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By Evan O. Jones

Processes involving distillation under reduced pressure were developed at the Pacific Northwest Laboratory several years ago to recover spent acid solutions generated during the manufacture of nuclear fuel for the N-Reactor at the Hanford site. Following construction and testing of a pilot-plant, the technology was licensed to Viatec Recovery Systems, Inc. for commercialization. The technology developed included specialized distillation and rectification of volatile acids, removal of water and/or volatile acid from sulfuric acid, and precipitation of salts. A key feature of the Waste Acid Detoxification and Reclamation (WADR) technology is the development and use of advanced thermoplastic and fluoropolymer materials of construction in all critical process equipment. The technology was then expanded to include crystallization to recover metal salts for possible reuse. Economic and environmental advantages of the procedures include recovery of acids for reuse, simplification or elimination of the disposal of waste solutions, and possible recovery of metals. Industries expected to benefit from such applications include galvanizing, electroplating, sand leaching and any where metals are cleaned in acid solutions. Currently a modular system has been assembled for recovery of several different spent acid solutions.

Jan 1, 1995

By O. E. Omotoso

This study is part of an ongoing investigation to understand the mechanism of stabilization/solidification of hazardous chromium wastes in ordinary Portland cement (OPC). Tricalcium silicate (C3S*),a major component of OPC is mixed with reagent grade Cr(lll) and Cr(VI) solutions, to simulate complex cementiCr waste systems. Scanning electron microscopy (SEM) and energy disperse spectrometry (EDS) were employed to provide microstructural and chemical information. Transmission electron microscopy (TEMlEDS), apart from complimenting the SEM, was used to probe the distribution of Cr in the hydration products of C3S and to provide crystallographic information. 29Si MAS NMR (magic angle spinning - nuclear magnetic resonance) Was used to characterize the influence of Cr on the hydrated silicate structure.

Jan 1, 1995

By J. A. Brierley

A biooxidation-heap pretreatment process was field tested to evaluate enhancing gold recovery from a preg-robbing sulfidic carbonaceous ore. Newmont Gold Company&apos;s Gold Quarry sulfidic carbonaceous ore was inoculated with an iron-grown culture of Thiobacillus ferrooxidans to form a 495 ton test heap. Biooxidation was conducted for a period of 100 days. The most active period of biooxidation occurred during the first 40 days of pretreatment? About 35 to 40% of the sulfide was oxidized. The extent of biooxidation was considered good as the ore particle size was relatively large 58% >1?9 cm (&apos;/< inch). The larger particle size ore limited the extent of bacterial activity. The field test demonstrated the ability to conduct biooxidation in a small pilot test heap. Thiourea was evaluated for extraction of gold from the biooxidized preg-robbing ore.

Jan 1, 1995

By F. Tailoka

In order to decrease the voltage required for electrorefining, a recessed electrode cell has been developed in which the anode and cathode have recesses machined into their faces. The anode and cathode plates are separated by a thin refractory cloth and the cell is filled with fused salt. Bismuth containing 10 to 90 % lead with copper and silver as minor impurities has been electrorefmed at a current density of 10,000 to 20,000 Am-2. The cell voltage was between 285 and 635 millivolts and the bismuth was refined to a purity of 99.9 %. Flow patterns were observed in a room temperature model of the recessed channel cell using water and mercury to simulate molten metal and the fused salt electrolyte. The flow in the electrode recesses is characterized by discrete droplets when the liquid flow rate is low and thin streams and rivulets at higher flow rates.

Jan 1, 1995

By P. T. Velu

Light weight aluminum alloys are the major construction materials for a number of structures in automobile and aerospace industries. Higher cost of production is the key impediment which restricts the usage of these alloys. A new electrochemical process route for the low cost production of aluminum alloys is being investigated, in which alloying elements are obtained from the dissolved compound. In the present investigation, solubility of lithium compound has been determined by measuring the EMF, when it is dissolved in the electrolyte. The solubility of Li2CO3 increased with temperature from 2.95 wt pct at 1063 K to 7.57 wt pct at 1093 K. Activities of the compound in the electrolyte were deduced using Temkin&apos;s ideal solution approach.

Jan 1, 1995

By Sudhir C. Dhara

An attempt has been made on the concentration of Platinum Group Metals (PGM) from the converter matte material by microbial .leaching. Biological oxidation of base metal sulfides such as iron, copper, nickel and free sulfur present in the matte material using Thiobacillus ferrooxidans is an alternative method to concentrate the PGM-and gold. The method which produces a platinum group metals concentrate is comparable to chemical processes and electrochemical process.

Jan 1, 1995

By R. H. Hanewald

INMETCO, a subsidiary of Inco Limited, is the only facility in North America that provides High Temperature Metals Recovery for nickel-, chromium-, and iron-bearing wastes. Since 1978, this process has prevented more than 775,000 tons of materials from becoming part of the nation&apos;s waste stream. The paper describes Inco&apos;s experience in metals recovery, traces the development and explains the operation of the High Temperature Metals Recovery Process, and examines the procedures and criteria used to determine whether spent catalysts meet process feed specifications. An overview of the current requirements for transporting spent catalysts is provided. The paper concludes with brief case histories of catalysts users employing High Temperature Recovery to manage spent catalyst.

Jan 1, 1995

By Michael L. Sorokin

The various methods of converter slag cleaning operation are analysed from the thermodynamk point of view: cleaning using coal, cleaning using combustion products of natural gas and cleaning in presence of matte. All calculations were done, applying the developing computer procedure based on the free energy minimisation algorithm. Three-suffix Margules equations were used to calculate thermodynamic properties of melts; The calculations resulted in recommendations for the practical appliance.

Jan 1, 1995

By Mark Tsirlin

Kinetics of the initial oxidation stages of diffusive silicide coatings on 8 molybdenum and niobium at 1100 - 1700 and under the pressure of 400 and 1330 Pa has been studied using methods of gravimetry and gas phase analysis of oxygen, as well as by SEK, XRD and EDMA methods. The first oxidation stage described by asymptotic equation in case of NbSi coating changed over to the stage described by parabolic equation. The asymptotic law was shown to depend on non - stationary conditions on the oxide layer boundaries. Interconnection between silicides and quartz structures, on the one hand, and peculiarities of oxidation kinetics, on the other, is [discussed. The possibility of estimation oxygen atom jump frequency in quartz and fractions of oxygen reacting with metal and with silicon proceeding from the analysis of the kinetic data was ascertained. Conditions of oxidation kine- tics transfer from asymptotic (or parabolic) stage to a non - protective "linear" stage, associated with volatile ~roduct formation, are also discussed.

Jan 1, 1995

By Satu Strömberg

A single-particle laminar-flow technique was used to study oxidation of two nickel concentrates and a granulated nickel matte (43 wt% of Ni). Experimental conditions were: reaction gas from N2 to N2 + 75 vol% O2; gas preheating temperatures ranging from 500 to 1100°C. The major nickel-bearing minerals in the two concentrates were pentlandite and violarite, respectively. Chemical analysis of the particles was used to determine the oxidation degree of the materials, and optical and scanning electron microscopy were used to detect their morphology and mineralogy. Total desulfurization of the nickel concentrates was achieved under the most oxidizing conditions, while the sulfur removal from the nickel matte was not as efficient, especially with the coarse size fraction. Pentlandite-based concentrate was found to be less reactive than the violarite-based.

Jan 1, 1995

By Fathi Habashi

The behavior of pyrite, covellite, and arsenopyrite during leaching is different from other sulfides due to the presence of the disulfide ion, Sl. Arsenopyrite contains in addition, the diarsenide ion, Asl. The disulfide ion undergoes auto-oxidation in high acidity leading to elemental sulfur and sulfide ion formation: The sulfide ion may oxidize further by oxygen to elemental sulfur if high acidity is maintained. In neutral medium, the disulfide ion does not undergo auto-oxidation but oxidizes to thiosulfate then to sulfate: This leads to the two overall reactions observed experimentally: In acid medium and in neutral medium Covellite and arsenopyrite behave similarly.

Jan 1, 1995

By F. Qian

An impinging gas jet on a liquid surface is found in many industrial process systems such as electric arc furnace, welding, steel-making operation and others. Fundamental understanding of the interaction of a gas jet on a liquid pool can provide important insights into process behavior resulting in improved efficiency. A numerical model is developed for solving the flow fields of both impinging gas jet region and liquid pool below, in which the deformed interface shape is predicted simultaneously. Using curvilinear coordinates, the Navier-Stokes equations of each phase are solved separately through coupling of static pressure, shear stress and velocity at the interface. Several cases for jet distances and flowrates were investigated both numerically and experimentally with an air-water model. Favorable comparison of numerical results with experimental data confirms the validity of the present numerical approach. An existing phenomenological model for &apos;penetration depth&apos; prediction was extended for smaller 3et exit height to jet diameter&apos; ratios.

Jan 1, 1995

By Lennart Hedlund

There is today a long and well-documented experience of the use of Boliden "Kaldo&apos; technology for treatment of various feed matedals. The process is In commercial&apos; operation in the Boliden Mineral&apos;s Rönnskär plant In Sweden for treatment of copper scraps and lead concentrates (In campaigns). This plant was built In 1976 for treatment of lead dusts from the copper plant but later modified to take other raw materials. Boliden&apos;s Kaldo techr:lology Is also In operation since 1991 for treatment of low-grade copper scraps In Enlrlsorse&apos;s plant In Porto Marghera (Venice), Italy. The plant is producing 25 000 tons of blister copper ,per year. The Kaldo furnace Isa high :Intensity smelting unit, where several successive treatment steps can be done In the same vessel. The furnace can be totally enclosed to protect the working environment, and the small off-gas volume can easily be dedusted. Input materials can vary over a very wide range, the products will be a dump slag with low (0,5%) copper and lead contents and black copper or blister copper. The dust from the process can be used for zinc production. A new development is autogenous smelting of scrap in a Pierce-Smith converter, implemented at Compagnie Générale d&apos; Èlectrolyse du Palais in France.

Jan 1, 1995

By F. K. Letowski

Leaching in froth is a particular case of a three phase (liquid-solid-gaseous) process which combines flotation with leaching by using a reactive gaseous reagent as a flotation carrier and a leaching solution as the reactive liquid medium to fonn the foam (froth) in&apos; which the solid particles are suspended. Some physico-chemical and engineering aspects of leaching in froth are discussed and illustrated by its application for cleaning the mineral graphite. Leaching of the graphite concentrate containing 4L4% of the elemental carbon and 3.16% of the sulphidic &apos;sulphur was canied out in the froth fonned by: (a) a concentrated chloride solution, with a small addition of nitric acid, in the foam state; (b) a mixture of gaseous O2, NO., and H20 encapsulated in the foam; and (c) notable particles of graphite suspended in the foam. The laboratory experiments werecanied out in a "flotation column"-type reactor ala temperature from 80 to !08°C and under total pressure of 100 to 200kPa. In the 3-stage leaching-flotation process, the non-flotable fraction of particles was separated three times from the notable fraction. The concentration of carbon and elemental sulphur in the final flotable fraction was 96% C and 0.38% S respectively. The expected advantages and possible application in hydrometallurgy are suggested.

Jan 1, 1995

By Richard D. Hagni

Reflected light microscopy is routinely applied to the study of ore minerals and textures in polished sections prepared from a wide variety of ore specimens. With the increasing interest in environmental problems, the important role of the reflected light microscope in the precise phase identifications and the determination of the textural relationships between those phases needs to be recognized. Among other environmental applications, the microscope has been applied to the recognition of lead smelter particles from remote collect sites in Missouri and those particles have been compared to dust particles from specific localities at the nearby lead sinter plant and lead blast furnace. Dust from a secondary copper refinery has been studied for its mineralogy. Soils in the vicinity of a Missouri lead smelter have been studied for their mineralogy in preparation to the clean up of those soils. Electric arc furnace (EAF) dusts, recently classified as hazardous waste by the EPA, have been examined for their mineralogy and textural intergrowth in order to better evaluate proposed metallurgical treatment procedures to render the dust non-hazardous. The initial products from experimental metallurgical treatment of EAF dusts also have been studied to aid in determining the effectiveness of those treatment procedures. Refractory gold sulfides that have been roasted in the presence of lime to retain environmental objectionable sulfur and arsenic while recovering the gold have been studied by RLM to determine their mineralogy, porosity, and permeability for cyanide leach solutions. These case histories illustrate the applicability of ore microscopy to the study of problems related to environmental concerns.

Jan 1, 1995

By P. R. Taylor

Titanium carbide and titanium diboride powders have been successfully synthesized by direct treatment of ilmenite concentrates in a non-transferred arc thermal plasma reactor. Methane gas was used as the reducing agent and boron oxide was used as the boron source in these processes. Free energy minimization plots were used to predict the behavior of each system under different molar ratios and operating conditions. Products were characterized by XRD, SEM and chemical analytical techniques. The average size of the ceramic product is in the submicron range. Metallic iron apparently is finely deposited on the surface of the titanium carbide or titanium diboride particles. Minor impurities such as silica, manganese and zircon were converted to the carbide form.

Jan 1, 1995

By Daniel C. McLean

Extraction data for Cu, Zn and Fe were obtained from 4.5" and 10" columns using massive sulfide ore and natural acid mine water. The purpose was to determine if recycling of solution through the column would produce leach liquors of 4 g/l Cu and Zn at extraction rates of 1 g/l per pass at typical flow rates of 0.002 to 0.006 gpm/sq.ft. Test results exceeded expectations. Cu and Zn concentrations of 4 g/l were obtrained within 4 to 6 cycles. Concentrations greater than 6 g/l Cu and 8 g/l Zn were reached within 10 cycles. Concentrations of greater than 40 g/l of Fe and free sulfuric acid were obtained with no decrease in biological activity being observed. No reagents were used.

Jan 1, 1995

By W. Gutmannsbauer

Thin films of TiO2 nanoparticles have been prepared by different reactive deposition methods, such as electron evaporation, ion plating and ion beam sputtering. Many properties especially the optical properties, are strongly related to the film morphology and surface roughness. Scanning force microscopy was employed to obtain information on the surface structure of as-deposited Ti(h thin films. The influence of the deposition conditions and the film thickness on the optical and structural properties has been investigated. The as-deposited films were found to be amorphous or polycrystalline with anatase structure.

Jan 1, 1995

By Gaballah Djona M.

Spent hydrorefining catalysts contain about 5 % of CoO and/or NiO, 12 % of MoO3 and up to 10 % of V205. They are generally supported by alumina and contain up to 25 percent of C, S and hydrocarbons. Such materials are potentially hazardous to the soil and to water resources. Selective chlorination of raw unroasted samples with Cl2 + air gas mixture had been investigated. At temperatures lower than 600 °C, it was possible to recover more than 90 % of nickel and cobalt chlorides, about 99 % of the molybdenum and up to 75 % of vanadium chlorinated compounds. CoCl2 and Ni/Cl2 were extracted from the chlorination residues by their dissolution with acidified water. Molybdenum and vanadium chlorinated compounds were recovered by selective condensation from the vapor phase. The chlorination of Al2O3 could be limited to less than 6 %. The scale up of this treatment was successful and a flow-sheet is proposed.

Jan 1, 1995

By John A. Mavrogenes

The Texaco gasification system developed at the Monte Bello pilot plant efficiently bums petroleum-coke thereby producing syn-gas and electricity. This system produces more electricity than conventional burners, yet the only by-products are pharmaceutical grade sulfur and V -rich slag. Vanadium is known to exist in multiple valence states in compounds which possess a wide range of melting points and physical properties. Consequently, it becomes important to carefully regulate oxygen fugacity throughout the system in order to control vanadium valence state. Vanadium phase equilibria is presently poorly understood, in large part because of the multiple oxidation states of vanadium (-I, 0, +2, +3, +4, and +5) and the difficulty of unequivocally identifying the valence state(s) in many compounds. The operation of these gasifiers at approximately 1400°C is well above the melting point of V20S but considerably below the melting temperature of V02 and V 203. If J02 can be regulated to keep the burner within the V 205 field, slag material would more likely remain molten and more easily flow out of the bottom of the burner. In pure V oxides. the oxidation state is readily determined by microprobe analysis. where V20S (V+5) is 56% V, V02 (V+4) is 61.4% V, and V203 (V+3) is 68% V. However, V valence in multi-element phases (especially phases containing other elements of variable valence) cannot be resolved by microprobe analysis alone. Petroleum-coke gasification slags collected from within the gasifier under different oxidation conditions were studied by electron microprobe analysis (EMPA). X-ray diffraction (XRD). X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. Raman spectrometry in conjunction with microprobe analysis was found to resolve the valence of vanadium in the phases of these slags. Raman spectra collected from homogeneous single phase V-oxide standards in vacuum at low temperatures (-150°C) yielded peaks characteristic to each valence state. Gasifier slag samples are, however, much more complicated. Oxidized samples contain: fine grained (Ca. Mg, Fe. V) oxide matrix of variable composition, (Fe. V, Ni) spinel. (Fe, AI, V, Ni, Mg) spinel, V205laths, AI-Si glass blebs and Ni sulfides. Reduced samples contain: crystalline Ca-siIicate matrix, subhedral to euhedral (V, Fe, Mg, AI) spinel, subhedral V02, Fe and Fe-Ni sulfides, Fe-Ni alloys, and complex Ca-oxide matrix. The different spinel assemblages, the characteristic V-oxides and the distinctly different character of the matrices makes the oxidized and reduced slags readily discernible.

Jan 1, 1995