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By Patrick R. Taylor

Keywords: Thermal Plasma, Electroreduction, Electrolysis, Transition metals, Waste treatment, Molten oxides, Chromium oxide. An innovative process to treat transition metal oxide waste materials from diverse sources is presented. This technology involves using reverse-polarity DC plasma driven electrolysis in molten oxides. The process results in the recovery of the transition metal and other heavy metals from waste. By-products generated throughout the processing was converted to environmentally acceptable slag. The significance of this technology is that the treatment of the waste is accomplished in one step which in turn lowers the cost of remediation. Moreover, this process uses high temperature properties of thermal plasmas, which makes it possible to use molten oxides instead of halides as electrolytes. Chromium was successfully reduced from chromium oxide through the plasma driven electro-reduction process. It was shown that the selection of the appropriate ionic conducting oxides was critical for the formation of a slag that would enhance the reduction of chromium oxide.

Jan 1, 2004

By G. Gomathi, K. Asokan, K. Subramanian

An electrochemical reactor with anode and cathode chambers separated by a composite perfluoro polymer cation exchange membrane was designed, fabricated and used for the reduction of dissolved carbon dioxide under ambient conditions to formate. The flow reactor enhanced the mass transfer of carbon dioxide compared to the batch reactor. Experiments were conducted using two different perfluoro polymer membranes - Nafion 961. Efficacy of CO2 reduction on various cathode materials (Cd, Pb, Sn and Zn plated stainless steel woven mesh) were determined. Optimum values of flow rate and current density were evaluated for the energy efficient formation of formate in aqueous KHCO3 (pH 7.5-8.5) buffer solutions.

Jan 1, 2008

By David B. George

Kennecott recently completed an $880 million modernization and expansion of its smelter and refinery to process all concentrates from the Bingham Canyon mine. This is the first application of Kennecott-Outokumpu Flash Converting. Molten material movement by overhead cranes is eliminated and high levels of oxygen enrichment result in very low process gas volumes and exceptionally control of sulfur oxide emissions. All existing in-plant hygiene, safety, and environmental regulations will be met and the smelter is positioned for anticipated more stringent future regulations. Sulfur capture is 99.9 percent resulting in sulfur dioxide emissions less than the 112 kg/hr Air Permit limit, making the smelter the cleanest in the world.

Jan 1, 1996

By Xin Li, Hai-Xing Fang, Bing Xie, Hong-Yi Li

Chromium-containing vanadium slag (V-Cr slag) was obtained by an industrial smelting process of Hongge Ore, which is valuable vanadium-titanium magnetite to extract V and Cr in China. Sodium roasting thermodynamics of V-Cr slag in presence of oxygen were calculated to evaluate the reactivity of chemical compounds. Results showed that the oxidation of FeV2O4 was intensified in presence of Na2CO3 while the oxidation tendency of FeCr2O4 was far lower than that of FeV2O4. It was probably that reactions of impurities including Al2O3, SiO2 and Fe2O3 with Na2CO3 happened and the products can promote the oxidation of vanadium or chromium compounds in lower valence. Based on thermodynamic analysis, a two-step selective extraction process of vanadium and chromium was proposed. Extraction rate of vanadium was 88.6% while 7.0% for chromium in the first extraction step; extraction rate of 90.7% and 95.4% for vanadium and chromium, respectively, were obtained in the second step.

Jan 1, 2014

By Xiaofei Guan, Adam C. Powell, Uday B. Pal, Srikanth Gopalan

This paper reports a solid oxide membrane (SOM) electrolysis experiment using an LSM– Inconel inert anode current collector for production of Mg and O2 at 1423K. The electrochemical performance of the SOM cell was evaluated by using various electrochemical techniques including electrochemical impedance spectroscopy, potentiodynamic scans, and potentiostatic electrolysis. The effects of Mg solubility in the flux on the current efficiency and the YSZ membrane stability during SOM electrolysis were discussed and examined through experiment and modeling. The electronic transference number of the flux were measured to assess the Mg dissolution in the flux during SOM electrolysis. A negative correlation between the electronic transference number of the flux and the current efficiency of the SOM electrolysis was observed.

Jan 1, 2014

By Kunibert Hanusch

Copper in recycling material is accompanied by various groups of metals: 1) Metals which are much more negative than copper, such as Fe, Al, Si, P, Be They are mainly removed by fire refining during the recovery of copper and leave the process in form of slag. 2) Metals which are more positive than copper or difficult to separate by fire refining and which are partly reduced together with the copper. These metals are for example As,. Sb, Ni, Ag, Pb, Zn, Sn. They are enriched in intermediate products and recovered from these or remain for their major part in the fire-refined copper and can be separated by electrolytic refining and recovered from the electrolyte or anode slime. This report describes the process of Hüttenwerke Kayser AG in Germany and illustrates how considerable returns of material are partly required to separate or recover associated metals. They are finally removed in saleable products.

Jan 1, 1995

By Jorge Gibson, P. Chris Pistorius, Megha Jampani

Increased utilization of natural gas in blast furnace ironmaking can decrease both the cost and the carbon intensity of ironmaking, given current US natural gas prices. In this paper, three ways to utilize natural gas are compared: tuyère injection, prereduction of iron ore, and shaft injection. The basis for comparison includes coke replacement ratios, carbon intensity and furnace productivity. These were calculated using relevant mass and energy balances, a blast furnace productivity correlation based on the bosh gas flow rate, and measured and modeled prereduction kinetics. Of the natural gas utilization methods, prereduction has the highest effective coke replacement ratio (and hence the largest advantage in raw material cost), but is likely to have the highest capital requirement.

Mar 1, 2017

By Zan Yao, Sha Lv, Geoff Wang, Baojun Zhao, Zongze Huang, Jin Zou, Xiaodong Ma, Zhouhua Jiang

55SiCr steel is one of the important spring steels widely used in automobile manufacturing. The presence of micro inclusions in the steel can significantly influence a number of spring properties such as fatigue strength. It is important to understand the mechanism of the inclusion formation so that size and proportion of the inclusions can be controlled. Inclusions in Si-killed 55SiCr spring steel have been analysed by scanning electronic microscopy and electron probe X-ray microanalysis. The chemistry of the inclusions observed in 55SiCr steels can be represented by the SiO2–Al2O3–CaO–MgO system. It was found that the compositions of the inclusions cover a wide composition range, which indicates that these inclusions were formed from different reactions. The possible mechanisms of the inclusion formation are discussed. It would be possible to characterize and manage the inclusions in the spring steels deoxidized by Si.

Mar 1, 2017

By L. Escudero-Castejon, S. Sanchez-Segado, A. Jha, Y. Hara, S. Parirenyatwa

In a world where declining ore grades are increasingly common, it has become necessary to process low-grade feedstock. Carbothermic reduction in the presence of alkali (Na2CO3) has been adapted to beneficiate waste that contains titaniferous minerals (TiO2 ca. 12 wt%), in order to recover valuable constituents such as TiO2, Fe and V2O5. The waste from vanadium metal processing has environmental legacy as it leaves nearly 1 wt% V2O5 process waste, which is environmentally problematic due to V5+ ions in contact with water and soil. This investigation focuses on the kinetics and mechanism for alkali reduction of mineral waste bearing 10–12 wt% TiO2, which we studied in the 1073–1323 K range. The thermogravimetric analysis (TGA) technique was used to record weight loss data. Two distinct regimes demonstrated mixed-control kinetics: (1) at low temperatures the activation energy was found to be 199 kJ mol−1, which corresponds to the outward diffusion of O2− ions; and (2) at high temperatures the calculated value was 130 kJ mol−1, which is consistent with the activation energy for the outward diffusion of Fe2+ ions. The metallic iron, sodium titanate and sodium aluminosilicate phases that formed were characterised using X-ray powder diffraction (XPRD) and scanning electron microscopy (SEM) techniques, and their significance for metal recovery is explained.

Mar 1, 2017

By Motang Tang, Chaobo Tang, Shenghai Yang, Lulu Guo, Yun Li, Yongming Chen, Jing He

A new innovative process for one-step and cleaner extraction of lead from spent lead-acid battery by reductive sulfur-fixing smelting was presented. This paper summarized and discussed several potential sulfur-fixing agents and molten salts which can be used in this new technique. Thermodynamic analysis involving reaction mechanism, ΔGT and predominance-area diagrams of different smelting systems were performed, respectively. The results proved the technical feasibility and high-efficiency of this process. Copper oxide ash (CuO), zinc oxide ash (ZnO) and iron oxide bearing residues (FexOy) can be used as sulfur-fixing agent to extract lead through exchange reactions. Sulfur-fixed efficiency of CuO, ZnO and FeO decrease slightly in turn. Sulfur contained in PbSO4 is fixed in form of Cu2S, ZnS and FeS respectively which avoids SO2 emission. The addition of molten salt can significantly decrease temperature of reductive sulfur-fixing reactions. Molten salt can be regenerated and recycled in smelting system after filtering solid residues.

Mar 1, 2017

By Long Meng, Kuiyuan Chen, Zhe Wang, Yiwei Zhong, Zhancheng Guo

Printed circuit boards (PCBs) contain plenty of toxic substances as well as valuable metals (e.g. Pb and Sn). In this study, supergravity as a novel technology was used to separate and recover different mass ratios (Pb/Sn) of Pb-Sn alloys from PCBs. In a supergravity field, liquid metal phase can permeate from the solid particles, and based on this, 200, 280 and 400 °C were selected to separate Pb and Sn from PCBs. The results showed that the gravity coefficient only affected the Pb-Sn alloy weight, and did not change the mass ratio of Pb/Sn. With the increase of gravity coefficient, the recovery values of Pb and Sn were increased. In the separation process, under the gravity coefficient of 1000 and separation time of 2 min, the recovery values of Pb were 33.13, 38.86 and 50.48% at the temperature of 200, 280 and 400 °C, respectively, and the recovery values of Sn were 23.31, 32.57, and 40.81%, respectively, and the mass ratios of Pb/Sn in the Pb-Sn alloys were 0.55, 0.40 and 0.64, respectively. This provided a new approach to recycle Pb and Sn from PCBs.

Mar 1, 2018

By Victoria Vaccarezza, Corby Anderson

Due to the demand for rare earth elements for everyday technology and applications, there has been much research initiation into the extraction and recovery of rare earth elements. An otherwise unknown mineral, eudialyte is a zircon silicate consisting of rare earth oxides, specifically the heavy REO yttrium (III), with only trace amounts of thorium and uranium. The first part of this project aimed at finding an efficient way to liberate and upgrade eudialyte to concentrate the REO content. A combination of gravity and magnetic separation techniques were employed, resulting in limited success. The second part looked at the hydrometallurgical processing of eudialyte through various leaching experiments with sulfuric acid. In all, this project will discuss why certain processes were utilized over others, as well as the difficulties that arose during processing.

Mar 1, 2018

By Niko Hellstén

To capture efficiently the valuable trace metals from nickel slag using electric furnace, it is important to study their distributions between the slag and metallic phases in the furnace. It is impossible to calculate accurately these distributions without experimental measurements. Therefore, in this work, selected trace metal distributions and phase equilibria between K2O containing iron-silicate slags and a metallic Ni-Fe-Cu alloy in nickel slag cleaning furnace conditions were studied. The experimental method developed and applied during the work, involved a modified quenching technique that included equilibration of the samples in semi-sealed quartz ampoules in an inert atmosphere and metallic Fe saturation. The use of the semi-sealed quartz ampoule prevents the escape of volatile elements from the sample during equilibration. Chemical compositions of the phases and the trace elements were analysed by EPMA. From the measured compositions, the trace metal distribution coefficients between the molten Ni-Fe-Cu alloy and slag were calculated.

By Lawrence L. Brown

As part of the Federal effort to help maintain an adequate supply of fertilizer materials, the Bureau of Mines conducted research to characterize complex low-grade Michigan phosphate materials and to devise methods for recovering fertilizer-grade phosphate concentrates. The rock is from middle Precambrian sedimentary formations in the Marquette Range located in the central part of the Upper Peninsula of Michigan. Occurrence of phosphate-bearing sediments in Precambrian rocks is rare. This deposit, containing 12 to 15 pct P2O5 is believed to be the richest Precambrian phosphate deposit in the United States. Petrographic examination showed that the conglomeritic rock contains crystalline apatite both in "black pebbles" and in quartz matrix. Attrition scrubbing and sizing tests showed that there is no tendency for phosphate to concentrate in any of the sized fractions. In beneficiation tests, which included grinding to minus 325 mesh followed by phosphate mineral flotation using a fatty acid-fuel oil collector, a phosphate concentrate was obtained that had a grade of 30 pet P2O5 and a P2O5 recovery of 72 pct. This concentrate should be suitable for fertilizer manufacture.

Jan 1, 1982

By George S. Dulikravich

An advanced semi-stochastic algorithm for constrained multi-objective optimization has been adapted and combined with experimental testing and verification to determine optimum concentrations of aJ10ying elements in heat-resistant and corrosion-resistant H-Series austenitic stainless steel alloys. The objective was to simultaneously maximize a number of alloy's mechanical properties. This research will result in a rigorous tool for the design of high-strength H-Series steels and other types of alloys unattainable by any means existing at the present time. Such a material-by-design tool will also be able to reduce or minimize the need for the addition of expensive elements such as Cr, Ni, Co, Nb, Ti, V, etc. and still obtain the optimum properties of an aJ1oy.

Jan 1, 2003

By Y. W. Chung, W. I. Chia

"The interaction of water vapor with single crystal Ni3(Al,Ti) and polycrystalline Ni3Fe, with and without the presence of oxygen, has been studied with Auger electron spectroscopy, photoemission spectroscopy, thermal desorption and isotope exchange. Water dissociates to produce atomic hydrogen above 200 K on both Ni3(Al,Ti) and Ni3Fe surfaces. For Ni3(Al, Ti), the reaction is structure-sensitive. Pre-adsorbed or co-adsorbed oxygen on Ni3(Al,Ti) and Ni3Fe significantly suppresses hydrogen production due to water dissociation. This suppression process occurs more efficiently on Ni3Fe than Ni3(Al, Ti).IntroductionOrdered intermetallic compounds such as aluminides, silicides and titanides are very attractive for structural applications at high temperatures. This is because these intermetallics tend to form adherent oxides in oxidizing environments which protect the base materials from excessive oxidation and corrosion. In addition, they have low density, relatively high melting points and good high-temperature strength. However, the moisture in air severely embrittles many ordered intermetallics such as FeAl [1-3], Fe3A1 [4,5], C03Ti [6,7], (Co,Fe)) V [8], Ni3Si [9], Ni3(Si,Ti) [10], Ni3(AI,Mn) [Ill, and Ni3A1 [12-14], resulting in low 'ductility and brittle fracture at room temperature. Recent studies by Liu and coworkers (see review by George and Liu [15]) provide a qualitative description of the mechanism for this moisture-induced embrittlement. During elongation testing, cracks are formed, thus exposing fresh alloy surfaces. One or more active components of the alloy react with water vapor in the environment to produce atomic hydrogen which penetrates into crack tips and causes hydrogen embrittlement. This is similar to that proposed for moisture-induced embrittlement of aluminum alloys [16]."

Jan 1, 1996

By Frank M. Kimmerle

Spent Potlining (SPL) contains recoverable chemical elements (C, F, Na and Al) which are lost in stabilization or immobilization processes primarily aimed at eliminating cyanides and reducing leach rates of soluble fluorides prior to landfiling. They can be recovered in a variety of mineral forms for recycling in the aluminum industry and elsewhere. Alcan has developed a cost-effective hydrometallurgical route, combining a number of proven unit processes to destroy cyanides, recycle the chemical values and provide a zero-discharge process. Pilot plant studies of this Low Caustic Leach and Liming (LCL&L) Process prove that the fluoride scan be converted to acid grade fluorspar, while the sodium and aluminum are recovered as a sodium aluminate and caustic feed to the Bayer Plant operations. The remaining brick and carbon fraction constitutes a high ash solid fuel which meets TCLP leach criteria and whose reduced sodium content enhances its value as a chemical reducing agent.

Jan 1, 1994

By Theodore Ineich

The “BIOMOre” project aims to prove the technical feasibility of indirect in situ bioleaching of sulfide minerals contained in a deep underground deposit, by bringing together the disciplines required to make a success. The underground location in Poland was provided by project partner KGHM inside an operating copper mine. Key components of this project were the design and construction of a pilot plant, and its operation in an underground environment. This project also included a ∼250 t (100 m3) fragmented rock reactor hydraulically connected to the pilot plant. The pilot plant consisted of several tanks and pumps, a fluidised bed ferric iron generating bioreactor containing immobilised acidophilic iron oxidation biomass, and all the required instrumentation and utilities. Before the bioleaching phase could start, the rock reactor had to be flushed continuously firstly with water to remove chloride salts that are corrosive and also harmful for the bacteria used in the bioreactor, and secondly, with sulfuric acid solution to react with the carbonates present in the ore matrix. This paper summarizes the design, construction, commissioning, and operation of the pilot plant.

By W. K. Tolley

The Bureau of Mines is investigating hydrometallurgical processing techniques to recycle metals from semiconductors and other advanced materials. Cadmium and tellurium were recovered from CdTe scrap produced in the manufacture of infrared optic devices. Sulfation, ferric chloride leaching, and oxygen-pressure leaching have been tested. Cadmium dissolution was achieved using oxygen-pressure leaching in dilute sulfuric acid. However, no satisfactory scheme for dissolution of the higher valued tellurium has been devised. Leaching the ground CdTe for 75 min at 110°C in 1.1M H2S0, under 120 psig 0, yielded 99.5% Cd extraction. Tellurium remained in the leach residue as TeO, and elemental tellurium; residual cadmium was less than 0.5%. The cadmium in the leach liquor was purified of coextracted metals such as gallium and iron by adjusting the pH. The cadmium was recovered as cadmium sulfate crystals by evaporating the solution. Recovery of by product metals, notably gallium, is possible.

Jan 1, 1991

By Heikki K. Jalkanen

Thermodynamic properties of copper-iron mattes and slag-matte distribution of copper and some minor matte constituents (Ni, Co, Mo, As, Sb and Bi) are discussed on? the basis of equilibrium measurements: a change from. oxidic to sulfidic solubility as the predominant form of dissolution of copper takes place as matte grade decreases. Distribution coefficients of minor matte constituents are complex functions of sulfur and/or oxygen potentials?. The distribution behaviour of different? metals can be qualitatively derived from their affinities to copper and stabilities. of their sulfides and oxides. The equilibrium results are compared with commercially observed values. from Outokumpu.Oy flash smelting furnace.

Jan 1, 1983