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By W. -D. Schneider, B. Schwab

Like all metals, zinc can be recycled theoretically without end. To demonstrate environmentally friendly use of zinc, it is necessary to increase the recycling rate. In this regard, the Imperial Smelting Process developed in the forties and fifties in the United Kingdom has become more and more important. This unique process combined with a sinter plant, hot briquetting, and direct injection through the ISP furnace tuyeres offers ideal possibilities to recycle all kinds of zinc and lead bearing materials. Possible secondary materials include Electric Arc Furnace (EAF) dust, zinc-containing sludges and even zinc/carbon batteries. This high temperature process also destroys all organic materials, like dioxin, and can be seen as a sink for many harmful substances.

Jan 1, 2000

By Leiting Shen

The thermodynamics of tungsten ore decomposition in mineral acid and alkaline solutions were studied. The published thermodynamic data of tungsten minerals were collected and assessed. The Gibbs energies of CaWO4 (−1538.43 kJ/mol), FeWO4 (−1053.91 kJ/mol), MnWO4 (−1206.08 kJ/mol), H2WO4 (−1003.92 kJ/ mol), and Na2WO4 (−1455.58 kJ/mol, aq) at 25 °C were adopted in the calculation using HSC software. The results show that CaWO4 is decomposed more readily in Na2CO3 solution than in NaOH,while FeWO4 andMnWO4 aremore reactive inNaOH solutions. Froma thermodynamic point of view, tungsten ore decomposes easily in acid solutions despite most ΔGo T increasing slightly with temperature. Oxidizing Fe2+ to Fe3+ in acidic solutions facilitates decomposition of FeWO4, and the reaction of CaWO4 in H2SO4 solution occurs more easily than in other mineral acids, due to the formation of sparsely soluble CaSO4. The results fit well with the experimental data and industrial experience previously reported in the literature.

By K. Osseo-Asare

It is possible to form a two-phase system in certain polymerlinorganic salt/water mixtures, such as those containing the polymer polyethylene glycol (PEG). Such aqueous biphase systems have many of the separation characteristics of conventional solvent? extraction systems, but are environmentally friendlier. Just like the well-known organic solvent/water two-phase system, the top polymer-rich phase is more hydrophobic. and the bottom salt-rich phase more hydrophilic. The partition of dispersed? particles is dependent on the interfacial interaction between the particles and the conjugate aqueous biphase solutions. In particular, the hydrophilic/hydrophobic properties of the surface determine the transfer of the dispersed particles into either the top (more hydrophilic) phase or the bottom (more hydrophobic) phase. Accordingly, differences in the surface chemistry of particles can be exploited to achieve selective separations. In this work, several approaches to separation control will be discussed. using pyrite (FeS2), alumina (AI203). hematite (Fe203), silica (Si02), and titania (Ti02) as model particulate materials. For metal sulfides, pH and redox potential can be used to alter the hydrophobicity/hydrophilicity of the particles. In ?the case of oxides. polymer adsorption and collector adsorption may be exploited to facilitate particle transfer.

Jan 1, 1999

By M. M. Kim

As-electrogalvanized coatings of pure Zn, Zn-11% Fe, and Zn-18% Fe coatings were characterized in terms of initial crystal structure and surface morphology. Samples were then subjected to heat treatments simulating the paint bake cycle of automobile manufacturers. Surface morphology changes were correlated with the process variables, and crystallo.graphic changes were interpreted by mapping heat treatment routes on the Fe-Zn phase diagram. The morphology of pure zinc electrogalvanized coatings with heat treatment from platelets to smeared platelets. The zn-11% Fe coating changes with heat treatment from tetrahedral nodules to a mixture of round and tetrahedral nodules, with the Zn-:18% Fe coating always having round nodules. Regarding crystal structure, a critical transformation time can be defined at any selected temperature, below which the crystal structure does not change. This temperature is related to iron content.

Jan 1, 1990

By Wiraseranee. Chompunoot, Kazuki Morita, Toru H. Okabe

"Aiming at the development of more effective recycling processes, dissolution behavior of rhodium into molten slag was investigated. Using a pure rhodium crucible and Na2O-SiO2 slag system, equilibration experiments were carried out for 18 h at 1423-1623 K under various oxygen partial pressures of 0.005-1 atm with varied slag basicity. Rhodium solubility increased with increasing oxygen potential, slag basicity, and temperature. Rhodium dissolved into slag as rhodate ion ([RhO2]-) by the endothermic reaction: Rh(s) + 3/4O2(g) + 1/2O2-(in slag) = [RhO2]-(in slag). In the dissolution reaction, the “rhodate capacity” of slag is newly-defined. The correlation between rhodate capacity and optical basicity is reported.IntroductionDue to its high chemical resistance and outstanding catalytic properties, rhodium (Rh), one of the platinum group metals (PGMs), is utilized in various applications such as catalysts, molten glass vessels and containers, and electronic devices. Owing to the rarity of Rh resources in nature, recycled Rh from scraps such as spent automobile catalytic converters is currently considered as an important source of Rh supply [1]. According to the recycling practices, Rh is currently mainly recovered from scraps along with other PGMs such as platinum (Pt) and palladium (Pd) by a dry process (e.g., smelting), a wet process (e.g., leaching and subsequent separation of PGMs from aqueous solution), or a combination of both processes [2]-[4]. Among these processes, smelting is commonly applied because PGMs can be effectively separated from a relatively large amount of various impurities coexisting in scraps. In the smelting process, Rh and other PGMs are collected in the collector metal (e.g., iron and copper), and impurities in scraps are removed into slag [4]-[6]. The process may be carried out at a temperature range of 1573-1973 K, in either an oxidizing or reducing atmosphere. Due to the high oxidation resistance at high temperatures, Rh is expected to be collected efficiently in the metal collector rather than being oxidized and forming RhOx in a molten slag. However, Rh loss into slag does occur in this process [7]."

Jan 1, 2011

By J. -S. Park, H. -S. Jeon

This study has been carried out to develop a relatively simple hydrometallurgical process for recovering nickel as nickel sulfate from the spent nickel-cadmium battery residue in which cadmium was removed by vacuum distillation. This residue is composed of 36 % nickel, 20 % iron, and other metals such as cobalt. First, crushing and selective classification were performed to separate iron to produce a nickel-rich product (over 40 % nickel). This product was dissolved in sulfuric acid to obtain a nickel sulfate solution. During the dissolution, nitric acid and air were added to the system to enhance the iron oxidation reaction rate. The free acid remaining in the dissolved solution was neutralized by adding nickel carbonate. Iron was precipitated as iron hydroxide and removed from the solution. The nickel sulfate solution was then fed to a vacuum evaporator to concentrate the solution by evaporation of water and crystallized at around 45°C to obtain nickel sulfate hexahydrate. A recrystallization process could remove other impurities such as zinc and manganese.

Jan 1, 2000

By Shoukun Wei, Cong Wang, Lin Cheng, Zhiyu Qiao, Jingkui Liang, Weidong Zhuang

"The subsolidus phase relations in the Sm2O3-CeO2-CuO ternary system sintered at 1000°C in air have been investigated by X-ray powder diffraction. The system can be divided into two ternary phase regions and three binary phase regions. Solid solution Sm2-xCexCuO4-y is the only ternary phase in the system. The maximum solid solubility was confirmed to be x = 0.2. The crystal structure, oxygen content and superconductivity of the solid solution Sm2-xCexCuO4-y have been investigated.I. INTRODUCTIONAfter the first discovery of the superconducting ceramic system La-Ba -Cu-O[l] with Tc = 30 to 40K, other families of cuprate-based ceramics have been synthesized with higher critical temperature. These oxides include the R-Ba-Cu-O (R: rare earth) systems (Tc=90K or so)[2,3], the Pb-Sr-(R,Ca)-Cu-O systems (T c = 50 to 100K), the Bi-Sr-Ca-Cu-O systems (Tc=80 to 105K)[4], the T1-Ba-Ca-Cu-O systems (Tc=85 to 125K)[5], the Hg-Ba-Ca-Cu-O systems (Tc=90 to 150K)[6,7], and some others. The improvement of Tc is very rapid. The measurement of the Hall and Seebeck coefficients shows that they all are p-type superconductors. In 1989, Tokura et al.[8] discovered the superconductors R2_XCexCU04_y(R = Nd, Pr, Sm) with Tc=20 to 24K (onset) and found that the charge carrier is electron in contrast to their hole doped counterparts. This discovery increases the fundamental understanding of the cuprate-based superconductors by comparing their characteristics and mechanisms to those of the p-type superconductors.One of the outstanding features of these n-type superconductors is the difficulty in obtaining samples in good charactors, such as the difficulty in obtaining zero resistivity state in single crystal or bulk samples; the semi-conductivity of bulk samples in ordinary state (opposite to the superconducting state) and a reducing reaction involved before the superconductivity has been found[9]. Therefore, it is necessary to optimize the sample preparation of the n-type superconductors. All the n-type superconductors have been found· considerable solid solubility. The compositional variations play a governing role in the carrier doping of the superconducting phases. Also, it is vital to the ceramic processing of superconductors to identify the compatible phases in the phase diagram. Finally, there is always the possibility of finding additional compounds, both superconducting and non-superconducting, in an unexplored system."

Jan 1, 1996

By J. K. S. Tee

Using a novel method, zinc has been selectively removed from galvanized steel scrap on a laboratory scale. The separation is based on thermodynamic principles: during chlorination in air-chlorine (10:l) mixtures at 800 OC, zinc forms a volatile product (zinc chloride) while iron does not chlorinate as its oxides are more stable than the respective chlorides. As much as 92 % of zinc is removed from the surface of steel within 10 minutes. This process overcomes tedious and costly preparatory stages associated with leaching - electrowinning methods.

Jan 1, 1999

By Kimio Itagaki

The distribution behaviours of the VA elements between the gas, slag and matte phases in copper smelting were evaluated on the basis of the thermodynamic data, most of which were determined by the authors. The distribution is basically dependent on the process factors such as temperature, the content of the element in charge, the amount of the waste gas and degree of vapour saturation with the elements. The thermodynamic quantities such as the activity coefficients of the VA elements in matte, the activities of iron and copper, SO2 or 02 potential and the distribution ratio of the elements between the slag and matte phases seriously affect the distribution, and the behaviours in various smelters could be explained systematically and reasonably by considering the changes in these quantities, In oxidation smelting at PSO2= 0.1 to 1 atm, the proportion of arsenic and bismuth in gas is predomi22t for the arsenic and bismuth distributions in both smelting and converting stages. The degree of vapour saturation has serious effect on the distribution, and sufficient contact between gas and matte phases is desirable for transferring arsenic and bismuth into gas phase.The elimination of antimony by means of vaporization is not significant. In reduction smelting at po2 = 10-11 atm, the proportions of arsenic and antimony in the gas phase are quite small, but the proportion of bismuth does not change significantly.

Jan 1, 1983

By Chunlin Chen

Nickel-sulfide minerals are normally associated with copper and iron sulfides and often contain a minor amount of valuable metals such as cobalt and detrimental impurities such as arsenic. Metal losses in slag vary from process to process during the pyrometallurgical production of nickel and, depend on the feed composition, slag chemistry and operating conditions. Maximiz the metal recovery is one of major considerations to optimize operating condition for nickel smelting/ converting processes. At the same time, the deportment of minor elements between various phases during nickel smelting is of great importance by smelter operators. The Multi-Phase Equilibrium (MPE) is a thermodynamic package developed by CSIRO for simulating reactions between phases in multi-component and multi-phase systems [1]. Over the years the capability of the MPE model has been extended to cover the behavior of a large number of elements in high temperature systems. The sulfide smelting module of the MPE, which covers the minor elements such as As, Bi, Sb, Pb, Se, Te, Sn, Co and Zn, is capable of modeling the deportment of major and minor elements between various phases during nickel smelting. In this article the application of the MPE model in modelling the nickel smelting process is presented. The modelling results on the majors and minors are compared with the plant data. The deportment behaviour of arsenic in nickel smelting was analysed and the impact of slag chemistry on slag properties was modelled. These results can assist process metallurgists in exploring the optimum fluxing strategy for smooth operation and the potential practices for improving arsenic removal.

By Donald R. Sadoway

"Molten salt electrolysis is a proven technology for the extraction of metals -- all· the world's primary aluminum is produced in this manner. The unique properties of molten salts also make them excellent media in which to treat a variety of forms of waste. Of special note in this regard is electrolysis in molten oxides, a concept put forward by the author, initially as a ""clean technology"" for producing primary metal. However, in the context of waste treatment, electrolysis in molten oxides is a process offering the prospect of changing the-valence of dissolved heavy metals while making pure oxygen gas as the main by-product. Laboratory tests conducted at a temperature of 1550°C on chromate sludge dissolved in an melt composed of Al2O3, SiO2; CaO, and MgO have confirmed electrochemical production of oxygen on a carbon-free anode. IntroductionMolten salt electrolysis is the electrolytic decomposition of a compound dissolved in an ionic melt. The prime example of this process can be found in the production of aluminum. The compound, alumina (Al2O3)' derived from the mineral bauxite, is dissolved in an ionic melt comprising a multicomponent solution of cryolite (Na3AlF6)' aluminum fluoride (AlF3)' and calcium fluoride (CaF2,). The products of electrolysis are molten aluminum and carbon dioxide, the latter due to the attendant consumption of the carbon anode. Primary aluminum is produced in a reactor known as the Hall cell.' Alternatively, the compound undergoing electrolytic decomposition can be derived from waste. Processing in molten salts, with their capacity to dissolve materials to very high concentrations compared to those attainable in aqueous solutions, can be rather advantageous. High solubilities lead to high limiting current densities, and this, in tum, results in high productivities: For a primer on molten salt electrolysis and a review of the basic literature in the field of molten salts the reader is directed to an earlier publication of the author (1)."

Jan 1, 1996

By K. Walanabe

Kosaka Smelter & Refinery has a history of more than a century as a metallurgical department belonging to Kosaka mine. It has treated for a long time the "Black Ore" or the complicated concentrates dressed from it. The "Black Ore" is composed of black sulfides. It contains not only valuable metals such as gold, silver, copper, lead and zinc but also some impurities like arsenic, antimony and bismuth. With the development of Kosaka's floatation technology, five kinds of concentrates (copper, zinc, lead, pyrite and barite) have been separated from the "Black Ore" but the separation was not complete and each concentrate contained some unfavorable impurities. In 1980s the highly appreciated yen and the drop of the metals prices forced many domestic mines to close their operations. Since then Kosaka Smelter has changed its way of operation to a custom smelter. Now more than 95% of copper concentrates are imported to take advantage of this technology of "Black Ore" treatment. It mainly treats the raw materials that contain high gold and silver like the "Black Ore". Recently, Kosaka has been working on the recycling of the metals from the printed circuit board scraps and sludge which contain some precious metals. The volume of the recycled metal is continuously increasing.

Jan 1, 2003

By Raj P. Singh

Applications of cementation in the recovery of metal ions from process solutions have been known for a long time. Cementation reactions involve electrochemical precipitation of a noble metal from solutions of its salts on a more electropositive metal which, in tum, progressively dissolves. For example, addition of zinc metal powder in a solution containing zinc and cobalt ions would allow for the precipitation (separation) of cobalt according to the following chemical reaction. This paper pertains to the recovery of cobalt from cobalt process solutions via a cementation reaction on aluminum shavings (metal scraps from cans etc). Specifically, we report on the characterization of cobalt process solutions, a by-product obtained from cobalt chemicals, and the kinetics of cobalt, nickel and manganese cementation from process solutions on aluminum shavings.

Jan 1, 2000

By Donald R. Sadoway

Molten salt electrolysis is a proven technology for the extraction of metals -- all the world's primary aluminum is produced in this manner. The unique properties of molten salts, also make them excellent media in which to treat a variety of forms of waste. Of special .note in this regard is electrolysis in molten oxides, a .concept put forward by. the author, initially as a ."clean technology" for producing primary metal. However, in the context of waste treatment, electroly-sis in molten oxides is a process offering the prospect of changing the. valence of dissolved heavy metals while making pure oxygen gas as the main by-product .Laboratory tests conducted at a temperature of 1550°C on chromate sludge dissolved in an melt composed of Al2O3 and MgO have confirmed electrochemical production of oxygen on a carbon-free anode.

Jan 1, 1996

By Du Sichen, S. Seetharaman, J. A. Bustnes

"The present study deals with the kinetic studies of reduction of some selected transition metal tungstates with hydrogen. The measurements were carried out by the isothermal thermogravimetric method. Shallow powder beds were employed in order to avoid the effects due to transport phenomena affecting the reaction rate. In this way, the chemical reaction rates could be selectively studied. The experiments were carried out in the temperature range 873 - 1173 K. From the experimental data, the activation energies were evaluated and were found to be around 88 kJ / mol in the case of both iron as well as cobalt tungstates indicating the similarities in W-O bonds in both cases. The activation energies obtained are discussed in the light of the position of the transition metal in the periodic table as well as the thermodynamic stabilities of the various tungstates.IntroductionThe tungsten containing hard metals, characterized by high density, belong to a class of two-phase metal matrix composites. While these types of materials have traditionally found their applications within the defence industry as armour-piercing projectiles, counterbalance in helicopters and military aircrafts, outer casings of hand-grenades, etc., commercial applications for this class of alloys also exist, including radiation shields, penetrators for the oil industry, turbines for turbo-jet engines and a wide range of sports related parts. A possible route to the production of these alloys is to reduce the tungstates such as FeW04, Co W04 and NiW04 using a reductant like hydrogen or carbon monoxide. In order to have a better understanding of the processes involved in the production, it is important to have a knowledge of the reduction kinetics for these tungstates. According to the knowledge of the present authors, while the reduction ofNiW04 by hydrogen gas has been investigated earlier in the present laboratorypl no systematic reduction study has been carried out previously for the tungstates of iron, cobalt."

Jan 1, 1996

By Qiu Dingfan

The Slurry Electrowinning Process (SEP) is a new hydrometallurgical method and clean technology, Sulfide ores can be treated by the SEP without S02 emission and the sulfur from the sulfides can be recovered in element form which is easy to stockpile and can be transported at low cost. In a special slurry electrowinning cell one can achieve at the same time the leaching of elements from the feed and the electrowinning of metals from the electrolyte, Because the anode reactions are utilized for leaching of some elements the consumption of the energy is decreased, SEP also has the advantage of separation some elements, It is especially suitable for treatment of complex concentrates containing Pb, Cu, Au, Ag and S, which could hardly be accepted by any smelter. In this work, the behavior of different metals in this process has been studied and it was found that the separation of metals in some minerals is possible through the SEP, Beijing General Research Institute of Mining and Metallurgy (BGRIMM) has studied the possibility of the SEP to treat bismuth concentrates containing S, Be and F in laboratory and pilot-test scale as well as in commercial plants, The commercial plant was set up in 1997, It has been in operation since that time, According to the results of laboratory experiments and pilot- plant test, a new plant to treat complex gold minerals was set up in 1998 and is in operation in 1999

Jan 1, 2003

By S. Yuan

Oxygen ion conducting yttria-stabilized zirconia (YSZ) tube was used to remove oxygen from molten Cu at 1373K. Outer surface of the tube was in contact with the melt and the inner surface containing a thin layer of porous Ni-ZrO2 cermet electrode was in contact with a reducing gas. The migration of oxygen species (O2-) from the Cu melt through the YSZ tube is accompanied by an equal and opposite flux of electrons maintaining electroneutrality. Without applying an external EMF, the fluxes are maximized by short circuiting the melt with the cermet electrode. For efficient oxygen removal, the YSZ tube must be thin, contact resistances should be negligible, and the electrodes must be porous and cover the entire electrolyte surface for charge transfer. This refining process is environmentally sound, can use reducing gases such as H2, CH4 and CO without running the risk of increasing H or C content of the melt.

Jan 1, 1993

By Uchil Jayagopal, P. V. Krupakara, S. Manjunath

"This paper deals with the corrosion characterization of quartz particlate ZA-27 alloy metal matrix composites (MMCs). Quartz particles of size 50-80 microns are used as reinforcement. MMC's are prepared according to ASTM standards. Composites containing. 2, 4, and -6% by weight of quartz and unreinforced matrix were tested using 1 -N hydrochloric acid: The composite was found to be more corrosive resistant than matrix alloy. In each test the corrosion resistance of both alloy and composites were found to decrease with the exposure time.1. IntroductionMetal matrix composites- (MMCs) offer designers many added benefits, as they are particularly suited for applications requiring good strength at high temperature, good structural rigidity, dimensional stability, and light weight 1-5. The trend is towards safe usage of the MMC parts in the automobile engine, which work particularly at high temperature and pressure environments Particles reinforced MMCs has been the most popular over the last two decades.ZA alloy MMCs have most popular families being represented by. ZA-27 alloy reinforced with ceramic particulate. Although the incorporation of the second phase into a matrix material can enhance the physical and mechanical properties of the base metal, it could also significantly change the corrosion behavior.ZA alloys have been used extensively in industry. This is attributed to their excellent fludity, castability and good mechanical properties. Among the zinc-based foundry alloys, the ZA family of alloy have been widely used during the past few years. ZA alloys have many advantage over aluminium based ones, especially high strength with a low casting temperature 8."

Jan 1, 2000

By V. P. Bystrov

Vanyukov process has been developed and investigated in Russia over the last 25 years. It has been established that various kind of material could be treated in Vanyukov process. The results of the pilot plant trials as well as industrial experience are presented in this paper.

Jan 1, 1993

By Theo Lehner

The Rönnskär smelter has wide experience in the field of recycling of non-ferrous metals. Today, smelting and refining from primary and secondary raw materials are integrated in a complex flow sheet. Boliden operates a lead flash smelter, a lead refinery, a copper smelter and refinery, a sulphuric acid and sulphur dioxide plant, a slag fuming plant and precious metal plant at its Rönnskär smelter in the North of Sweden. The Business Area Smelter Operations also incorporates Boliden Bergsöe, Sweden's lead-acid battery recycler, and Norzink, Norway, where recycled zinc accounts for more than 20% of it's production. Raw materials for the Rönnskär smelter include concentrates, ashes, slags, metallic scrap, electronic scrap and electric arc furnace (EAF) steel-making dust. This paper briefly describes current operations and illustrates current measures to improve productivity. Limits to recycling as experienced by a non-ferrous smelter are, illustrated. The deportment of critical elements contained in raw materials is also discussed.

Jan 1, 1998