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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 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 C. Dresen

This paper discussed the reaction kinetics of the reduction of industrial phosphate pellets for P4 production. In the reduction process of various phosphate ores, the following parameters were investigated: Diffusion of the phosphorus oxide and other gaseous products from the reaction mixture after having been reduced on the reductant (coke) surface. Influence of silica on reaction kinetics. Temperature influence. Influence of mineralogy and morphology (different ores). Particle size influence of silica and coke. Experiments were carried out in a vertical tube furnace with 2 ores, 2 types of silica and one type of coke. Selected experimental conditions simulated furnace conditions. The following conclusions could be made: Reaction rate increases with the addition of SiO2 into the pellet. The reaction rate increases above 1350°C (melting temperature of the slag). Mixing different ore types in the pellets leads to differences in reduction kinetics. Particle size of the coke particles influence reduction kinetics. The amount of slag formation is influenced by silica addition, coke size and temperature.

Jan 1, 2002

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

Direct electrowinning is an electrochemical process which has been developed for the extractive recovery of copper from dilute, acidic leach solutions. In passing through a thin particulate coke cathode. copper is reduced and electrodeposited in a thin layer forming a solid copper-coke sheet. The product is melted in a furnace to separate the coke, then the molten copper is fire refined to produce a salable product. A description is given of a prototype unit which is designed to treat 20 gpm leach liquor and recover over 100 pounds of copper per day. Economic analyses show that in a commercial facility producing about 25.000 TPY copper.*the direct electrowinning process has lower overall cost than either conventional iron-cementation or the newer liquid ion exchange-electrowinning when the leach liquors contain less than 2 grams per liter of copper.

Jan 1, 1976

By Richard Elliott

Current methods for producing low-carbon manganese alloying materials for the steel industry are energy intensive and costly. To enable wider implementation of high Mn steel alloys, a novel solid-state Mn ore reduction strategy is therefore being investigated. This solid-state process, modelled on existing Direct Reduced Iron technology, employs a methane-containing atmosphere to reduce Mn ore pellets to a metal carbide. These pellets may then be smelted, yielding a Mn-rich master alloy. It is well established that CH4 is a suitable reductant for Mn ore powders; however, the reduction behaviour of industrially relevant Mn ore pellets by CH4 is poorly understood. The present work reports the results of an investigation undertaken to address this knowledge gap. The results of this study highlight the significantly different reduction behaviour exhibited by the Mn ore pellets relative to the ore powder under similar conditions and suggest that the diffusion of CH4 into the pellet interior is the limiting factor in achieving complete reduction.

By Donald Voit

"The reaction between zirconia/zircon, coke, and chlorine involves a slow reaction between the coke and the zirconia/zircon and a fast reaction with chlorine. Because of the fast chlorine reaction, the reaction rate for zirconia/zircon is nearly independent of chlorine concentration for most conditions. The reaction between zirconia/zircon and coke is particle size controlled and related to the degree of physical contact between the zirconia/zircon and the coke. Since particle-particle contact is critical, compaction of finely ground coke and zirconia/zircon produces the highest reaction rates. Uncompacted, coarse coke and zirconia/zircon has the slowest reaction behavior with static bed tests.SummaryZirconia reacts with chlorine in the presence of carbon to form zirconium tetrachloride, carbon monoxide, and carbon dioxide. A similar reaction occurs with zirconium silicate with the additional formation of silicon tetrachloride. The reaction rate depends primarily on temperature and the intimacy of contact between the zirconia and the coke. The reaction is multi-stepped with a slow reaction between coke and zirconia to form an intermediate that reacts rapidly with chlorine, causing the order of the reaction for chlorine to be near zero. Chlorination rates in the range of 1 µmole/hr/cm2 are seen for fluid bed reactors. Plug flow, and static bed reactors have reaction rates of the order of 1 mmole/hr/cm2, where the area is based on the zircon surface area in plug flow and fluid bed reactors and the boat cross sectional area in a static bed. Chlorination rates measured in zirconia/coke briquettes are higher with rates as high as 400 mmole/hr/cm2 reported. High chlorine diffusion resistance, not accounted for in the analysis of experimental results, has led to a lot of confusion in the literature interpretation of chlorination data.In general coke and zirconia/zircon particle size, coke and zirconia/zircon intimacy, coke to zirconia/zircon ratio, chlorine concentration, and temperature are important variables for chlorination. Decreasing the coke and zirconia/zircon particle size generally increase the reaction rate. The coke to zirconia/zircon ratio affects the reaction in a more complex way. Increasing the chlorine concentration generally increases the reaction rate, but the effect appears to be more related to the concentration dependency of diffusion than to its role in the kinetics. The reaction rate increases with temperature but the exact behavior is complicated by temperature effects on diffusion."

Jan 1, 2011

By Nickolas J. Themelis

The flash oxidation and smelting of mineral sulfides is a very prominent metallurgical achievement of the second part of this century. Its initial industrial implementation owes much to the work of Petri Bryk, in Finland, and Paul Queneau, in Canada. However, attempts to develop flash reduction pro- cesses, such as the reduction of iron oxide concentrates with hydrogen, have not yet been successful. The author, on the basis of experimental studies on both kinds of flash reaction systems, examines the respective rate controlling phenomena and the relative rates of flash oxidation and flash reduction.

Jan 1, 1993

By Hye-Sung Kim, Dong-Wha Kum, Gyeungho Kim

"Mechanical alloying is an effective way to finely distribute inert dispersoids in AI-TM (TM is a transition metal element) systems. It is considered that high melting point aluminides are formed by precipitation from the supersaturated aluminum matrix. The analysis is based on the fact that much higher content of TM than the solubility limit can be dissolved in alpha aluminum during the high energy ball milling. Nonetheless, the role of undissolved TM particles affecting the formation of aluminides is not suitably considered. In this paper, authors present experimental observation on the formation of Ab3Ti particles from mechanically alloyed AI-Ti alloys in the hyper-peritectic region. This study showed that, in the mechanically alloyed AI-20wt%Ti specimen, intermediate phase of cubic Ab3Ti and tetragonal AIz4Tis formed at 300 - 400°C and 400 - 500°C, respectively, before the MA-state reaches to the global equilibrium at higher temperatures. The formation behavior of Lh- Ab3Ti is interpreted by interdiffusion of Al and Ti in solid state based on the fact that large amount of nano-sized Ti particles exist in the milled powder. Present analysis indicated undissolved Ti particles of nanosize should have played an important role initiating the formation of Ab3Ti phase during annealing.IntroductionInterest in the hyper-peritectic AI-Ti alloys is based on industrial demand for high-modulus and high-temperature aluminum alloys. Earlier works on hyper-peritectic AI-Ti alloys with 4 to 12wt%Ti show that these alloys are strong at ambient temperature and maintain high strength above 300°C when titanium-trialuminide (e.g., Ab3Ti) is finely distributed in the aluminum matrix [1,2]. High melting point and high stiffness with low density of AbTi make the AI-Ti alloys strong with greater thermal stability while keeping weight savings as much as possible. Titanium in aluminum shares other merits of transition metal additions because Ti solubility in Al is low (i.e., 1.l5wt%Ti at 665°C and virtually zero below 400°C), and fine dispersion of Ab3Ti particles is readily accomplished and resists grain coarsening effectively."

Jan 1, 1996

By Zdzislaw Miczkowski

At KGHM Polska Miedz S.A, a direct flash smelting process is used for smelting of chalcocite concentrate for the production of blister copper. The paper presents a model of complex oxidation process of single concentrate grains smelted at KGHM. The description covers main chemical reactions, phenomena of heat and mass exchange inside the grains and between a grain and the surrounding space. In the model, two zones describing the course of process inside the grain were distinguished: ? The first one, which moves faster towards the centre of a grain, both organic and carbonate carbon are freed, The process takes place without the presence of oxygen and results in an increase of the temperature in the core of the particle. ?The second zone moves slower into the grain and the rate of the movement is determined by the presence of oxygen, In that zone the sulphur is eliminated and the oxidation of the organic compounds vapours moving from deeper layers of a grain takes place. Based on the results of laboratory tests, the coefficients that describe the oxygen transportation into the grain and decide the progress in the chemical reaction were determined, The paper contains the results of model calculations for single grains reacting in environment of various content of oxygen as well as the results of model calculations for the laboratory reactor system.

Jan 1, 2003

By N. Panagiotopoulos

A low-grade (1.06% Ni, 0.06% Co) hematitic type lateritic ore from Triada, Euboea Island, Greece, has been leached with sulfuric acid at atmospheric pressure for the extraction of the contained Ni and Co values. The effect of various parameters, including reaction time and leaching temperature, acid strength, pulp density, etc., on Ni, Co extraction and Fe dissolution was determined. By leaching at 95°C for 4h with a 3N sulfuric acid solution at 25% pulp density, Ni and Co extractions were 82 and 75% respectively, and Fe co-dissolution 28%, yielding a pregnant solution containing 2.7 g/l Ni, 0.16 g/l Co, and 33 g/l Fe. Overall acid consumption was 850 kg/t ore (or 100 kg/kg Nil. Preheating of the laterites at 600°C before leaching resulted in much faster leaching kinetics for Ni, but the final extraction and acid consumption remained unaffected; Fe extraction was not influenced. Three-stage counter-current leaching at 9S°C, using 2N acid strength at each stage and 35% pulp density, reduced acid consumption to 350 kg/t ore (41 kg/kg Nil, and yielded 81% Ni recovery. Percolation leaching of -10 mm laterite at ambient temperature with 3N acid for 7 days resulted in 58% Ni extraction.

Jan 1, 1988

By Charles H. Rawlins

Reported is work done on processing of steel mill effluents in the areas of dewatering and separation. Much of the waste from these operations is in the form of sludges from scrubbers, in which the primary constituent is iron oxide. Recycling of the sludge&apos;s magnetic fraction has become economically attractive in order to reduce the overall volume placed in landfills. The objective of this research is to determine the effectiveness of combining magnetic and cyclonic forces, to recover iron oxide particles from waste water stream, while decreasing the volume to be disposed. Three different size hydrocyclones, operating within the field of a quadripole magnet, were tested using varying feed pulp densities of magnetite, magnetite/dolomite, blast furnace (BF), and basic oxygen furnace (BOF) slurries. In the first three cases, the percentage of magnetics recovered increased to greater than 95%. The limiting operational factors are; high pulp density for small cyclones, which can cause flow blockage within the magnet field, and extremely fine particle sizes (<2 microns), which cannot be recovered. The results indicate this technique can remove virtually all the magnetic particles from some steel effluents to a 40-50% weight percent solids pulp, on an in line continuous basis.

Jan 1, 1994

By Fathi Habashi

During the recovery of copper, nickel, zinc, and lead from their sulfide ores, large amounts of sulfur dioxide are generated. A fraction of this gas is captured and transformed into sulfuric acid and liquid SOl and the remainder is emitted to the atmosphere. Numerous proposals were made to solve this problem. Hydrometallurgy offers the only valid solution by which elemental sulfur instead of sulfur dioxide can be produced. Sulfur can be easily stored, transported long distances, or transformed into S02 and H2S04 when desired.

Jan 1, 1996

By Lanre M. Oshinowo, André Bakker

"An understanding of the parameters that govern the just-suspended impeller speed, Njs, and the distribution of solids, is critical to the efficient operation of hydrometallurgical and other processes involving solid-liquid suspensions. In this paper, the distribution of solids in stirred tanks under a range of solids loadings (0.5 to 50 vol%) was predicted using CFD and validated against experimental data obtained from the literature. The multiphase flow is modeled using the Eulerian Granular Multiphase model. This paper will also review the established design parameter Njs in the context of scale-up and compare it to the quality of solids dispersion as a means of assessing correct scale-up in suspension tank design. The results of this study will describe a straightforward procedure to obtaining comprehensive information about reactor behavior with complex CFD models.The performance of hydrofoil impellers and a 45° pitched-blade turbine at suspending solids under different agitation speeds was studied. Both single and dual impeller operation have been evaluated. The settled solids fraction for speeds below N js, and the cloud height for impeller speeds above Njs were predicted. The CFD predictions are in good agreement with experimental literature data on velocity distribution and cloud height."

Jan 1, 2001

By Bengt T. Andersson

Outokumpu Consulting Engineers, Outokumpu Oy SF-02200 Espoo 20, Finland This paper describes experiences from some operating non-ferrous flash -smelters and focuses on the advances in smelter byproduct and gas treatment engineering design. In this context a summary is given of the specific technical and economic benefits achieved-by flash -smelting technology and oxygen enrichment. The paper will also briefly outline a few new process and equipment developments.

Jan 1, 1983

By G. R. Adams, N. Y. Tang, N. Qiang

"Aluminum is the most important alloy addition to Zn baths for controlling the reaction kinetics between the steel substrate and molten Zn in continuous galvanizing operations. Due to the complexity of the Zn-Fe-Al ternary system, the measurement and control of effective bath Al remains a challenge for modem galvanizers. The successful development of Al sensors has made the real-time measurements of bath Al contents possible. To facilitate their application, a computer interface and a palm-size data logger have been developed by Cominco. Plant applications indicated that the sensor possessed sufficient accuracy for process monitoring and control. The working mechanism of the Al sensors and Cominco's development work is described, and the results of sensor applications are presented.IntroductionControl of bath Al content is critical in modem continuous galvanizing because it has a strong influence on coating structure and properties and the overall product quality. The control of effective bath Al content (Al in liquid solution) is particularly critical for galvannealing where a high bath Al content may lead to incomplete alloying during post annealing, and a low bath Al content may result in other operation problems, such as excessive bottom dross accumulation and difficulties in coating thickness control. The desirable accuracy of the Al control is within ±50 ppm of target levels. In principle, such an accuracy is achievable for modem chemical analysis facilities, such as atomic absorption photospectrometer (AAS) and induction-coupled plasma (ICP). However, a recent study carried out by the International Lead and Zinc Research Organization (ILZRO) indicated that such an accuracy is rarely achieved in the zinc and steel industries.(1)"

Jan 1, 1997

By T. R. A. Davey

A simple model for metal solution behaviour may be derived, on the basis of dilute solution solubilities (where? log concentration of solute varies linearly with reciprocal temperature) and not-so-dilute region solubilities (where the log of the alpha-function at saturation frequently varies linearly with reciprocal temperature) and assuming activity to vary according to the quadratic formalism in between. Matte binary systems usually exhibit regular .solution behaviour when the constituent species are chosen appropriately. In many recent papers, metal solubilities in .slags are expressed as the sum of several different and supposedly independant molecular species (e.g. oxides, sulfides, chlorides), Such a view is untenable because of the now proven ionic nature of slags. Some possible reasons for the great effect of sulfur on copper solubilities in slags are discussed.

Jan 1, 1985

By T. T. Lin, N. H. Madsen, K. Groom, B. A. Chin

"The objective of this research is to investigate the feasibility of using infrared sensors to monitor the welding process. Data were gathered using an infrared camera which was trained on the molten metal pool during the welding operation. Several types of process perturbations which result in weld defects were then intentionally induced and the resulting thermal images monitored. Gas tungsten arc using AC and DC currents and gas metal arc welding processes were investigated using steel, aluminum and stainless steel plate materials. The thermal images obtained in the three materials and different welding processes revealed nearly identical patterns for the same induced process perturbation. Based upon these results, infrared thermography is a method which may be very applicable to automation of the welding process.IntroductionAutomatic welding is commonplace in industry today. However, most, if not all, involves preprogramming for performance of a repetitive task. These systems are incapable of correcting for perturbations which arise during the welding process. Control of the welding process requires the identification and monitoring of perturbations in a wide variety of parameters. The varied nature of these parameters and the large number of variables involved have thwarted previous attempts at closed loop control of the welding process. The sensor(s) employed by a control system need to meet rather strenuous requirements. First and foremost of these is that such a sensor must be able to identify and discriminate between perturbations that might affect the quality of the weld, including such geometrical perturbations as a change of direction in the seam between the parts being welded, gaps in the seam or a misalignment of the parts being welded. The sensor should also be able to locate and identify contaminants and impurities in the weld puddle and ahead of it while monitoring the extent of the heat-affected zone and the cooling rate of the metal. The sensor(s) should, additionally, be able to perform these tasks in a time frame that is consistent with automatic control of the welding process. This paper presents results that could aid in the assembly of such a controlled welding system."

Jan 1, 1986

By Rodney L. Williamson

Optimal estimation theory has been applied to the problem of estimating process variables during vacuum arc remelting (V AR), a process widely used in the specialty metals industry to cast large ingots of segregation sensitive and/or reactive metal alloys. Four state variables were used to develop a simple state-space model of the V AR process: electrode gap (G), electrode mass (M), electrode position (X) and electrode melting rate (R). The optimal estimator consists of a Kalman filter that incorporates the model and uses electrode feed rate and measurement based estimates of G, M and X to produce optimal estimates of all four state variables. Simulations show that the filter provides estimates that have error variances between one and three orders-of-magnitude less than estimates based solely on measurements. Examples are presented that verify this for electrode gap, an extremely important control parameter for the process.

Jan 1, 2001

By Peter Ehren

Global Geoscience is developing a Rhyolite Ridge project, a shallow boron-lithium resource deposit, located in Nevada about 25 km from Albermarle’s Silver Peak operation. The main minerals of interest are the boron mineral searlesite (40%wt) and lithium containing clay minerals. These minerals are found among principally calcite, feldspar, muscovite, dolomite, and quartz. The equivalent commercial value is about 7–9% boric acid (H3BO3) and 0.8–1.0% lithium carbonate (Li2CO3) equivalents. Selective agitated leach tests at SGS Lakefield laboratory showed that searlesite can be acid leached between 20 and 75 °C and at a pH lower than 4. On the other hand, lithium can be leached between 20 and 75 °C and at a pH lower than 1. In other words, lithium can be recovered at low temperatures if sufficient free acid is available, which gave the motivation to investigate heap leaching of the mineral. The PLS contains boric acid, magnesium, sodium, lithium, potassium aluminium, and iron sulfates.