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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 Djona M. Gaballah I.

Selective chlorination of unroasted and roasted spent hydrorefming catalysts was studied between 300 and 600°C using the following gas mixtures : C12+CO, C12+N2 and CI2+air. Such materials contain Co, Ni and Mo compounds supported by alumina and/ or silica. They also contain variable amounts of V compounds, C, S, etc., accumulated during the life time of the catalyst. Direct oxychlorination of the C+S rich sample allows higher extraction rates than those obtained by the carbochlorination of the same roasted one. It seems that the roasting step doesn't favor the economic metals' recovery. Results of the chlorination of C+S poor spent catalysts, in the presence of CO, in the chlorinating gas mixture, or of carbon added to the sample, were comparable. Cobalt and nickel chlorides were .extracted from the chlorination residues by their dissolution with acidified water, whereas molybdenum and vanadium chlorinated compounds were recovered by selective condensation from the vapor phase. The recovery rates of valuable metals as well as the selectivity were higher for the chlorination of spent catalysts than results obtained by the hydrometallurgical processing of the same sample. Results of the scale-up of the oxychlorination of the unroasted sample confirmed those of the laboratory scale. The global recovery rates were about 88 pct of cobalt, 93 pct of molybdenum and 76 pct of vanadium. The carbochlorination was applied to the recovery of W and Ti from Denox catalyst that is a carbon and sulfur free one. Recovery rates higher than 99 pct at temperatures lower than 500 °C could be obtained. This may indicate that the chlorination process can be applied to the treatment of various industrial wastes or by-product containing transition and/or refractory metal compounds A flow - sheet for the pretreatment of these materials is proposed.

Jan 1, 1995

By Federico Chavez

The process for recovering lead from battery residues used in several Mexican Plants include lead blast furnace and rotary furnaces. The formers are basically fed with recycled batteries together with the necessary additives to produce metallic lead. One of the by-products generated in the blast furnace is a dust mainly formed by lead sulfide. The rotary furnace is used to recover lead .from lead batteries, dross from the refining-alloying process and the leady fines produced in the blast furnace. This paper describes thennodynamic analysis made to the rotary furnace process to understand the effect that each component of the system has upon the lead recovery. In order to enhance the process, the influence of iron chips composition and excess coke on slag viscosity is discussed. A computer optimization program . has been developed to design the furnace charge based on material and energy balances, .together with the thennodynamic equilibrium calculation.

Jan 1, 1995

By Andrew Case

The Port Nickel facility in Braithwaite, Louisiana, is known for pioneering hydrometallurgical processes for the 'separation and recovery of nickel, cobalt and copper. Ten years ago, in 1985, a new CRI-MET process for the recovery of molybdenum, vanadium, nickel, cobalt and alumina from spent catalysts was developed and implemented. Spent- catalysts from the petroleum industry consietute the majority of feed. These are not only a valuable-source of metals, but due to EPA regulations are frequently classified as hazardous under RCRA. Molybdenum and vanadium are selectively leached in an oxidative hydrothermal step. Alumina is then extracted in a caustic digestive leach. The unique technology produces four primary commercial products l molybdenum trioxide, vanadium oxide, aluminum trihydrate and nickel-cobalt concentrate. This paper discusses the process, modifications. during ten years of operation, and the relationship of these modifications to the future of the catalyst recycling business.

Jan 1, 1995

By Baozhong Zhao

The direct smelting of copper concentrates to copper metal in a single furnace offers environmental and energy advantages over conventional two-stage copper smelting processes. However, the direct copper making results in unacceptably high level impurities (As, Sb and Bi) in the anode copper. Experimental studies have shown that it is possible to remove these impurities from molten copper by injection of sulfur-hexafluoride. This paper discusses the experimental findings on the influence of various factors on the rate of removal of impurities, such as the impurity inter-effects, initial oxygen content in the metal and injection rate of SF6.

Jan 1, 1995

The generation of acid mine water is? due to the oxidation and weathering of sulfide bearing tailings and overburdens. Ferrite precipitation prooess has been applied to treat acid mine water. The conventional ferrite preC1pitatlon requires air oxidation at high temperature, or long aging time or addition of magnetite powder ,as promoter. In this investigation, a modified ferrite, precipitation process is developed by which magnetic ferrite can be produced at an ambient temperature. Acid mine waters from Berkeley Pit (Montana, U. S. A.) and from Noranda Tailings (Quebec, Canada) were used. The co precipitation of heavy metals from these two acid mine waters is studied as a function of FeIM molar ratio, oxidation time and settling rate under applied magnetic field. The investigation indicates that the modified ferrite co precipitation can remove substantially all of the, dissolved metal ions from acid mine water. The ferrite product obtained after precipitation' is characterized by XRD, SEM, BET and saturation magnetization. The results show that spinel ferrite, precipitation can be achieved at room temperature and the saturation magnetization of ferrite product from,acid mine water is comparable to that of pure ferrites.

Jan 1, 1995

By William D. Riley

The U. S. Bureau of Mines has developed technology to recover by-product materials from aluminum scrap using engineered scavenger compounds (ESC). ESCs are structural oxides with a channel or tunnel structure that allows them to hold ions of a specitksizes and charges. The scavenging reaction is easily reversible allowing the ESC to be recharged for continued use and the ion is recovered as an electro deposit. Key features of this novel technology are; a) ESC ,systems are designed to have a high degree of selectivity for a desired ionic species. b) The recovered mater.ial requires little or no additional reprocessing prior to reuse. Two current uses for the ESC technology that are described in this paper are the removal and recycle oflithium (Li) from lithium aluminum (Li-AL) alloys; and, using ESCs as a replacement for the conventional demaging (magnesium removal) technology used by the secondary casting industry. Research indicates that the ESC technology proposed for both these applications has either 'distinct economic and/or environmental advantages over previously employed methods of recovering. metal values from aluminum scrap.

Jan 1, 1995

Numerical simulation of the fluid flow and heat transfer has been carried out for a waste-heat boiler in an Outokumpu type copper flash smelter. In this boiler, SO2-containing off-gas flows into the waste-heat boiler radiation section at about 1350°C. A fraction of cooler off-gas from the electrostatic precipitator at about 200°C was recirculated into the radiation section, and a small amount of ambient air was leaked into the boiler from the bottom. The computational results show that the flow is strongly recirculating and distinctly three dimensional in most of the boiler, particularly in the radiation section. The hot off-gas cooled down rapidly after entering the radiation section due to radiation. The predicted flow pattern and temperature distribution were in a good agreement with laboratory models and industrial measurements.

Jan 1, 1995

By Rajesh K. Mishra

In secondary precious metals refining, the feed to the plant itself is a waste generated in manufacturing processes. Constant changes in manufacturing processes produce ever changing feed materials to the secondary PGM (platinum Group Metals) refineries. After extracting the precious metals, secondary wastes are generated. The discharge of effluent is dictated by both the PGM losses in wastes and the regulatory mandates. This paper will discuss some. of the conventional as well as some newer approaches to face both the challenges.

Jan 1, 1995

By S. C. Sharma

The aluminium matrix composites with ceramic dispersoids can be separated by density difference concept. In the proposed work composite scrap is recycled using an oil fired furnace. The scrap is melted in the furnace and temperature is maintained below 740 degree centigrade. Because of the density difference the lighter dispersoids will float and heavier dispersoids will settle down. The clean melt is separated be removing the floating and settled disperssoils, and then filtering using ceramic filters.

Jan 1, 1995

By Kenichi Moriyama

The Sumitomo Toyo Copper Smelter started operation in 1971, as an epoch-making smelter at which 9996 of the charged sulfur could be captured. In the past ten years, the amount of treated copper concentrate has-been increased from 1,300 l/ day to 1;900 t/ day by the extremely effective application of the oxygen enrichment for a flash smelting furnace and converter furnace. The sulfuric acid production capacity at the acid plant has also been increased up to 1,900 t/ day corresponding to the increase of copper concentrate smelting rate without installing an additional acid plant. Furthermore the sulfur fixed ratio is kept at a high level, more than 99.996. despite the SO. strength fluctuation of the wide range of 596 to 1396 which is attributed to the combination of flash smelting furnace and, P.S. converter. These -operational results at the? acid plant were achieved by several modifications. and two examples are briefly described as follows; (1) Converter modifications in order to cope with the high SO, strength -gas (2) Introduction of the anodically protection shell and tube type acid coolers In addition. the quality of sulfuric acid has been positively increased. For example, the concentration of iron and arsenic, which were the main Impurities in ?sulfuric acid, was successfully .reduced.

Jan 1, 1995

By J. D. Miller

Low-level radioactive contaminated soils (10-500 pci/gm) created by defense-related activities at certain superfund sites, such as Nevada Test Site (NTS), is a current environmental concern. Many of these contaminated sites may require appropriate cleanup and restoration, which could cost billions of dollars and put tremendous pressure on our limited financial resources. Therefore, the development of a selective flotation process to separate such radionuclides from contaminated soils should be considered. In this study, both a pure depleted UO2 sample and three synthetic UO2/soil mixtures were used to evaluate surface chemistry features and to examine the possibility for the flotation of fine UO2 particles from selected soils. It was intended that this model system would be a reasonable representation of contaminated soils such as those found at the Nevada Test Site which are reported to be contaminated by PuO2 fallout. The effect of reagent schedule, particle size distribution, and surface charge are discussed with respect to the flotation separation of the UO2/soil mixtures. It was found that both commercial fatty acids and reagent grade sodium oleate are effective collectors for UO2 flotation provided the pH is adjusted to the range of pH 8-9. The bench-scale flotation results successfully demonstrated that froth flotation technology can be used to remove UO2 from such model contaminated soils with appropriate flotation chemistry conditions which depend on the soil characteristics and other pretreatment procedures. In the best case, 90.2% of the UO2 was removed from a UO2/NTS soil mixture (119 ppm UO2) and the soil reduced in UO2 contamination from 119 ppm to 17 ppm in a single stage bench flotation. The impact of clay slimes present in the soil is revealed by the results which show that, for example, for a deslimed soil (28x400 mesh and 100 mg UO2/kg soil) 85¬90% UO2 recovery can be obtained with a reduction in contamination to 4.6 mg U02/kg soil.

Jan 1, 1995

By John M. Boyle

The use of high vacuum mercury retort recovery as a safe and effective means of removing mercury from mercury hazardous waste solids rendering them non-hazardous and recovering mercury suitable for recycling.

Jan 1, 1995

By Luis M. Chia

The direct dissolution of zinc in an organic solution of di-(2-ethylhexyl) phosphoric acid (D2EHPA) and kerosene was studied. The objective was to gain a better understanding of the fundamentals involved in the anodic step of the galvanic stripping process. Results showed that metallic zinc does dissolve spontaneously at ambient temperature by an electrochemical mechanism and the presence of additional oxygen activated the process. When oxygen was removed by prior nitrogen sparging, dissolution did not occur indicating a depolarizing cathodic reaction is necessary. The concentration of water in the organic also affected the rate of dissolution. A factorially designed experiment was made using four variables at two levels selected by evaluating results from previous screening tests. D2EHPA concentration, surface area and agitation were all found to be significant for the values chosen. Temperature was less significant and it was found that zinc dissolution is probably a diffusion or mixed controlled process, as indicated by the calculated activation energy of 6 kcal/mole.

Jan 1, 1995

By Ivo André

Sorption of copper ions from aqueous solutions by dried biomass of the aquatic plant Potamogeton luscens was studied at laboratory scale. The aquatic plant was collected in water resources in Brazil, washed, dried at 60°C and ground in a bladed mixer. Sorption experiments were conducted in agitated flasks and in a packed bed column. Maximum copper removal was obtained between pH 5.0 and 6.6 when copper was present in the ionic form Cu'. Sorption followed the Langmuir isotherm with saturation attained at 35 mg/g. Free energy of sorption was found, to be of the order of -25 kJ/mol. Sorption kinetics data were better described by a second order reaction and rate constants were calculated in 0.030 1/(min.mg) for - 4.0 mm particles and 0.081 1/(min.mg) for - 0.59 mm particles. Removal of metal ions in a packed bed column showed that Potamogeton luscens biomass can be used in several sorption/dessorption cycles. After sorbent saturation, copper ions can be recovered from the loaded biomass by elution-with H2SO4, solution. Main mechanism responsible for heavy metal uptake was found to be ion exchange. Results are discussed in terms of the surface properties of the biomaterial, solution chemistry of copper ions and thermodynamics parameters.

Jan 1, 1995

By A. Jakobsson

Studies of the rate of interdissolution in oxide systems in the solid state are of importance in materials processing through the powder-metallurgical route. As there is a need for following the rate of the such reactions continuously, a new method based on high temperature X-ray diffraction was developed. Mechanical mixtures of the oxides were placed in a high-temperature X-ray diffraction unit and the changes in the intensity and position of the peaks with highest intensity for both the components were followed as functions of time. A suitable theoretical model has been developed in order to interpret the experimental data and evaluate the diffusion coefficients. The method was applied in the case of the system MgO-NiO. The results obtained are compared with those obtained by another new method, based on solid-state galvanic cell technique with calcia stabilized zirconia electrolyte, developed in the Department of Theoretical Metallurgy. The advantage of the present techniques to monitor the progress of the reaction continuously make them suitable for computer control of such processes.

Jan 1, 1995

By E. Allaine

Carbochlorination kinetics of pure MoO3, Nb2O5, Ta2O5 and V2O5, by Cl2+CO+N2 gas mixtures was investigated between 380 and 1000 °C. Standard free energy of carhochlorination reactions and phase stability diagrams of these refractory metal compounds were calculated. The influence of total gas flow rate, temperature, reactants partial pressures on the reactivity of these oxides were investigated. The apparent activation energies were found to be about 83, 75, 110 and 100 kJ/mole below 650°C for MoO3, Nb2O5, Ta2O5 and V2O5, respectively. Above this temperature, the Arrhenius plots exhibit a rate anomaly attributed to thermal decomposition of COCl2 and/or structural changes of these refractory metal oxides. The apparent reaction order of carbochlorination of these oxides with respect to Cl2+CO was determined. For these refractory metal oxides, the reaction rate was maximum for a Cl2/CO ratio of about 1 in the chlorinating gas mixture. Results of carbochlorination of these oxides are compared and discussed.

Jan 1, 1995

By N. L. Piret

Primary and secondary copper smelting dusts are being generated in varying quantities with very dissimilar characteristics due to the different compositions of feed materials and the type of process utilized. After categorizing the multitude of dust types, the criteria for on-site and off-site recycling of smelter dust in terms of type and concentrations of the accompanying elements are established. Thereby, consideration is given to the important aspects of: ? optimization of copper recovery ? quality of copper product ? valorization of accompanying elements ? elimination and disposal of deleterious impurities ? minimization of impact on operation ? effects on operating costs ? environmental impact of dust treatment on overall process Existing commercial, emerging and proposed copper smelting dusts, pyrometallurgical as well as hydrometallurgical, treatment schemes are reviewed and evaluated technically, economically and environmentally in an attempt to streamline the vast number of proposed options. Thereby, the high selectivity achievable in hydrometallurgical dust processing due to it being complementary to the smelting process is expected to be given increased consideration.

Jan 1, 1995

By Henrlk Gripenberg

To solve the environmental and financial problems of the traditional Rotary Salt Furnace process, a new salt-free method for aluminum dross and scrap melting, ALUREC, has been developed by AGA and its partners, Hoogovens Aluminium and MAN GHH. AGA and Hoogovens Aluminium developed the main process concept and jointly carried out trials on pilot plant scale. Owing to excellent results" the partners decided to jointly erect a commercial scale test plant. The order for the design and erection of the furnace went to MAN GHH. The three companies designed the test plant and began operation in the spring of 1994. The results have been excellent and the process is expected to be a technical and commercial success.

Jan 1, 1995

By T. Yoshida

The Ni-MH (nickel metal hydride) rechargeable battery was developed several years ago. Its higher electrochemical capacity and greater safety compared with the Ni-Cd rechargeable battery have resulted in very rapid Increase in its production. The Ni-MH rechargeable battery consists of Ni. Co and rare earth metals, so that recycling is important to recover these valuable mineral resources. In this study. a basic recycling process for used Ni-MH rechargeable batteries has been developed, in which the Ni. Co and rare earth elements are recovered through a combination of mechanical processing and hydrometallurglcal processing.

Jan 1, 1995