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By Dachun Liu, Yifu Li, Baoqiang Xu, Yongnian Dai, Bin Yang

"The removal of impurity arsenic from crude tin is one of the major problems in the process of tin refining. Through a thermodynamic analysis on vacuum refining process of crude tin, the vapor pressure of impurity arsenic under different temperatures can be obtained, which demonstrates that it is possible to separate tin and arsenic by the vacuum refining process. This paper attempts to verify the behaviors of impurity arsenic. The experiment result shows that through vacuum distillation, crude tin with 0.16% arsenic can be refined from crude tin with 0.96% arsenic, and about 50% impurity arsenic can be collected in the form of metallic arsenic.PrefaceThe crude tin obtained by the reduction process is insufficiently pure for most applications, even smelting from tin concentrate. Arsenic is a common impurity in crude tin and also one of the predominant elements to affect tin performance. Arsenic is a poisonous metal that has long been linked to an increased risk of cancers, diabetes, thickening of the skin, diseases of the liver and digestive complications, so there is a mandatory limit on the amount of arsenic (<0.015%) in tinfoil wrapper and tin layers for food packaging. Arsenic causes a poor appearance and plasticity, and increases viscosity. The impurities content of crude tin fluctuate over a wide range; a lot depends on composition of tin ore concentrate, treatment method and technological process before reduction smelting. And the content range of arsenic is usually 0.5~4%, but it is higher in some factories."

Jan 1, 2012

Convential smelting of copper - cobalt - iron sulphide concentrates result in th eoxidation of cobalt and iron, which are subsequently lost into the slag. The emission of SO2 bearing gas from smelting causes serious health and environmentsl problems. In this investigation, three different types of copper - cobalt - iron sulphide concentrates, derived from froth flotation, were investigated, the concentrates, each containing more than 40 wt % percent gangue material, were directly reduced in the presence of lime and corbonin the temperature rnage of 1073 K - 1573 K, fo rthe production of an alloy containing copper, cobalt and iron. We demonstrate the basic principles of process physical chemistry for the recovery of alloy by carrying out a detailed process analysis utilising the predictions from thermodynamic equilibrium and results from the kinetics of reduction reaction. The effect of temperature on the reduction kinetics and alloy formation were determinedand analyzed in detail.

Jan 1, 2012

By Ana Bohé

Nowadays, Gas-solid processes are widely used in the industry. The chloration and carbochlorination of metallic compounds are some of this kind of non catalitic heterogeneous reactions. In particular those related with extractive metallurgy of refractory elements (Zr, Ti, Nb, Ta, RE, etc). The development of materials to be used in reactors at elevated temperatures and with high corrosion performance, enhance the application of this kind of processes. Although they are currently carried out in the production of many comodities, the mechanism of most of them are yet not well understood. The present work is a deep discussion on the most important aspects to take into account for determining the mechanism of gas- solid reaction, and those criteria fulfil in this analysis were applied to chlorination and carbochlorination examples. The microstructural characteristic of solids, the mass and heat transfer phenomenon, the adsorption and desorption of gaseous species on active surface, surface diffusion processes and chemical elementary steps, which are the mainly contributions to the mechanism of these reactions were analysed. Furthermore, the effect of them on the reactivity of solids and the control step of the reactions were determined. The application of catalitic mathematical models to this kind of reaction and the modification for the better interpretation of experimental results is also undertaken. The most appropriate experimental procedures for following these reactions and the microstructural characterization techniques needed to be use in each case, there limits and applicability are also indicated.

Jan 1, 2006

By Yoshio Waseda

A laser flash method has been applied to obtain the thermal diffusivity values of Zr55Al10Ni5Cu30 alloy in the liquid, glassy, crystallized and supercooled liquid states. The electrical resistivity of this particular alloy was measured in the glassy, and crystallized states by a direct current four probe technique. A specific heat of Zr55Al10Ni5Cu30 alloy was also determined by a differential scanning calorimeter in the glassy state. On the other hand, thermal diffusivity values for two alloys of Zr60Al15Ni25 and Zr65Al7.5Cu27.5 were measured in the crystallized and liquid states. The thermal diffusivity values of three Zr-based alloys in the liquid state are summarized in the linear equations with positive temperature dependency and it is noted that the lower the thermal diffusivity values of Zr-based alloys at liquidus temperature, the lower the critical cooling rate to obtain metallic glass phase becomes. The thermal diffusivity values of Zr-based alloys were compared with those of Pd-based alloy case. These results suggest that thermal diffusivity of alloy liquids might be an indicator of the glass-forming ability of Zr-based and Pd-based alloys.

Jan 1, 2006

By I. Sofia Fernandez del Rio

This paper describes a process for the treatment of the dusts generated during the operation of blast and reverberatory furnaces in the lead smelter, to remove zinc, cadmium, arsenic and halides from the circuit. The process consists of a Pefloles' developed leaching/purification stage and a solvent extraction process developed by Lurgi. The plant capacity is 5,000 tonnes Zn/year. The feed to solvent extraction contains 8 g/1 Zn. Impurities such as copper, iron, arsenic and cadmium are removed by conventional cementation processes. The cadmium product is 99.99 % pure. The solvent extraction process consists of two extraction stages, one washing stage and two stripping stages. D2EHPA is used as the extraction agent and 25% ammonia as the neutralizer. The rich-zinc solution is sent to the electrolytic zinc plant for zinc recovery. The raffinate produced, which is a mixture of ammonium sulfate and chloride, is used for agricultural applications.

Jan 1, 2000

By G. C. Yao

Branch and needle-shaped intermctallic compounds of iron, silicon and aluminum normally exist in the molten aluminum. If a suitable amount of manganese metal is added into molten aluminum, the shape of the intermallie compound particlcs may become lumpish and spherical. According to the difference in electric and magnetic properties of these impurity particles and molten aluminum, these impurity intermctallie compound particles can be separated by applying an alternating magnetic field. In this experiment the alternating magnetic field was formed by a "C" type loop with AC (50Hz) current. The inner vacuum of the fireclay refractory separator is 25>< 15" 130mm3 with a lateral baffle inside. The separator was put into the interspace of the "C" type loop. It was found that the longer the separation time, the larger the amount transferred of impurities. The amount of transferred impurities increases with the increase of separation time and intensity of magnetic field. The addition of manganese metal enhanees signifieantly the efficiency of impurity separation.

Jan 1, 2003

By James C. Barker

Near Rainbow Mountain in the east-central Alaska Range an ultramafic complex forms a sill-like intrusion composed of dismembered bodies exposed along the south side of the Denali Fault and Broxson Gulch Thrust. The complex comprises dunite and peridotite with lesser gabbro, which together exhibit poorly defined, steeply-dipping compositional layering. The complex hosts four types of copper-nickel occurrences which have characteristic platinum-group elements (PGE), gold, and cobalt distributions. Three of the occurrence-types are considered to have formed as a result of primary mineral segregations which developed during intrusion of the complex. The fourth type of copper-nickel occurrence formed as a result of post-magmatic hydrothermal fluids at intrusive contacts. Scanning electron microscope examination indicates that PGE occur as micron-size telluride and arsenide minerals.

Jan 1, 1987

By Tae-Hyun Kim, Shun Myung Shin, Jin-gu Kang, Jeong-Soo Sohn

We investigated about synthesis of Mn-Zn ferrite with spinel structure using sulfuric acid leaching solution of mixed spent zinc-carbon batteries and spent alkaline batteries. The waste batteries were prepared by physical treatment such as crushing, magnetic separation, and screening. After screening, the crushed batteries were separated to +8 mesh and -8 mesh powder. Among these, under 8 mesh powder was selected for leaching test. The leaching test was investigated at 2 M H2SO4, 4 vol.% H2O2, reaction temperature 60 ?, agitation speed 250 rpm, solid/liquid ratio 50 g/ 500 ml, reaction time 1 h. The leaching efficiency of zinc, manganese and iron were 99.0%, 98.9%, 58.5%, respectively. For co-precipitation of zinc, manganese and iron, 5M NaOH solution was used for pH control. Then in order to synthesize Mn-Zn ferrite powder, it was investigated according to reaction temperature, agitation speed and O2 partial pressure. We could synthesize about 20 nm of Mn-Zn ferrite with spinel structure.

Jan 1, 2008

By Peiwei Hu, Min Lu, Tiejun Chen

Based on the analysis of properties of vanadium tailing (VT), the surface modification study was carried out as a polymer filler. The modification effects of the three kinds of coupling agents on VT and the mechanical properties of polypropylene (PP) composites with a modified vanadium tailing (MVT) were compared to determine the suitable surface modification agent and modification processes for VT. The results show that the best one is aluminate coupling agent DL-411. When the content is 1.2 wt% and the temperature was 100 °C, the activity index of modified vanadium tailing (MVT) is 95.53%. FTIR analysis shows that DL-411 has the strongest binding ability on VT. XRD analysis shows that VT has a heterogeneous nucleation on PP to induced b form formation, and DL-411 could enhance this nucleation. So the composites has higher strength and better toughness. When the content of MVT is 10 phr, the tensile strength, impact strength, flexural strength and flexural modulus of the composites are 47.51 MPa, 38.43 kJ/m2, 59.57 and 1654.36 MPa, respectively.

Mar 1, 2018

By Reuben John Mathew

"Oxygen evolution is the main anode reaction in industrial copper electrowinning. The oxygen bubbles do not conduct electricity, thus increasing the electrolyte resistance. The oxygen bubbles formed at the anode rise to the surface, occupying a larger volume of the electrolyte at the top of the cell than at the bottom. This oxygen bubble concentration gradient contributes to a gradient in electrolyte resistance and consequently a tendency toward uneven current distribution. This phenomenon increases the chance for uneven growth on the cathode and/or short-circuits, particularly on the lower portions of the cathode. This issue may be ameliorated by increasing the charge transfer resistance for oxygen evolution down the height of the anode. This concept was studied by solving the current distribution for a 2-D model of a copper electrowinning cell using COMSOL.IntroductionA copper electrowinning tankhouse aims to operate at the highest current density that will deposit on the cathode a layer of copper metal possessing the desired physical and chemical characteristics. The operating current density is directly related to the physical nature of the copper deposit on the cathode (Figure 1), limiting a copper electrowinning tankhouse to some operating current density that produces acceptable copper deposits.[!] The ratio of the operating current density to the limiting current density is typically around 0.3.[2] If the limiting current density for a cell could be raised, the operating current density could also be raised and thus result in savings in capital cost for a tankhouse. [3]The average operating current density in a copper electrowinning plant is 270A·m- 2 .[4] The value for average current density, however, obscures the fact that the face of a cathode does not experience this value equally. Indeed, the current density varies along the height of an electrode and is independent of the height of the electrode.[5] This phenomenon partly explains why the lower portions of a cathode tend to display a rougher copper deposit.In order to utilize a higher operating current density but still remain at 30% of the limiting current density, the limiting current density must be raised, but it is affected by the mass transfer regime at the electrodes. The mass transfer regime is currently poorest at the lower portions of the cathode and this is part of the reason for the tendency for poor cathode deposits to occur at the lower portion of the cathode.[6]"

Jan 1, 2012

By Jin Liu

In the early 1990?s, Inco successfully installed two new flash furnaces as part of their SO2abatement project to reduce SO2 emissions from the Copper Cliff Smelter by 60%. The flash furnace off-gas is cooled and cleaned through two new Monsanto Dynawave gas cleaning systems that replaced the traditional venturi scrubbing system. It was discovered that the flash furnace production capacity is often limited by the capacity of the gas cleaning system. The key task is to eliminate pressure drop from the system. The froth column is responsible for by far the largest pressure drop in the gas cleaning system. Initially, the column was fitted with 22 plates. In 1994, both #1 and #2 froth columns were modified by reducing the number of plates in each column from 22 to 18 and increasing the interplate spacing on lower plates. With increasing demand for more throughput in the flash furnaces, further modifications on the froth columns were made in 2005. This paper describes these modifications and results together with some fundamental analysis of the froth column characteristics.

Jan 1, 2006

By Wang Shuchan, Zhang Zimu, Zhang Dianhua, Liu Yan, Zhang Ting-an, Zhao Qiuyue, Lv Chao

Rare earth extraction tank has many adverse effects like big floor space and high production accumulation during industrial production. Current researches usually focus on changing the device structure without making a breakthrough towards gravity clarification. This paper attempts to achieve this goal by using both the action of clarification by gravity and clarification by stirring. Because many physical parameters affect the clarification and separation rates, the density, viscosity and surface tension of the two phases were determined at different temperatures and different concentration of aqueous solution. The innovation of this research involves adopting the Karl-Fischer method to investigate water content in oil phase during the stirred separation process. In this paper, the separation effect of different physical parameters was studied and the dimensional equation between water content and the physical parameters was established by combining with the experimental data.

Jan 1, 2014

By A. Rohkohl, R. Piillenberg

The QSL plant at "BERZELIUS" Stolberg GmbH in Stolberg, Germany was commissioned in 1990, introducing a new era of lead smelting in the more than 150-year-old history of the lead smelter. The lead smelter in Stolberg has changed its appearance several times during its existence. Therefore, at many locations on the site, old and obsolete buildings and equipment parts can still be seen. They are often located side by side with new modern constructions like the QSL-plant and the mercury removal plant, and reflect the specific contrast between tradition and modern technology. After a brief description of the development of the smelter and its decision to implement the current novel plant, the most recent operating results are reported. Following some modifications to the process and equipment, which had become necessary along with the implementation of the new technology, the plant is in operation today at approximately 30% above its design capacity. These achieved production levels are not restricted by the QSL-reactor but by precedent and subsequent available equipment. The QSL-plant entirely complies with the demands of modern, energy-saving, ecologically compatible lead production technology. Stringent environmental standards are maintained on a continuing basis. The demonstrated viability and flexibility of the overall process permits the operation to adapt quickly to the prevailing economical situation worldwide.

Jan 1, 2000

By Vladimir Lobanov, Pritchinm Alexander, Nikifor Ageev

"Sulfuric anhydride is one of the most voluminous technological emissions. The possibility of high-temperature SO2 oxidations without catalyst in presence of calcium-bearing filling materials (CaO, Ca(OH)2 and CaCO3) with obtaining of binding material on the basis of waterless calcium sulfate is studied. Due to application package HSC-4 the thermodynamic analysis of the specified interactions is made and following conclusions are drawn: 1) Reactions are feasible in the all range of investigated temperatures (400 – 1000 °?); 2) The best results should be expected at use of ???; 3) The heat of reaction does possible autogenous behavior of process. The researches have shown: 1) Practical possibility of the process; 2) SO2 oxidation without the catalyst is feasible in presence of ???, Ca(OH)2 and CaCO3; 3) The optimum temperature range is 600-800 °?; 4) The content of waterless calcium sulfate in a product reaches 48% that makes it possible to use as the binding material; 5) At excess of ??? the degree of SO2 collection is nearer to 100%. Introduction At processing of sulfide raw materials in metallurgical furnaces the significant amount of sulfur, mainly in the form of sulfuric anhydride is escaped. Rich gases (SO2>3 %) are used for the sulfuric acid or element sulfur production. Chemism of sulfuric acid manufacturing is based on catalytic high-temperature oxidation of anhydride. Poor gases of metal works (SO2 =2,5 %) and power combustion units (SO2 =0,5 %) after clearing discharge into the atmosphere. Commonly, to recovery of weak sulfuric anhydride the chemical and physicochemical methods are applied. A few chemical ways of recycling sulfur dioxide are applied practically. In a number of methods for SO2 recovery a pulp of metals oxides (magnesium, zinc, etc.) with formation of sulfites is used. In other case sulfuric anhydride is catch by weak sulfuric acid in the presence of an oxidizer (pyrolusite ore). Methods of absorption SO2 by solid sorbents, (carbon fibers, silica gels, zeolites) are known and put into practice. Regeneration of the saturated sorbents is realized by thermal decomposition or extraction. Obtained as a result high-concentrated solutions are a commercial product."

Jan 1, 2008

By Ricardo Morales

Reactions between solids and a gas phase have many interesting theoretical aspects as well as technological applications. The present group had carried out experimental investigations as well as theoretical studies of a number of gas-solid reactions over the past decade and was able to derive interesting results. Studies of the decomposition of alkaline earth carbonates were carried out by thermogravimetric analyses. The experiments were carried out using thin powder beds as well as iso-statically pressed compacts with thermocouples embedded in the same. The investigations revealed the complexity of the reactions and the impact of the heat- and mass transfer aspects on the reaction kinetics. In the case of BaCO3, the kinetics of decomposition was complicated by the formation of a liquid phase. In the case of SrCO3, the reaction kinetics could be simulated by theoretical modeling. Gas-solid reactions were also employed as a versatile process tool towards the production of alloys and intermetallics involving transition elements by hydrogen reduction of complex oxides involving transition metals. Thin powder beds were employed to examine the micro-kinetics, while fluidized bed technique was utilized to produce bulk alloys. Preliminary correlations could be drawn between the thermodynamic stabilities of the oxides and the activation energies of chemical reduction steps. Adjusting the process parameters, products at nano-scale could be produced. The structural, mechanical and thermal properties were investigated in the case of these products. The potentialities of this method as a green route to produce industrially important alloys and intermetallics with unique properties are demonstrated.

Jan 1, 2006

By Jianhui Wu, Jing Zhan, Chuanfu Zhang, Zhijian Wang, Chu-ping Xia

"A novel technology about interactive roast of complex bismuth sulfide ore with low grade and Pyrolusite was put forward using the low-grade bismuth sulfide ore and pyrolusite as raw materials. The predominance diagram of Bi-Mn-S-O system was drawn by thermodynamic calculations. Stable coexistence area ofBizO3 and MnSO4 and its control condition was obtained. The interactive roast conditions including roasting temperature, roasting time, the ratio of n(MnO2)/n(S), ventilation rate and so on are investigated systematically. The results show that the sulfur-retained ratio reaches about 98%, in which formation rate of MnSO4 was 94.04%, most of the residual sulfur in the ore exist in the form of BhsO32(SO4)10 in the roasting products The optimum roasting conditions were as follows: roasting temperature of 650°C, roasting time of2h, 1.4 for n(MnO2)/n(S) and 140L/h for ventilation rate.IntroductionBismuth is a ""green"" rare metal with the characteristics of safe, nontoxic and low melting point[l].The use of bismuth and its oxides is extending from traditional fields such as pigment, fusible alloy, bismuth class of drugs and metallurgical additives to the high-tech fields such as semiconductor, high-temperature superconducting materials and nuclear power and so on. Bismuth is one of the precious advantageous resources in China which owns the most abundant bismuth resources in the world. Bismuth metallurgical process is divided into the pyrometallurgy and hydrometallurgy [2-4]. Hydrometallurgy for bismuth is mainly used for the processing oflow-grade complex bismuth ore, whose key steps are oxidative leaching process of the bismuth sulfide ore by strong oxidants(FeCb, Clz, HNO2 etc) in hydrochloric acid system. Therefore, the corrosion of strong oxidants, high demand for equipments and poor operating environment are its inherent disadvantages. Pyrometallurgy for bismuth is mainly used for the processing of high-grade bismuth raw materials or concentrate, which is the main method for bismuth metallurgy at present."

Jan 1, 2013

By Xingming Zhang, Huawei Zhang, Yanxiang Li

"A hybrid porous metal with nano-micro double scale pore size and regular-random bimodal porous structure has been fabricated by unidirectional solidification of a lotus-type alloy followed by dealloying treatment to the base alloy. The base alloy selected is a Cu-Mn binary alloy. The lotus-type porous Cu-Mn alloy with straight pores of several hundred micrometers in diameter was manufactured by unidirectional solidification with a mould casting process. Dealloying treatment was then done to the lotus-type porous structure of Cu-Mn alloy. The solid Cu-Mn alloy wall of the lotus-type porous structure was transformed to random porous structure of dozens to hundreds nanometers. The influence of corrosion parameters, such as the current and time in electrochemical corrosion, temperature and corrosion agent in chemical corrosion, on the nano-porous structure formed has been studied systematically.1. IntroductionA hybrid porous metal is a kind of cellular structure with different porous or cellular forms inside, which possesses special properties and can be applied in many fields as fuel cells, catalysis, sensors, etc. Several means have been developed to fabricate this kind of porous material [1-2]. In this paper, a novel process of Gasar plus dealloying is introduced to fabricate a new form of hybrid porous metal with nano-micro double size and regular-random bimodal structure.The Gasar process, also called the metal-gas eutectic directional solidification, that invented by Shapovalov [3] in Ukraine and now in USA some twenty years ago, is used to fabricate porous metals with regularly aligned pores basing on the solubility difference of a gaseous element in solid and liquid metal. Nakajima and his colleagues [4] in Japan studied this process further and called this kind of structure a lotus-type porous metal. They put more attention to various fabrication techniques and properties of lotus-type porous metals. Li heading a group [5-6] in P.R. China studied the mechanism of Gasar process and process controlling techniques. The Gasar pore structure and porosity can be controlled by processing parameters, and a regular Gasar structure with oriented pores distributing uniformly in the solid matrix can be obtained under optimized processing parameters."

Jan 1, 2014

By E. M. Timoshenko

Autoclave technology can be effectively used for liberation of complex mineral raw materials to transfer valuable constituents into solution for their subsequent recovery or to refine feed material in order to remove deleterious impurities, e.g. arsenic. The high efficiency of autoclave processes is attributed to the fact that they are suitable for processing of refractory raw materials, have low capital costs, high productivity, ensure integrated utilization of the feed materials, produce innovative saleable products, completely eliminate any air emissions, provide low-waste or waste-less technology, mechanization and automation of production processes. In the immediate future, it might be expected that autoclave processes will find use on commercial scale for production of heavy non-ferrous metals in combination with other processes (hydrometallurgical, upgrading, sorption and solvent extraction, electrolytic, etc.) to ensure: - Integrated processing of refractory ores and concentrates (pyrrhotite, zinc, copper-zinc, lead-zinc, nickel-cobalt, copper, pyrite); - Production of metallic powders of base metals as commercial products (copper, cobalt, nickel, etc.), composites on their bases, final products and saleable salts. Processing technologies incorporating autoclave processes, especially at the stage of liberation (chemical upgrading) of raw materials are characterized generally by high overall recoveries of valuable constituents significantly exceeding recoveries common for conventional pyrometallurgical processes (for some elements by several tens of percent).

Jan 1, 2006

By Sung-Joo Lee, Gi-Chon Han, Nam-Il Um, Hee-Chan Cho

"In Korea, almost all of bottom ash produced by coal power plants is disposed of in ash ponds. Ash storage areas comprise more than 80% of most coal power plant sites. This disposal method is causing environmental problems and a managerial burden for plant operators. In this study, investigations to develop a beneficiation process for separating coal pond ash into various products were undertaken. To improve efficiency of the separation, coal ash was separated by sizes and each size fraction was subject to various beneficiation processes. The separation process used were flotation (-200 mesh size), hindered settling (16x200) and tabling (16x200 and 8x16 mesh). The results showed that various marketable products, such as lightweight aggregate, sand, high-carbon fuel, could be recovered from coal pond ash using simple physical separation techniques.IntroductionDue to the increased use of coals every year, about fifty million ton of coals were used in 2007 alone. As a result, about 6 million tons of coal ash were generated. In Korea, the coal bottom ash is classified as a general industrial waste and is usually disposed of in ash ponds. The costs for this disposal method continue to increase due to rising costs of site management and development and more strict environmental regulation. Therefore, utilities are constantly looking for ways to increase utilization of coal ash. In this study, various beneficiation processes were evaluated to examine the possibility of separating coal pond ash into various products which can be used as aggregates and high-carbon fuel."

Jan 1, 2008

By Jeong-Soo Sohn

Physical treatment and chemical treatment of spent lithium-ion battery were studied in our research team. Especially we developed two types of acidic leaching for crushed powders containing LiCoO2 of spent lithium ion battery. One of them is sulfuric acid leaching with H2O2 as a reducing agent. The leaching rates of cobalt, lithium and the other metals were above 99 % at the condition of 2 M H2SO4, 10 vol. % H2O2, 75 °C, 300 rpm agitation speed, 250 g/5L solid liquid ratio and 75 minutes reaction time. And the other leaching process is the oxalic acid leaching. In this process more than 99% of Li and less than 1% of Co were dissolved at the condition of 3M oxalic acid, 80°C reaction temperature, 300rpm agitation speed, 50g/L initial solid/liquid ratio and 90min extraction time. Each process has its advantage and disadvantage. In sulfuric acid leaching, leaching reagent is very cheap and cobalt could be recovered into cobalt hydroxide. On the other hand, oxalic acid is more expensive than sulfuric acid but lithium could be dissolved selectively. Also cobalt could be recovered into cobalt oxalate and it could be changed into cobalt oxide after heat treatment. In order to select the effective recycling process, recovery rate and purity of cobalt hydroxide and cobalt oxalate were compared and it was investigated which process was more environment-friendly and economical.

Jan 1, 2006