation of solid surface, on the properties of the solid-liquidgas system etc."

Jan 1, 2004

By Sarah Beutner Mavrogenes

The mineralogy of three slags from a domestic secondary copper refinery were studied by applied mineralogical techniques to determine the: 1) phases present, 2) phase chemistry, 3) phase abundance, 4) associations, 5) crystalline habit, 6) grain size, 7)microtextures, and 8) causes for certain metallurgical problems, such as metal losses to the slags. The slags were produced by skimming the bath prior to melt-down to allow heat from the flame to reach the bath. The first slag is highly viscous and all three slags contain a large amount of copper. The "first slag", which is skimmed prior to treatment of the bath with fluxes, contains metallic copper, cuprite, delafossite, magnetite, Mg-hercynite, common spinel-chromite solid solution, picrochromite-chromite solid solution, common spinel-picrochromite solid soiution, gahnite, cassiterite, silica-rich glass, and corundum. Its abundant solid refractory phases make the slag difficult to skim. The "soda-rich slag", skimmed after the treatment of the bath with sodium carbonate flux, contains cuprite, delafossite, magnetite, cassiterite, Na-Al-silicate, and Na-Al-Ca-silicate. It contains less metallic copper than the first slag and lacks the refractory minerals. The "phosphorus-rich slag", skimmed after treatment of the bath with a copper phosphide flUX, contains metallic copper, cuprite, delafossite, berlinite, cassiterite, silica, apatite, Cu-Fe-rich apatite, copper phosphate, Cu-Fe-phosphate, and a Pb-phosphate. In contrast to the above three copper-rich slags, recent charges have produced a silver-copper-rich slag. The "silver-rich slag", skimmed after the treatment of the bath with a copper phosphor ide-borax flux, contains, cassiterite, delafossite, cuprite, a Na-Al-silicate, magnetite, metallic copper, MgO, common spinel-chromite solid solution, and wollastonite. Silver ranging from 0.05 to 2.02% was found by atomic absorption and inductively coupled plasma spectrometry analyses in the metallic copper phase.

Jan 1, 1989

Reduction of titania and ilmenite ores by Cf4-H2-Ar gas mixture was investigated in a laboratory fixed bed reactor. Titania was reduced to titanium oxycarbide in the temperature range of 12OO-1500°C. At 1400-15000C, the extent of reduction of titania to titanium oxycarbide achieved more than 85% in 90 min. Optimum conditions for titanium oxycarbide synthesis by reduction of titania include temperature in the range of 1300-1450°C, methane content 8 vol% and hydrogen content above 35 vol%. Ilmenite ore was reduced by Cf4-HrAr gas mixture to metallic iron and titanium oxycarbide. Metallic iron catalyzed methane cracking and solid carbon deposition. Titanium oxycarbide formed at temperatures as low as 950°C. The optimum temperature for reduction of ilmenite is 1200°C and the optimum methane content is 8 vol%. Increase in hydrogen content increased both rate and extent of reduction. With 5 vol% CH4-75 vol% Hr20 vol% Ar gas mixture, the reduction of ilmenite completed in 60 min. Reduction of titanium oxides to oxycarbide with following chlorination may be an efficient alternative technology for processing of titanium minerals.

Jan 1, 2001

By Zhang Duomo

A novel homogenous precipitation method, including microwave heating, solution conductivity controlling and freeze drying, was developed for the preparation of US nanoparticles. The effects of the precipitation conditions on the structure and morphology of CdS particles were discussed individually. It was found that under the experimental conditions the particle sizes were controllable in the range of 14nm to 100nm. Blend-type CdS was obtained from nitrate or sulphate solution and the more stable wurtzite-type US was obtained from chloride solution, which was ascribed to the coordination of C1 and Cd2+ altering the supersaturation of the solution as well as the different growth units and their connecting patterns, In the precipitation process the surface of US nanoparticles were surface modified with CH3CHSCOOH. The results demonstrate that the bifunctional thiols of thioglycolic acid modified the surface through Cd-S coordination bonding and the induced counter ion AOT-SO3 as the balance charge further increased the stability and dispersity of US nanoparticles. This surface-modified US nanoparticles had been used to prepare nonlinear optics and self-assemble catalysts.

Jan 1, 2003

By William Petrul

Image analysis studies were performed on mill products from laboratory flotation tests of the Zn-Pb ore from the Faro deposit in Yukon, Canada, to determine mineral liberations at specific grinds and to predict recoveries at optimum flotation conditions. The minimum and optimum grinds for liberating sphalerite and galena were predicted from size analysis data for the minerals in large ore pieces, and determined by image analysis studies of the mill products. The determined optimum grinds are about 2 Tyler mesh sizes larger than predicted because sane of the fine grained sphalerite and galena occurs in interstices between coarser grained pyrite and is liberated when the pyrite grains are broken apart. Materials balance calculations were performed on the analyzed values for the liberated and unliberated sphalerite and galenaa to determine their distributions in the mill products. The laboratory flotation tests recovered 74% of the sphalerite and 83% of the galena in Zn and Pb concentrates respectively. The mineral evaluation study indicates that the optimum recovery for sphalerite and galena are 85 and 83% respectively. The company is currently recovering 80% 'of the sphalerite and 82% of the galena.

Jan 1, 1989

Thermodynamics and kinetics? of the removal of Va elements (As,Sb,Bi) from copper were investigated 1n the fire relining by alkaline carbonate fluxes such as Li 2co3 , Na 2CO3 and K2CO3. The distribution coefficients of As, Sb and Bl between alkaline carbonate fluxes and mo) ten copper were ?obtained at 1200°C under the different oxygen potentials. As and Sb were easily removed from copper to fluxes as pentavalent oxide form. On the other hand, Bi was hardly removed except by a Ll2CO3 flux. The removal rates of Va elements from copper were also measured In the temperature range of 1150°C.- 1250°C. The removal rates of As and Sb were much higher than that of Bi. The removal rates of Va elements showed the same order of the distribution coefficients. The removal rate could be expressed by following equation. (1).

Jan 1, 1987

By James E. Simpson, Suresh V. Garimella, III de Groh

"An experimental and numerical study of the horizontal Bridgman growth of pure succinonitrile (SCN) and of a succinonitrile-1.0 mol. % acetone alloy (SCN-1.0 mol. % ACE) has been performed. Experiments at growth rates of 0, 2 and 40 µmis were investigated. The solid/liquid interface was stable (non-dendritic and non-cellular); however, it was not flat. Rather, it was significantly distorted by the influence of convection in the melt and, for the growth cases, by the moving temperature boundary conditions along the ampoule. For the alloy, the interface was determined to be unstable at growth rates greater than 2.8 µmis, but stable for the no-growth and 2 µmis growth cases. When compared to the pure SCN interface, the alloy interface forms closer to the cold zone,· indicating that the melting temperature has been suppressed by the addition of the alloying element. Two-dimensional computer simulations were performed for the no-growth case for both the pure and alloy materials. These simulations indicate that a primary longitudinal convective cell is formed in the melt. The maximum magnitude of velocity was calculated to be 1.515 mmls for pure SCN and 1. 724 mm/s for the alloy. The interface shape predicted by the computer simulation agrees well with the experimentally determined shape for the pure SCN case. In ongoing work, numerical simulations of the process during growth conditions are being performed.IntroductionIncreasingly, advanced materials used in the aerospace, automotive, optics and electronics fields require low levels of defects and high levels of solute uniformity. Directional solidification by the Bridgman process is widely used for synthesis of these high-quality materials. During Bridgman crystal growth, heat and mass transfer by both thermal and solutal gradient-driven convection and diffusion influence the shape of the solid/liquid interface and dopant segregation levels, and hence, directly determine the final crystal quality. Key process parameters include the applied furnace temperature distribution and rate of translation, ampoule properties and furnace orientation."

Jan 1, 1999