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By G. Belardi

A study has been conducted to assess a new wet beneficiation treatment for the recovery of the sulphuric-acid-soluble titanium oxide contained in the waste from an Italian TiO2-pigment facility. The waste is produced during treatment of a Ti-enriched slag and contains as main components TiO2 (54%, of which 42% acid-soluble and 12% insoluble), SiO2 (27%) and A1203 (6%). Eighty percent of the material is finer than 50pm. The first step was to ascertain the possibilities offered by size classification, wet gravity separation, froth flotation and wet high-intensity magnetic separation to improve the grade and recovery of Ti02 and reduce the SiO2 content. The next step was to optimize the operating conditions of the various separations and assemble them into a complete flow- sheet. Beneficiation ensures potentially 70% recovery of the TiO2 with a concentrate grade of 80%.

Jan 1, 1998

Lead removal has been problematic in nickel production by electrowinning from chloride solutions, as developed by Falconbridge. The C12 leach liquor needs to be diluted by electrolyte to allow precipitation of the lead prior to electrowinning. This results in higher solution purification costs and an aversion to consider lead contaminated (secondary) feeds. In this paper, the electrowinning of nickel chloride is carried out in a membrane equipped electrolytic cell. When lead containing nickel solutions are fed into the anode compartment and the anolyte is separated from the catholyte with a cation exchange membrane, lead remains in the anolyte due to the presence of a negatively charged chloride complex. The positive nickel ions migrate preferentially through the membrane to the catholyte, allowing a lower lead nickel cathode to be produced. Lead concentration in the catholyte and the cathode product has been tested as a function of lead concentration in the anolyte. Results are presented and discussed.

Jan 1, 1998

By F. A. Steward

Copper is one of the trace minerals essential to life. It is added, usually in the form of copper sulfate, to virtually all formulated feedstuffs and to dietary supplements fed to animals on forage. Over the past five years, an improved inorganic copper source trademarked Micronutrients TBCC™, has been developed, tested and commercially introduced. TBCC is a crystalline form of basic copper chloride. Synthesis is accomplished in a continuous neutralization I crystallization process. In current commercial production, the primary sources of copper currently used as feedstocks are the etching solutions used to manufacture electronic printed wiring boards. These solutions have traditionally been managed as hazardous wastes, but their use to manufacture TBCC™ exempts them from regulation as wastes under the "Use/Reuse" provisions of RCRA. Research conducted over five years at multiple universities has shown that animals are healthier when fed this source of copper and that vitamin losses in feed are reduced by its use.

Jan 1, 2000

By Hiroshi Ono

"By newly developed ICP method, trace amounts of As(III), As(V) .,Sb(III) and Sb(V) were precisely determined within accuracy of sub ng/ml. As(III) and Sb(III) were separated from As(V) and Sb(V) by extracting into ·xylene as diethyldithiocarbamate complexes using diethylammonium diethyldithiocarbamate (DDDC), and then back-extracted into nitric acid for a quantitative determiruition by ICP-AES equipped with hydridegeneration system The recoveries of As(III) and Sb(III) were satisfactory throughout the extraction with 0.04mol/l DDDC in xylene from lmol/l hydrochloric acid solution and the back-extraction with 7 mol/l nitric acid. As(V) and Sb(V) were reduced to As(III) and Sb(III) by ascorbic acid and potassium iodide, and their quantities were determined as mentioned above. The detection limits were found to be 0.58ng/ml for As(III), 0.63ng/ml for Sb(III) using 50ml of a sample. The proposed method was applied to analysis of the real sample.Introduction In drain, arsenic(AS) concentration is prescribed below 0.lmg/l, so As must be removed. As is existed at .the form of As(III) or As(V) in solution. For t1Jeir difference of chemic;µ property, it is not easy to remove As in solution. So it is an urgent necessity to develop for determining concentration of As(III) and As(V). Antimony( Sb) has resemblance .chemical property to As. So Sb was experimented the same as As.The separation and determination of As(III) and As(V) have been carried out using several methods, such as ICP after copreclpitating separation, HPLC, direct hydride generation atomic absorption. However these methods have some problems. One of main problems is that HPLC and direct hydride generation atomic absorption methods are influenced by coexisting elements."

Jan 1, 2000

By H. J. Thevik, A. K. Dahle

"A mathematical model that calculates the stress development in a coherent and stationary dendritic network due to interdendritic flow is proposed. The fluid flow is assumed to be related to the solidification shrinkage, and under the assumption of no porosity formation and unidirectional solidification, the shrinkage-induced flow within the mushy zone is calculated analytically. The interdendritic melt flow exerts a force on the solid network and an analytical expression for the stress build-up in the network is developed. Parameter studies illustrating the influence of cooling conditions, mushy zone length, dendrite coherency, fraction solid, volume fraction of eutectic, and solidification shrinkage upon the stress development within the solid network are presented. Comparing the magnitude of the calculated stresses to measurements of the strength in equiaxed mushy zones shows that it is possible for the stresses to exceed the strength, thereby resulting in reorientation or collapse of the dendritic network.IntroductionInterdendritic fluid flow is at present regarded as a very important mechanism for feeding of shrinkage during solidification of metal alloys. Solidification of many alloys is often characterised by heterogeneous nucleation of the primary phase on substrates in the melt with subsequent evolution of equiaxed dendrites. These equiaxed dendrites can initially grow freely, but impinge on each other and form a continuous dendritic network, ie. dendrite coherency, quite early in the solidification process. Measurements of the dendrite coherency point have shown that the dendritic network is established at solid fractions ranging between 0.1 and 0.5, and most often around about 0.2 [l]. Depending on the alloy composition this means that as much as 70 to 80% of the volumetric shrinkage has to be compensated by flow of liquid through the interdendritic network. Interdendritic flow occurs with a much larger resistance compared to free flow of the liquid and flow of a liquid with dispersed crystals. The pressure drop associated with the interdendritic flow increases rapidly with decreasing fraction ofliquid."

Jan 1, 1999

By Yasuyuki Murayama

MF is the semi-blast furnace which has been developed at Mitsui Miike Smelter in the 1960's to treat vertical retort residue. The MF has also been tested for treatment of various recycling materials and wastes. Now various secondaries and wastes (steel dust, zinc leaching residue, Cu-Ag sludge, spent catalyst and spent rubber, etc.) are mainly treated. Powder materials are briquetted with reductant before being fed to the furnace. Products are crude zinc oxide, matte, non-hazardous slag and steam. Zinc and lead are recovered in oxide dust, and copper and silver are recovered in the matte. The MF furnace can be widely applied to many kinds of materials which contain such non-ferrous metal-valuables. In addition, the improvement in operation and technology has effectively made the unit capacity much larger. The MF furnace now has many advantages for these treatment processes.

Jan 1, 1992

By P. Klut, D. Groult, R. Marechalle, B. T. H. Bonnema

In the past 5 years, Compagnie Europeenne de Dezingage (CED) has developed a successful dezincing process and the St. Saulve pilot plant has evolved into a commercially successful production plant. Currently the plant meets all the required standards for scrap and zinc quality, output capacity, availability, and meets the prescribed environmental emissions standards. The initial process problems relating to zinc recovery, uncontrollable explosions and sodium hydroxide aerosol emissions have all been solved. Presntly, the yearly production of dezinced scrap is around 50.000 tonnes/year; this capacity is enough to supply the local market. This capacity can be increased easily to 65.000 tonnes/year or more. The market for dezinced material is growing due to the increased consumption of galvanized material on one hand and on the other hand the higher demand for high quality scrap. The proven technology of CED is currently patented worldwide, but CED is inviting licensees to implement the dezincing technology in other parts of the world.

Jan 1, 2000

In the new flowsheet for Inco Limited's S02, Abatement Project at the Copper Cliff, Ontario operations, a copper/nickel sulphide flotation concentrate will be flash smelted, then converted to Bessemer matte. As in current practice, this will be slow-cooled and separated into components by magnetic separation and flotation. The copper content will emerge as a chalcocite concentrate (impure Cu2S), containing some nickel. This copper sulphide will be converted to copper metal.

Jan 1, 1993

By N. A. Vatolin, L. I. Leontjev, S. V. Shavrin

The ever growing interest to the complex iron ores may be attributed to possible production of the naturally alloyed metals and the efficient recovery of the associated elements. However, the conventional technique for complex ore processing is complicated and in some cases even impossible. A pyrometallurgical benefiation of such ores without melted slag formation has been advanced. A version of the technique assumes pellet production with metal coagulated within a slag shell on grinding the pellets, the metal phase is mechanically separated from the slag shell. The technique has been run up with ferro chromo nickel, high-titanium, high-magnesia, alumina phosphorus ores and concentrates. Another version of the pyrometallurgical benefication without melted slag formation in a rotary kiln has been developed from the schemes for processing red mud of alumina manufacture and high-titanium concentrates. Means have been put up to improve schemes available for lex iron ore processing with primary emphasis on material pretreatment before blast furnace and steelmaking processes. Vanadium-bearing titanomagnetite conentrate oxidized pellets possess low strength at reduction. The technique suggested for pelletizing in the controlled atmosphere improves the afore said pellet metallurgical properties. Prodution of metallized pellets in a conveyor roasting machine holds considerable promise for blast furnace and steelmaking processes. In processing the high-sulphur iron ores still another technique is proposed to roast the fluxed pellets with 95% and more desulphuration.

Jan 1, 1988

By U. Meyer, A. Alonso, P. Banios

The sampling of cathodes has changed with the introduction of the ISA-process in copper refineries. A Jernkontoret joint working group of refineries and rod plants from both primary and recycled copper plants has been investigating whether the actual sampling of cathodes is representative for this type of cathodes. As a first stage, samples were sent to the members of the working group with the objective to find an easy basis for a comparison of the results of the next stages. All samples show the same tendency for nearly all elements. In some cases, there may exist differences in calibration and for some elements the detection limits are too high, especially when Optical Spectrometry is used. In the second stage, discs were compared with melted samples to answer the question whether the punching of discs is sufficient for the quality control of the cathode. The analyses of the discs represent fairly well the cathode quality. There are differences between cathodes from different crops. Three punches are sufficient to determine the cathode quality. Finally, samples from various lots of cathodes were compared with samples from the rod produced from these cathodes. The impurity content of the rod corresponds to the impurity content of the cathode.

Jan 1, 2000

By Toshihiko Emi

The quest for cleaner steel is driven by increasingly stringent requirements from the manufacturing and construction industries. Key issues are the occurrence and removal of inclusions; These are discussed in the context of the unit processes of deoxidation, refining, transfer and casting of molten steel. Process thermodynamics and kinetics are also discussed. Recent progresses achieved and problems yet to be solved are elaborated, and an integration of the unit processes into a system to produce extra clean, steels with better performance is presented.

Jan 1, 1999

By T. Shimizu

In Japan, the emission standard of selenium in effluent was set at a maximum of20 mgll in Feb. '94 for the first time, and it is scheduled to be further decreased to a maximum of 0.1 mg/I from Feb. '97 due to tightening of the Water Pollution Prevention Act. Selenium (IV) and (VI) are generally found in effluent from precious metals refineries. Although selenium (IV) can be easily eliminated by some reducing agents, selenium (VI) is more difficult to be reduced. Therefore, many smelters are having difficulty in complying with the new emission standard. At Mitsubishi Materials' Naoshima smelter, the behavior and the elimination of selenium in effluent have been extensively investigated. As a result, it was found that two strategies were particularly effective. One of them is improving the overall operation of precious metals refinery, that is, feeding uniformly the effluent to the waste-water treatment plant, reducing the effluent volume by recycling and recovering more selenium (IV) in the effluent. The other is eliminating selenium (VI) in the effluent from the precious metals refinery. It was found that selenium (VI) can be effectively reduced by using hydrazine under high? sulphuric acid concentration and high temperature conditions. By using these measures, it is considered that Naoshima Smelter will be able to comply with the new emission standard.

Jan 1, 1996

By Wei-feng Liu

On the basis of the brief introduction of the gold-antimony concentrate smelting process in China, some problems in the original process were analyzed and the corresponding improvements were introduced in this paper, such as the treatment of antimony matte, the refinement of gold-silver alloy, the concentrating gold from gold-antimony alloy, the treatment of soda slag. The roasting method that was used to treat the antimony matte was transferred to the ore dressing method. The solvent extraction was used to refine the gold-silver alloy instead of the electrolytic method. The technology of selective chlorination leaching under controlling potential was applied to concentrate gold from the gold-antimony alloy and gold-lead alloy instead of the electrolysis method. Soda slag was recovered by the second reducing smelting method substituting for the mixed-salt method of sodium arsenate. After those improvements, the process has been done smoothly; the direct recovery rate of metals has been greatly increased. Meanwhile the procedure

Jan 1, 2008

By L. Becze, S. J. Hock, G. P. Demopoulos

"Regeneration of HCl from chloride solutions is commercially practiced by high temperature (800-900 °C) pyrohydrolysis associated with high energy consumption and capital cost. As an alternative to pyrohydrolysis a novel low temperature ( <200 °C) non-autoclave hydrolytic process has been studied in this research work, which comprises two steps. In the first step, ferrous chloride is oxidized by oxygen at 1;150 °C, followed by hydrolytic decomposition of ferric chloride to coarse hematite particles and superazeotropic hydrochloric acid (8-9M) operated at approximately 180 °C. This paper provides a summary of the laboratory results related to both oxidation and hydrolysis and presents a newly designed conceptual process flowsheet.IntroductionRecovery of base, noble and rare metals from ores and secondary materials (slags, dusts, residues) by chloride-based hydrometallurgical processes holds a lot of promise if a low cost HCl process becomes available. This is particularly so due to the high activity of HCl or more accurately activity of hydrogen ion [1] in concentrated chloride media and the formation of chlorocomplexes allowing for effective leaching under atmospheric leaching conditions and simultaneous ease of metal separation. However, during leaching significant amount of iron, which is associated with most of ores and secondary materials, goes into the solution. Hence, the obtained leach solution has to be treated to convert iron chlorides into easily filterable iron oxide and simultaneously produce concentrated hydrochloric acid. Apparently the critical operation of these processes is the regeneration of the lixiviant (HCl). Currently in the industry, its regeneration is accomplished by high capital and intensive pyrohydrolysis which operates at 700- 900 °C. Aimed at lowering the operational cost of pyrohydrolysis a process called PORI [2] was developed and tested in pilot plant scale in the 1970s for the purpose of treatment of pickle liquors without, however, resulting in industrial application."

Jan 1, 2011

By Tao Jiang

Germanium is widely used in many fields, and the production of germanium is very important. The effects of initial sulfuric acid concentration, liquid to solid ratio and other parameters on the leaching rate of germanium and zinc from germanium-bearing zinc oxide has been studied. The occurrence and form of germanium and other elements in the leach feed and the leach residue were studied by EPMA, XRD and chemical analyses. The experiments showed that the leaching rate of germanium and zinc was 91% and 88%, respectively under optimal conditions. Wurtzite was the main limiting factor for the leaching rate of zinc while the leaching rate of germanium was limited by insoluble germanium compounds. Furthermore, it was found that some germanium was bound up in galena in the leach residue. These results may be helpful for further improving the leaching rate of germanium in germanium-bearing zinc oxide.

By Gustavo Díaz, Miguel A. García, Carlos Frías

"Under the auspices of the Commission of the European Union, a consortium composed of six European organi~ations has conducted a project to scale up the PLACID electrowinning cell to industrial size within the Placid process development. This paper is concerning the results and achievement of the industrial cell prototype after more than 1,000 hours operating time and about 10,000 Kg electrolytic lead production. In general, results have been very satisfactory, demonstrating the ability ofthe PLACID electrowinning cell to produce top quality electrolytic lead (> 99.99 %) with high current efficiency and low energy consumption.IntroductionThis paper is concerning the development of an industrial size PLACID electrowinning cell within the PLACID process development. This project began on January 1993 and was finished on April 1996.Lead metal production and manufacturing industries produce large amounts of dusts and also lead bearing slags. Spent lead-acid battery recycling also produces lead oxides from the battery pastes rather similar to those mentioned above. Those lead secondary materials are hazardous and difficult to handle by usual procedures.Existing processes to treat-lead oxides may inflict considerable damage on the environment, incur high operating costs and have limitations to produce top quality lead.The main aim of this project has been to develop a novel hydrometallurgical process able to deal with different lead bearing materials, mainly lead oxide secondaries: lead-acid battery pastes, lead fumes, furnace slags, oxide residues, etc., producing ""four nines"" pure lead in an efficient manner with a benign influence on the environment; it is called the PLACID process."

Jan 1, 1997

By T. T. Chen, J. E. Dutrizac

"Grooved cast Pb-Ag anodes are used by some zinc refineries to improve current efficiency. It was found that the manganese oxide scale formed on a grooved Pb-0.75% Ag anode consists mainly of MnO2, which occurs characteristically in rhythmically banded colloform structures and adheres to a layer of ""Pb02+PbS04"" that oxidized from the anode. The relatively homogeneous and nearly fracture-free morphology of the ""Pb02+PbS04"" layer suggests the relatively uniform corrosion of the anode. Deposition of the Mn oxide initially follows the contours of the anode surface, but the grooves eventually become filled with Mn oxide and gypsum. Hydrous Mn oxides and amorphous Mn oxides are believed to be also present in the manganese oxide scale. Tiny particles of PbS04 and SrS04, together with gypsum, other impurities and micro-pores, tend to concentrate in the grooves.IntroductionManganese is a common impurity in hydrometallurgical zinc processing circuits. The manganese originates from sphalerite (Zn,Fe,Mn)S and from the Mn02 added to the leaching circuit to oxidize ferrous ions [1]. Manganese in the sphalerite follows Zn through the roasting, leaching and purification processes, and is present as Mn(II) in the purified ZnS04 solution. The Mn in the added Mn02 is reduced to Mn(II) during the oxidation of the ferrous ions present in the leach solutions. In both cases, MnS04 is generated, and the MnS04 accumulates in the purified solution. In the cellhouse, Zn is plated at the cathodes to produce high quality metal. The Mn(II) is partly oxidized at the anode surface to Mn(IV), and the Mn(IV) precipitates as a scale on the surface of the anode and as a sludge on the bottom of the electrolysis cells. The presence of a thin layer of manganese oxide scale on the surface of the Pb-Ag anode can minimize the corrosion of lead and, accordingly, reduce the contamination of the electrodeposited zinc. However, a heavy manganese scale build-up can cause ""staining"" of the zinc deposits and reduced current efficiencies. Consequently, periodic anode cleaning to remove excess manganese oxide scale is carried out routinely in commercial operations."

Jan 1, 2011

By Nils Eivind Kamfjord, Mari K. Næss, Halvard Tveit, Edin H. Myrhaug

"As a part of the FUME research programme being done by the Norwegian Ferroalloy Research Association (FFF), the SINTEF Group and NTNU, several measurements towards quantifying the gaseous and solid emissions from the draining of the silicon furnaces for metal have been carried out.Based on the measured size distribution of the formed fume particles and known particle growth theory, an estimate of the growth time for the given particles has been calculated. The formation time for the measured NO amount has also been calculated based on the fume measurements and a thermodynamic model of the furnace gases combusting with air. The two “formation” times are in the same order of magnitude and they are therefore used as parameters in a CFD model, modelling that the formed fume particles are heating up the surrounding air and thereby forming NO according to the Zeldovich mechanism. The measurements show an approximately equal constant NO formation per fume particle. The CFD model shows results in the same order of magnitude, supporting that the particle growth and NO formation happen under near stoichiometric conditions and are controlled by the formation of SiO2 fume.IntroductionNOx is the common notion for the two gases nitric oxide (NO) and nitrogen dioxide (NO2) formed during combustion of fuels. The main sources for human made NOx emissions is on-/offshore transportation industry, power generations based on fossil fuels, agriculture and other industries [1]."

Jan 1, 2012

By Pedro Lobarinhas

In the present work a two dimensional computational model is derived for the description of the time dependent heap leaching process. The flow inside the heap is calculated using the diffusion equations for the flow in porous media. The soil conductivity is also estimated assuming a close packed structure for the grain packing inside the heap. These equations, with appropriate boundary conditions, are solved using a time step splitting scheme. From this calculation the amount of leaching reagent in contact with the ore at any position inside the heap can be calculated and, once coupled with appropriate reaction equations, the amount of metals extracted can be computed and leaching agent concentration updated. The model is tested with available experimental data and the results have shown to be in a very good agreement. The model predicts all the transient features of the data.

Jan 1, 1999

By Nobuyuki Masuda

In Japan, the municipal solid waste, which amounts to 50 million tons, is generated every year and most of it is incinerated. The fly ash from the municipal waste incineration (the primary fly ash) contains heavy metals, such as lead and zinc, etc., and dioxins. In case of melting, the fly ash from the process (the secondary fly ash) contains high concentration of heavy metals (e.g., Zn; 1-20%, Pb, 1-10%). Metal Mining Agency of Japan launched a four-year project in 1999 to establish the integrated technologies to recover the valuable metals from, and to decontaminate, the primary and secondary fly-ashes in the practical scale by utilizing the existing metallurgical processes and facilities, along with the energy saving. The segregation, flotation and chemical treatment are applied to the treatment of the primary fly ash. The secondary fly ash is treated with MY (Mitsui-type blast furnace) Process after the chlorine removal to recover the heavy metals in the ash, In this paper, the segregation and flotation process for primary fly ash and MF process for secondary fly ash are explained. The main results of experiments done from 1999 to the mid of 2001 to design the pilot plants and to optimize the operating conditions are described. The main results of the experiments are as follows: - The segregation reaction of Cu was confirmed by the experiment on the treatment condition of 800 and 900`C with adding oil cokes and water to the primary fly ash, and 99.98% (toxicity equivalent) of the dioxins were decomposed by the treatment. - Washing tests of secondary fly ash to feed MF resulted that more than 70% of chloride were removed, but still lower than expected, and agglomeration tests were successful by the results of the sufficient strength of briquettes produced though a little more binder for the agglomeration is required than usual operation. - Smelting experiment by downsized MF showed that valuable metals, such as zinc and lead, are recoverable in the furnace dust. Recovery ratios, Zn: 58% and 67%, Pb: 74% and 83%, are accomplished.

Jan 1, 2002