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By W. W. Albrecht

I. Introduction Refractory metals like tungsten, molybdenum, rhenium, tantalum and niobium and their compounds are essential ingredients of our modern technology. Especially in purified form, they are used in special alloys, electronics, optics and ceramics. The processing route from raw material to high purity refractory metals and their compounds includes, as a prime option, the following steps: - dissolution of raw materials. - liquid liquid extraction. - precipitation of high purity intermediate compounds. - calcination/reduction to high purity oxides/metals. Especially in the first three steps, major amounts of chemicals like acids or sodium hydroxide are used and, as by-products, substantial quantities of residues and effluents are generated. The impact of environmental regulations on these by-products and the attempt to reduce or minimize the amount of residues and effluents produced will be discussed in this presentation using Ta/Nb chemistry as the example. The basis of our considerations will be the way these by-products are handled at HCST, a major, and in some cases, the biggest producer of refractory metals (tungsten, molybdenum, rhenium, tantalum, and niobium).

Jan 1, 1992

By Ramona Prillhofer

Salt slag is a waste product produced by the recycling of aluminum. In most European countries (e.g. Austria, Germany) the landfill disposal of this waste is forbidden because the slag contains soluble salts and these represent a potential source of pollution to the surface and groundwater. Additionally, consisting metal and some compounds in the salt slag can react with water and resulting from this, noxious gases are generated. The recovery of useful materials from these wastes is accordingly both environmentally necessary and economically feasible. This study describes a complete recycling-process for the salt slag, which includes a leaching-cristallization-process to obtain the oxidic residue, a pyrometallurgical-step to clear the oxidic residue and finally an extensive characterization of the achieved products. Due to the increasing price of raw materials, the utilization of the oxidic residue into commercial products has been investigated and application possibilities will be discussed.

Jan 1, 2009

By S. S. Chabot, S. E. James

A recent survey of CEOs from major steel companies worldwide revealed the importance of recycling zinc units from EAF dust, mill scale, blast furnace dust, and other zinc containing streams in their plants. Many processes were developed and installed in response to this challenge. The most successful approach involves the production of a crude zinc oxide and selling it to primary zinc producers to recover the metal value. The problem with this process is the high concentration of halides in the crude oxide. This type of material cannot be processed directly in an electrolytic zinc plant because of corrosion problems it will cause in electrolysis. In 1999, BRZ installed a zinc oxide receiving and washing plant to minimize the impact of halides to its circuit. A description of the washing plant and initial operating results are included.

Jan 1, 2000

By S. S. Chabot, S. E. James

A recent survey of major steel companies worldwide revealed the importance of recycling zinc units from electric arc furnace (EAF) dust, mill scale, blast furnace dust and other zinc containing streams within the steel industry. Many processes have been developed and installed in response to this challenge. The most successful approach involves the production of a crude zinc oxide and its sale to primary zinc producers to recover the metal values. The problem with this process is the high concentration of halides in the crude oxide. This type of material cannot be processed directly in an electrolytic zinc plant because of the corrosion problems it will cause in electrolysis. In 1999, Big River Zinc installed a zinc oxide receiving and washing plant to minimize the impact of halides in its electrolysis circuit. A description of the washing plant and the initial operating results are presented in this paper.

Jan 1, 2000

By Carla Lupi, Alessandro Pescetelli

"Spent lead battery recycling still shows few weak points in the achievement of a 100% recycling of different waste matters and by- products arising from the recycling process. Some of said problems are dealing with aqueous streams outgoing the recycling plant, and more particularly, a) the waste waters discarded from the breaking and separation unit, b) purification of the spent electrolyte drained from waste batteries and upgrade to a quality compatible with full re-use by the batteries’ manufacturers, c) purification of the mother liquors discarded in the sodium sulfate crystallization process so to produce a salt of commercial grade. All of the above listed problems have been satisfactorily overcome applying an electrochemical process that, through different process conditions and parameters, is able to remove the harmful impurities that hinder the successful commercialization of such by products, or, at least, that can avoid heavy and expensive treatment plant and operation.IntroductionAlmost 100% of commercial lead and lead alloys produced by secondary lead plants is recycled to the new lead accumulators manufacture. The other by-products and residues produced through the lead recycling process may be classified into two groups:a) matters reusable in the new accumulators production processb) matters produced as a result of various reagents and additives used in the recycling process, to be sold to different market sectorsQuality and saleability of by-products are significant points for the economics of the secondary lead plant operation, because, if said by-products are not saleable, they are just wastes, so offsetting potential revenues, and, at the same time, adding a heavy burden to operating cost, like disposal cost [1]. When looking at a typical, modern lead scrap batteries recovery cycle, it is quite evident that we are still rather far from dealing with a waste-less technology (fig.1).The group a) includes 3 by-products produced through the breaking process: among those matters the polypropylene only usually reaches a standard quality suitable for sale to lead manufacturing sector or to other sectors as well. The other two by-products, electrolyte and separators, do not still reach, through a viable and effective regeneration process, a quality standard sufficient for their re-use in the lead batteries sector ."

Jan 1, 2008

By Gaballah Djona M.

Spent hydrorefining catalysts contain about 5 % of CoO and/or NiO, 12 % of MoO3 and up to 10 % of V205. They are generally supported by alumina and contain up to 25 percent of C, S and hydrocarbons. Such materials are potentially hazardous to the soil and to water resources. Selective chlorination of raw unroasted samples with Cl2 + air gas mixture had been investigated. At temperatures lower than 600 °C, it was possible to recover more than 90 % of nickel and cobalt chlorides, about 99 % of the molybdenum and up to 75 % of vanadium chlorinated compounds. CoCl2 and Ni/Cl2 were extracted from the chlorination residues by their dissolution with acidified water. Molybdenum and vanadium chlorinated compounds were recovered by selective condensation from the vapor phase. The chlorination of Al2O3 could be limited to less than 6 %. The scale up of this treatment was successful and a flow-sheet is proposed.

Jan 1, 1995

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 W. Kunda

A laboratory study was carried out on the treatment of sulphidic copper concentrates in aqueous chloride systems under elevated temperatures and oxygen overpressure. Exploratory tests showed that chalcopyriteoxidizes with various chloride salts to form, depending upon the pH of the system, soluble copper chloride or insoluble copper oxychloride salts; the copper can then readily be recovered from the solution or residues respectively. During the leaching, iron was oxidized to iron oxide and remained in the leach residue while the bulk of the sulphide sulphur was oxidized to the elemental form with a minor portion oxidized further to sulphate. The presence of metal chloride salts in the system increased the oxidation rates of chalcopyrite and depressed the solubilization of iron in the system. A systematic oxidation leach study carried out in (1) ammonium chloride and (2) sodium chloride systems showed that the former system required little or no HC1 addition while the latter required 2 mol of HC1 per mol of dissolved copper (plus zinc). The copper was recovered from the cuprous or cupric chloride leach solutions by cementation with iron. Extractions of 99% copper and zinc, 97% silver, and negligible iron were obtained. Sulphur was oxidized to the elemental or sulphate form; the relative proportions of the total sulphur were 60 and 30% for system (1) and 80 and 10% for system (2). A flowsheet for a conceptual process with minimal reagent requirements was proposed.

Jan 1, 1976

By J. H. Meza

La Caridad copper smelter is located in the magnificent but rugged Sierra Madre Mountains. This project presents unusual challenges that require the utmost in detailed analysis and planning. The smelter, owned by Mexicana de Cobre, S.A. de C.V., has an annual production capacity of 225,000 metric tons of copper and 600,000 metric tons of sulfuric acid. It utilizes only the Flash Smelting process. This project will expand the annual production capacity to 270,000 metric tons of copper and 1,000,000 metric tons of sulfuric acid. Offgases from the Flash Furnace and the Teniente Converter will be sent to a mixing chamber, from which it will be led to two sulfuric acid plants. This project will then produce a high quality sulfuric acid.

Jan 1, 1995

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 Bora Derin, Sertac Yazici, M. Seref Sonmez

"In this study, the recycling conditions of waste liquor obtained after the production of tungsten boride powder from calcium tungstate by self-propagating high temperature synthesis (SHS) and the following hydrochloric acid leaching were investigated in detail. Environmentally unfriendly and extremely acidic (pH~ -0.3) liquor consisting of calcium, magnesium, and boron ions was treated with 1 M sodium carbonate solution to precipitate magnesium carbonate and calcium carbonate phases. The obtained amorphous precipitates were heated up to the temperature of 400°C for re-crystallization. As a result, MgO, CaC03 and CaMg(C03)z phases were obtained, while sodium, boron, chlorine ions were remain in the solution. The present study is still in progress.IntroductionSelf-propagating high temperature synthesis (SHS) is one of the techniques used in the production of a variety of advanced ceramics, inter-metallic, organic and inorganic compounds, oxygen free single crystals, and polymers [ 1, 2]. The reaction becomes selfsustaining and propagates in the reactant mixture, after initiation in SHS process. SHS products may contain the mixture of several unwanted compounds and elements. Therefore following acidic leaching process may be needed to purify the target product. In the previous study, calcium tungstate (Ca W04), magnesium (Mg) and boric acid (B20 3) mixture were reacted to produce tungsten boride powder by SHS process according to the Reaction 1. Then, magnesium and calcium containing byproducts (i.e. MgO, Mg3B206 and Ca3B206) found in the SHS product were leached out by using concentrated hydrochloric acid (HCl) solution to obtain pure tungsten boride powder [3].Ca W04 + 0.5B203 + 4.5Mg = WB + 4.5Mg0 + Cao (1)After the leaching, filtrate solution consisting of different amounts of magnesium, calcium, and boron requires additional treatment for the environmentally acceptable disposal.Several works were carried out about magnesium precipitation conditions and kinetics from brines. Rabadzhieva et al. investigated the precipitation of Mg(OH)z from brines by using NaOH as well as caustic soda [ 4]. Turek ve Gnot investigated the precipitation efficiency of Mg(OH)z for the temperature range between 10-40°C, while the reaction was kinetically experimented by Alamdiri et al [5, 6]. Homogeneous precipitation of nesquehonite (MgC03.3H20) by the reaction of MgCli with (NH4)2C03 in supersaturated solutions and factors that influence the precipitation of MgC03.3H20, such as reaction temperature, initial concentration, stirring speed, titration speed, equilibration time, have been studied by Wang et al [7]. The precipitation of Mg(OH)z by calcium hydroxide from aqueous solutions was studied by Baird et al. [8]. Stratful et al. focused on conditions influencing the precipitation of magnesium ammonium phosphate from wastewaters [9]. 1031"

Jan 1, 2011

By P. R. Khangaonkar

The industry of tin ore mining, beneficiation and smelting gives rise to a number of waste products like the beneficiation plant wastes (called amang), tin smelting slags, refinery dross etc. Some of the wastes deserve treatment to obtain economically useful products or to recover the metal values. The paper describes studies conducted on two materials, viz., struverite-middling (struverite-magnetic tin), which is an intermediate product of beneficiation circuits of tin tailings, and tin-smelting slags. The struverite middling was studied for treatment by chlorination using carbon tetrachloride, so as to yield vapour products separable by convenient condensation. The treatment was also found to lead to a tin-rich product amenable for treatment by known hydrometallurgical routes. The tin smelting slag was studied by alkali-leaching so as to avoid any dissolution of iron and it was possible to obtain an iron-free product solution suitable for high purity tin recovery.

Jan 1, 1996

By He De-wen

The influence of wastewater containing benzene from chemical industry by technology combined blow-off with Fenton reagent oxidation was experimentally studied. The present results suggest that the technology combined blow-off with Fenton reagent oxidation can effectively remove benzene pollutant in wastewater. The main factors that influence the removal benzene such as temperature and blowing time and volume, pH and reagent dosage of H2O2 and Fe2+ are studied and the optimal experimental conditions are as follows: time 20min, temperature 40i, air-blowing volume 0.4L/min, pH value 5, and H2O2 and Fe2+ dosage 2mL/L and 200mg/L respectively. Under the above conditions, benzene pollutant can be removed up to 97%. Compared to other removal ways of wastewater containing benzene, the technology combined blow-off with Fenton reagent oxidation is more effective and has the advantage of high speed.

Jan 1, 2009

By Min Xiaobo

As for treatment of zinc-containing wastewater, traditional SRB (Sulfate Reducing Bacteria) process was used, however, there exist two defects, like toxicity of heavy metal ions and high effluent COD (Chemical Oxygen Demand) value. In this study, a new technique, called ISIS process (Immobilized SRB sludge beads with Inner cohesive carbon Source), in which SRB sludge is embedded in carrier of PVA (Polyvinyl Alcohol) with carbon source that adsorbed on certain material, is put forward for the first time to overcome the two defects existing in traditional SRB process. Furthermore, it has been shown that compared to traditional SRB process, ISIS process increases average zinc removal rate up 30%, average sulfate reduction rate up20%, and decrease average effluent COD value to meet discharge standards. If activated carbon is selected for carbon source adsorption and fixing material, and PVA for immobilization material, the zinc removal rate can reach above 98% under the conditions of 35 and pH 6. Meanwhile, the mechanism of zinc removal has been determinated according to the results from SEM (Scanning Electronic Microscope) and XRD (X-Ray Diffraction).

Jan 1, 2006

By V. M. Paretsky

Recent developments made in the Gintsvetmet Institute in the field of autogenous smelting processes have confirmed that autogenous smelting continues to be the main prospective technology for pyrometallurgical processing of sulfide raw materials. This technology ensures energy conservation and environmental safety conforming to the current world standards for production of heavy non-ferrous metals. Two alternative processes of single-stage autogenous smelting producing white metal as well as high-basic ferrite-calcium slags have been developed and can be recommended for technical modernization of Russian copper smelters.

Jan 1, 2002

By J. E. Allen

The trend in refractory technology for the copper and nickel industries has been to higher quality raw materials and improved processing technology. These changes have been dictated by the changes in pyrometallurgical processes in these industries. For example the introduction of flash smelting, reaction type smelting and auxiliary slag cleaning furnaces havedemanded better refractories materials. Extensive field applications and improved laboratory testing procedures have helped make this transition possible. Changes in refractory technology, primarily in basic refractories, are followed from the late fifties to the present and into the future.

Jan 1, 1994

By S. q. Honingh, G. Van Weert

Currently produced zinc-enriched blast furnace dust is stored on site at CORUS IJmuiden. To end this practise, a research program was started in 1996. Four technologies were studied: oxidative autoclave leaching in a chloride medium, fluid bed pyrohydrochloridisation (pyrohydrolysis) to yield lead-zinc-free (hematite) calcine, EAF (plasma) smelting/zinc fuming, and incorporation of the dust in 'iron foundry cupola charges. All aim to remove zinc and lead, recycle the iron residue internally, and produce a saleable zinc-lead product.

Jan 1, 2000

By P. Tapp, T. Evans, N. A. Molloy, J. Lucas

"Consideration of the protoype tuyere geometry for injection of inert gas through the bottom in a basic oxygen steel furnace and a requirement to specify an optimal flow for bottom wear and metal penetration led to experimental investigations[l,2] to apply the results of previous workers to this specific case, Flow velocity profile development within the tuyere was proposed as significant and the experimental scheme was designed to test this. It is proposed that the design criterion for the conditions of optimal flow of the prototype geometry be based on the non-dimensional mass velocity.INTRODUCTIONSharma[3] tested small diameter tuyeres in a laboratory hot model using molten iron to define a flow criterion for prevention of penetration of the bath liquid into the tuyere. Using argon, nitrogen and helium through a range of tuyeres (1 to 3 mm ill ) he proposed the jet Froude number C Fr' ) with the critical value being 2400 - 2500 or higher. Sonic or supersonic velocity was not a sufficient criterion. The tuyere design was a parallel tubular duct of moderate aspect ratio CAR) i.e. the ratio of length to diameter ranging from about 22 to 36 in the experimental furnace.Farmer et al[4] stated their their aim ""to develop a unifying explanation and procedure for the proper design of tuyeres"" but disagreed with Sharma's jet Froude number criterion. Recalculating Sharma's data they proposed instead a fully expanded Mach number of 1.75 with an initial expansion angle of ten degrees as the lower bounds of flow to meet the design requirement. They experimented with tuyeres in a water model using tubular, annular and convergent-divergent nozzles. The aspect ratio of the parallel duct tuyeres was from 533 to 762 using diameters of 1.4, 1.7 and 2.0 mm C the diameters being of tubes to be used full scale). Subsequently these results were applied to a prototype tuyere using a diameter of 1.7 mm with beneficial results in practice. This tuyere had an aspect ratio of 1067."

Jan 1, 1996

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 160,000 tpy of copper in concentrates. Through several expansion projects, the total smelting capacity of both processes is expected to reach 430,00Otpy 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 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