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By Giuseppe Granata

An innovative process using titanium tetrachloride (TiCl4) gas as reactant has shown successfully to obtain titanium through electro-winning of TiCl2 formed in-situ on titanium cathode. The process involves a continuous feed of TiCl4 gas reacting onto a titanium cathode immersed in a molten salt (NaCl-KCl), whereby in-situ formation of titanium dichloride (TiCl2) through a disproportion reaction. Simultaneously, the TiCl2, thus in-situ formed in the molten salt media, has been reacted into chlorine gas and titanium, the latest electrodeposited on the titanium cathode by electrowinning. The reaction kinetic of this innovative process was investigated in terms of TiCl2 in-situ formation rate and galvanostatic electrodeposition rate, where, in particular, the effect of operating variables such as TiCl4 partial pressure and flow rate, as well as temperature and galvanic potential applied was investigated.

Jan 1, 2014

By Oleg Ostrovski

Industrial pyrometallurgical processes in ferrous metallurgy are based on carbothermal reduction of metal oxides. Carbothermal reduction of stable oxides requires high temperatures. Lowtemperature reduction can be implemented by using methane-containing gas with high carbon activity, or by carbothermal reduction under reduced CO partial pressure. Under standard conditions, methane is thermodynamically unstable above 550 °C and decomposes to solid carbon and hydrogen. At appropriate CH4/H2 ratio and temperature, carbon activity in the methane-containing gas phase can be well above unity relative to graphite, which provides favorable thermodynamic conditions for reduction. To maintain these conditions, the rate of reduction/carburisation should be higher than the rate of solid carbon deposition. The paper discusses reduction of pure manganese and chromium oxides at relatively low temperatures, and constraints in reduction of manganese and chromium ores. Reduction of metal oxides by carbon in hydrogen as an alternative use of natural gas is also discussed.

Jan 1, 2014

By Young-Chul Kang

The Onsan Copper Smelter of LG-Nikko Copper Inc. is a unique plant, which has been operating two smelting processes since 1998. The operation of the first one was started in 1979 with a capacity of 80,000tpy of copper in concentrates utilizing Outokumpu flash- smelting technology. The other one was started in 1998 based on Mitsubishi continuous process with a capacity of 160,000tpy of copper in concentrates. Through several expansion projects, the total smelting capacity of both processes is expected to reach 430,000tpy of copper in concentrates towards the end of 2002. This article describes operation advantages of having two different processes at one plant and comparative operation results in terms of productivity, impurity distribution, energy consumption and environment issues and etc?

Jan 1, 2003

By Oscar Perales Perez, Atsuo Kasuya, Kazuyuki Tohji, Yoshiaki Umetsu

"The removal of iron and various heavy-metal ions by their incorporation into stable ferrite-type precipitates at 25°C is a promising alternative to clean up large volumes of polluted aqueous effluents. Our research work investigated the conditions to produce magnetite and various M-bearing ferrites (where M: Zn, Cu, Co, Ni, Cd, etc.) directly from aqueous solutions at 25°C by simultaneous control of the oxidizing conditions and pH. The formation of the solids was followed by monit9ring the oxidation-reduction potential (ORP) and rate of proton release during the aerial oxidation of the suspensions at constant pH (contact stage). Only mildly oxidizing conditions, represented by ORP values between -110 mV and -150 mV and a moderate oxidation rate of Fe(II) species were conducive to well-crystallized ferrites at ambient temperature.' It was also found that increasing the Fe/M mole ratio in starting· solutions enhanced the stability ·of the M-bearing ferrites at ambient temperature. When the formation of the ferrite was incomplete, aging of the sludges in their mother liquors at 25°C promoted the crystallinity of the precipitates. The mentioned conditions ·favored the suitable progress of the ferrite-forming reaction involving the oxidation of Fe(II) entities, subsequent hydrolysis of produced Fe(III) species and dehydration of the intermediate:· Furthermore,· the ferrite formation at· low temperature permits the elimination of iron and co-existing heavy metal ions to sufficiently low concentration.In tum, the characterization of the precipitates evidenced their magnetic nature (room-temperature saturation magnetization above 60 emu/g) as well as the effective incorporation of target metal ions into the ferrite structure."

Jan 1, 2000

By Liu Chunpeng

Under an inert atmosphere, the temperature enhancement of nickel bearing pyrrhotite irradiated by microwave was measured with a special metal-sheathed thermocouple and the non-isothermal rate equations were obtained. Under the controlled oxygen potential of the reacting gas in the microwave field, over 90% sulfur contained in the pyrrhotite is converted into elemental sulfur directly, the iron and the nickel are transformed into FeO,, NiO, NiFe,O, and FeSiO,. According to the experimental data the rate of the elemental sulfur produced is in diffusional control and the non-isothermal equation derived is

Jan 1, 1993

By Shufang Ding, Fukun Yan, Zhiqiang Shan, Wei Chen, Cuicui Ji

"To remove aluminum ion from chlorinated rare earth solution, this paper used hydrolysis method to explore the hydrolysis behavior of aluminum ion in aluminum chloride solution and confirm the optimum conditions of aluminum ion hydrolysis, which are pH value, temperature and initial concentration of Al203 and so on. The experimental results show that single treatment can make aluminum precipitation rates of chlorinated rare earth solution reach about 90% by hydrolysis precipitation; and then several recycle disposal can get precipitation rates of 89% for aluminum and 2.86% for rare earth.IntroductionIn China, rare earth resources are very rich and unique minerals, complete variety, and rare earth products are very large in the domestic reserves. Rare-earth and application products have been deep into all areas of our life, permanent magnet material of rare earth is one of the most popular application areas[11. Binary oxides such as praseodymium neodymium have been widely applied in the fields of glass, ceramics, magnetic materials, catalysts and so on. Especially, the advent of the Pr-Nd-Fe-B magnets which makes the world magnetic material into a new stage of development [2•3]With the development of science and technology, for industrial, physical and chemical indicators of raw materials Pr-Nd oxides (such as particle size, specific surface area and non rare earth impurities etc.) are also getting higher and higher. The oxide size has an important influence on sludge formation in the electrolytic process. If the size is too large, added oxides have settled on the bottom of slot before melting, and then generated sludge; if the particle is too small, it can cause dust dispersion, enlarge oxide unit consumption and increase the cost of production in the charging process. Some early processes use oxalic acid to make chloride neodymium praseodymium settle, and impurity can be removed cleanly, but the cost is high, it is not suitable for production. At present, most enterprises are using ammonium hydrogen carbonate to precipitate chlorinated neodymium praseodymium, but chlorinated neodymium praseodymium such as iron and aluminum and so on can easily form gel in the precipitation process, seriously affect the growth of neodymium praseodymium carbonate crystal and often leads to particle meticulous, even may also generate gel-like neodymium praseodymium sediments and cause centrifugal or suction filtration difficult. Now the actions and their removal of impurity such as iron and aluminum have done a lot of research in the production process of rare earth, removing aluminum craft with alkaline (sodium hydroxide) and acid (oxalic acid) has good effect, but the cost is higher[41; used adding complex agent to remove aluminum method which is simple and easy to operate, but aluminum removal rate is not high, and also changed the sediment of crystal type[51, and etc. This paper discusses the removal of chlorine from rare earth solution on the basis of the hydrolysis property differences betweenAJ3+ and rare earth ion."

Jan 1, 2013

By Anne Kvithydl

Printed circuited boards contain considerable quantities of valuable metal, while also containing many environmental pollutants making them unsuitable for landfill. In this study the decomposition of common plastics used in printed circuit boards were studied. Polytetrafluoroethylene (PTFE), polyvinyl chloride (PVC) and polyethylene (PE) were heated in both CO, and argon atmospheres using a thermo-gravimetric furnace (TG) coupled to a mass spectrometer (MS). Soda ash Na,C03 and baking soda NaHC03 were used as reactants. The degradation temperatures and evolved gases are presented for single plastics and mixtures. Mixed plastics are shown to behave as a sum of the individual plastics. The mass loss temperature is the same in CO, and argon. However, less residue is formed when heated in CO,.

Jan 1, 2008

By A. E. Torma

In recent years the copper industry has gained considerable economic stability. An essential part of this industrial wealth is attributable to the successful application of bio-mediated heap and dump leaching techniques in the recovery of copper from low-grade resources. This study evaluated the leachability of a chalcopyrite conlentrate using naturally occurring mixed culture of predominantly Thiobacillusferrooxidans and Thiobacillus thiooxidans. For the effects-of pulp density, the overall reaction rate constant (k) and the order of reaction (n) have been determined to be 1.93 h-1 and 1.36, respectively. Cyclic voltammetric measurements revealed that intermediate reactions are involved in the chalcopyrite oxidation. Using the Price approach, it was shown that the dissolution of chalcopyrite is solid state diffusion controlled.

Jan 1, 1992

By Gordon Irons, Kevin Graham, Krishnakumar Krishnapisharody

Ladle or secondary metallurgy in steelmaking is an essential process step for the production of high-quality steel. Professor David Robertson was a pioneer in the modeling of these processes, in particular gas-metal fluid dynamic interactions and the rates of slag-metal reactions. This is now a highly active area of research, and some of the recent developments in this area will be reviewed.

Jan 1, 2014

By A. V. Tarasov, S. D. Klushin

493 The most common method for minimizing the copper content of residual slag in the process of autogenous smelting of sulfide raw materials is treatment of molten slag in an electric furnace, with optional addition of solid reducing agents, such as coke, and/or sulfiding agents such as pyrite. A drawback of this technique is the fact that the final slag produced still contains 0.5% or more Cu. We have tested a method for treating molten slag obtained as a result of autogenous smelting by a gaseous mixture of sulfur dioxide and methane at a ratio of. SC:SO2 = 0.75 :1.0 in the presence of oxygen. Interaction reaction within the SO2-O2-CRi system proceeded at a high rate at 1373 to 1573 K to form reducing and sulfiding agents: H2S, S, COS, CO, CO2, H2, H2O. The gas mixture requirement was about 100 to 150 Nm3 per 1 tonne of slag. A decrease in the ferric iron concentration (Fe3+) from 10-15% down to 2-3% resulted in lower solubility of copper in slag, and agitation of the melt with gas stream accelerated. the separation of the sulfide phase and slag. Removal of copper from slag was performed in a pilot unit within the second V anyukov furnace zone where slag arrived with a copper content of 0.8-1.3%. The temperature of molten slag was maintained within 1523 to 1573 K. The copper content of the final slag was at a level of0.12 to 0.14%. The matte sent to converting was a mixture of bottom matte from the smelting zone and the slag treatment zone. It had a copper content of about 50 to 55%. Process gases from both furnace zones were combined and sent to the acid plant for sulfur recovery. This process was offered for commercial use at two copper smelters in Russia and CIS.

Jan 1, 2000

By Guangchun Yao, Chuan Li, Hongjie Luo, Zhuokun Cao

"The expansion rate and collapse time of liquid aluminum foams are essential for the determination of operating time and quality of the resulting foam. In the present paper, liquid aluminum foams was fabricated by adding in TiH2 as blowing agent, and the variation of expansion rate with foaming time was non-contact detected by a laser distance measurer. The influence of different stabilizing agent and alloying elements was studied. The results show the fact that the fraction of stabilizing agent only perform little effects on the maximum expansion rate of liquid aluminum foams, while the influence of alloy elements are remarkable. The maximum expansion rate would increase much when Mg is added, and the liquid foam also collapse at a shorter time. Comparison was made between experimental results and mathematic calculations, which reveal the fact that it is the change of TiH2 decomposition responsible for the change.IntroductionMetal foams, combining light weight with other unique mechanical and physical properties, have gained wide interest and been developing fast during past few decades. However, manufacture of this new material is quite challenging since it involves simultaneous occurrence of gas, liquid and solid phase at high temperature [1-2].Quite some manufacture routes have been developed for manufacturing metal foams, and the structure and quality of resulting foam are remarkably improved during the last decades. However, most of the past works seems to be experiential, and because the lack of basic knowledge of foaming process, the start material is limited and the production technologies are far from reliable and reproducible.[3-4]In direct foaming process, decomposition of blowing agents, TiH2 for example, is the main force for foam expansion. The density and foam structure changes with time during the foaming process, so it is expected that foams of certain structure can be obtained by solidification of the liquid foam at a certain time [5-6]. However, the foaming process is weak in reproducibility and the influence of stabilization additives and alloying elements is unclear."

Jan 1, 2011

By M. Ide, K. Takemura, S. Taenaka, K. Shinzawa

"The laser characteristic is strongry dependent upon the stoichometry of forsterite (Mg2Si04) and YSO (Y2Si05) single crystals, because of change in the valency and occupied sites of doped Cr in the lattice so that mole ratios of Mg0/Si02 and Y203/Si02 in the above single crystals must be precisely analyzed. In this study ICP-AES was applied for analyzing the mole ratios. Emission intensities corresponding to Si and Mg or Si and Y were measured at the same time with internal standard method. Preparation of sample solutions, measurement conditions of ICP-AES and interferences by coexisting components were discussed, resulting in excellently precise detennination of stoichometry of the above single crystals.IntroductionIn conventional stoichiometric analysis of single crystals, the stoichiometry is detennined by analyzing each component separately with titrimetry and gravimetry techniques. On the other hand, by stoichiometric analyses using ICP-AES, emission intensities corresponding to components are measured at the same time with internal standard method. Consequently erros caused by variation of analytical condition are canceled out.Cr-doped Mg2Si04 and Y2Si05 syngle crystals are known as laser materials. The change of valency and occupied sites of doped Cr affect the characteristic of single crystal as aleser materials. The change of state of doped Cr.Stoichometric composition of Mg2Si04 is constructed by 2mole of MgO and 1mole of Si02, and Y2Si05 is constructed by 1mole of Y203 and 1mole of Si02. In this study, required analytical precision in component mole ratio is within an error of 0.0010 for Mg2Si04 (CV=0.05wt%), and within an error of 0.0030 for Y2Si05 (CV=0.05wt%) (Table I )."

Jan 1, 1998

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

"In the duplex melting process, chromium forms chromium spinels, the study of which will help to exploit the Hongge ores (rich in chromium) in the Panzhihua-Xichang area in China. Mimicked chromium slag was synthesized. The oxidation and decomposition mechanism of the Fe-Cr spinels contained was studied in a sodium roasting process. The effects of temperature, roasting time, amount of soda added and filling reagents were investigated. The leaching-reduction-precipitation-calcination procedure to extract Cr2CO3 was optimized. The results showed that the optimized roasting temperature was 1000~1020°C with a stoichiometric Na2CO3 addition and without any filling reagents. Roasted materials were leached with distilled water and were filtered to obtain a chromium-containing solution, which was adjusted to pH 1.60-1.80. A reducing reagent, NaHSO3, was added in a stoichiometric ratio and the solution was then adjusted to pH 7.25~8.25. Maximum Cr2O3 precipitation was obtained and the precipitate was calcined at 1050°C for 2h to obtain Cr2Ü3 with recovery rate over 96%.IntroductionChromium is widely applied in the metallurgical industry, in refractory materials and in the chemical industry with its particular properties of hardness, wear-resistance, high temperature resistance and corrosion resistance [1]. There is no free state of chromium in nature and chromite is the main chromium containing mineral [2], China is poor in chromium resources, despite its large demand, and there are few deposits of high grade of chromite ores except in some regions in Tibet and Xinjiang province [1, 4]. Hongge, one of largest titanomagnetite mines in Panzhihua-Xichang area, is a polymetallic deposit mainly containing iron and titanium; it is also associated with various beneficial elements such as chromium, copper, nickel, etc. [3]. As investigated in Reference 3, the chromium reserves of Hongge ores are so large that it is of great importance to study how to extract the chromium from them."

Jan 1, 2012

By Alejandro R. Alonso, Lizet Alvarado, Gretchen T. Lapidus

"Cobalt and lithium recovery from spent Li-ion secondary batteries has been increasingly studied in recent years due to the high value of both metals and the low proven reserves for lithium. The standard method employed until now has been the deactivation and crushing of the batteries, followed by leaching of the L1C0O2 spinel from the battery cathode using acid solutions, such as 1.5 to 2.0 M HC1 or H2SO4, in a temperature range from 120°C to 250°C. Once leached, the cobalt is separated by electrodeposition and the lithium by precipitation, using large amounts of carbonate to bring the solution to alkaline pH values. In the present work, citric-thiosulfate solutions are used for the spinel leach at room temperature, favoring a reductive environment at room temperature, which stabilizes the cobalt(II) as cobalt citrate and lithium(I) at pH 5, and recovers approximately 99% of both metals.IntroductionThe Li-ion batteries industry has become an important economic sector in recent years. This type of battery is the most promising system for energy storage, because of its high efficiency in charge-discharge cycles, and its adaptability to many configurations. The demand will probably increase because of the need for mobile energy sources in many types of devices ranging from cell phones, tablets, and laptops to medical, navigation and sophisticated communication equipment and even in automobiles.One major problem related to the use of these batteries is the method employed for recycling the components, mostly cobalt and lithium. Currently, there are two processes employed on an industrial scale: the Sony/Sumimoto process, used since 1990 [1] and the Toxco Process [2]. In the first case, incineration is used to open the batteries and at same time volatilize the organic solvents. After that, the metals (copper, iron and aluminum) are physically separated. The cobalt and lithium are recovered as oxides and then thermally treated in order to recycle them for new batteries manufacture."

Jan 1, 2012

By Fuqiang Zheng, Yufeng Guo, Pengfei Li, Guanzhou Qiu, Tao Jiang, Andrew Yakovlevich Travyanov

Low content of TiO2 and high impurities content of Ca and Mg are the shortcomings of domestic ilmenite. To meet the requirements of the material in the titania produced by chlorination process and titanium sponge industry, enrichment of ilmenite is necessary. In the process of enriching ilmenite, high temperature and reductive condition were beneficial to the formation of anosovite, but the high content of magnesium oxide which was solid soluble in anosovite baffled the following separation. So the effects of pre-oxidation and reductive conditions including reduction temperature, reduction time and hydrogen concentration on the phase composition and metallization rate were studied. The characteristics of reduction samples were analyzed by X-ray diffraction and optical microscope. Results have shown that the reduction product is mainly composed of Fe, Fe(Mg)TiO3 and TiO2 at 1123K, its metallization rate is about 65%,magnesium exists in Fe(Mg)TiO3.

Jan 1, 2015

By Zhihong Liu

In recent years, the removal of arsenic from different types of high arsenic containing materials produced in nonferrous metallurgical processes have been experimentally studied in the complex materials processing research group from Central South University. These materials include arsenic and antimony bearing flue dust, arsenic sulfide residue and arsenate bearing flue dust. The separation of arsenic from other valuable metals was carried out hydrometallurgically; for each type of arsenic bearing material, different processes have been employed individually to remove the arsenic effectively. In this paper, the flowsheets and typical experimental results have been summarized.

By Marco Antônio Siqueira Rodrigues

The possibilities for treating rinse waters fiom chromating bath by electrodialysis are discussed together with the possibilities of optimizing the treatment process for waste reduction and reuse of water and chemical products. An industrial effluent with 4600 ppm of Cr(VI), besides other metallic contamination, was used as work solution. This solution has been recirculated on an electrodialysis cell of three compartments, using exchange membranes Selemiom AMT and CMT. A migration of dichromate ions into the anodic compartment was obtained, so that an extraction of circa 99.9 % of Cr(VI) present on the solution was observed, resulting in water with a Cr(V[) concentration of 4 rnd. These results show that electrodialysis can be used to treat these effluents, and this water could be reused as rinse water. The solution of the anodic compartment, consisting at the beginning of the experiment of H2S04, 0.1 N, reached 7200 mg/l of Cr(VI). This concentrate could be reused on the chromating bath itself.

Jan 1, 1999

By Takeshi Ohgai, Hisaaki Fukushima, Tetsuya Akiyama, Joon-Seo Ki

"Recently, an intensive attention has been paid to the electrodeposition of Zn-Cr alloy in the field of the production of super-highly corrosion-resistant alloy plated steel sheets for the next generation. In this study the electrodeposition of Zn-Cr alloys from the sulfate baths was conducted to investigate the codeposition mechanism of Cr with Zn. As a result, Cr was codeposited with Zn at higher current densities in both polyethyleneglycol(PEG)-free and PEG- containing baths. However, PEG made it possible to reduce Cr+ to the metallic state and Cr existed in the form of Cr(III) hydroxide in the deposits obtained from PEG-free bath. The measurements of the partial polarization curve of Zn and the pH in the cathode layer revealed that PEG acted as a polarizer to shift the cathode potential to the reduction potential of the composited hydroxides of Zn and Cr formed due to the pH rise in the cathode layer.1. IntroductionRecently, much attention has been paid to the electrodeposition of Zn-Cr alloys because of its application to the production of super-highly corrosion-resistant alloy plated steel sheets for the next generation1Hl_ Some researches have already tried to commercialize this type of steel sheet. High corrosion-resistance of this steel sheet is brought about by codeposited Cr in the alloys. According to Piontelli's classification5l concerned with metal deposition from aqueous solution, Cr belong; to an inert metal and its deposition is associated with a large amount of hydrogen evolution. Therefore the current efficiency for Cr deposition is extremely poor. It has been also reported that Cr is unable to codeposit in the electrodeposited Zn film in the absence of a certain additive in the solution. 0-compounds group colloids7l, ether group organic compounds8), 9>, peptide based compounds10l, etc., have been found to be effective additives to induce the codeposition of Cr with Zn. However, few studies have been made on the codeposition mechanism of Cr with Zn. In this research, the fundamental electrodeposition behavior of Zn-Cr alloys from sulfate baths was investigated to clarify the codeposition mechanism."

Jan 1, 1998

By Michael K. Rhodes

A 120 tonne per day BacTech bacterial oxidation plant treating refractory gold concentrates for Gold Mines of Australia's Youanmi project in Western Australia commenced operation September 1994. This was the first commercial application of the BacTech process. A pilot plant trial on concentrates produced from Youanmi ore was carried out at BacTech's laboratory in Perth. Results and measurements from this trial were used by Signet Engineering Pty Ltd to design the commercial plant. This paper cover the results obtained from the piloting, their implementation in the plant design and the initial commissioning of the full scale plant.

Jan 1, 1995

By Xirneng Zhu

The electrochemical behavior of Pittsburgh and Illinois coal pyrite in basic and neutral borate/sulfate solutions was investigated. In the transpassive region, aggressive oxidation of pyrite occurred. The reaction products in this region were Fe(III) oxide, sulfate ion and partially oxidized sulfur intermediates. The formation of sulfur and polysulfides was identified by in-situ Raman spectroscopy. The growth kinetics of the reaction product film, resulting from transpassive oxidation of coal pyrites, were studied using chronoamperometry measurement with both stationary and rotating disk electrodes. The reaction rate was well correlated by a paralinear rate equation. The effects of electrode rotation speed, solution pH and temperature were examined. The kinetics were compared to those for mineral pyrite.

Jan 1, 1994