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By A. S. Rao

In the original roast-leach-electrowin (RLE) circuit at the Chambishi Cobalt Plant, commissioned in 1978, the separation of nickel and zinc from cobalt in aqueous streams was achieved by successive stages of precipitation using lime. However, this technique was not able to meet the increasingly stringent metal quality requirements of customers whilst maintaining acceptable process recoveries. Intensive process development work was carried out and, in July 1988, an ion exchange circuit for nickel removal was commissioned using DOW XFS 4195 resin and for the first time Z.C.C.M. produced high purity cobalt metal containing less than 0.10% nickel. Following further work, a solvent extraction circuit for zinc removal, using DZEHPA, was commissioned in February 1991 in order to enhance cobalt recovery by reducing co-precipitated cobalt losses. This paper outlines the process development, design, commissioning and subsequent operation of these nickel ion exchange and zinc solvent extraction circuits.

Jan 1, 1993

By Mitsuhiro Ito

"To allow various wastes containing high levels of chlorine to be used as alternative raw materials for Portland cement, two practical methods of chlorine removal were developed. In the first method, chlorine is extracted from the wastes during the cement manufacturing process. In the second, ash-dust waste with high chlorine content is first washed and then dehydrated to cake before being introduced to the cement manufacturing process. This cake can be used as an alternative for some cement raw materials. By combining the two methods, various wastes previously considered unsuitable for recycling due to their chlorine content can often now be used in cement manufacturing plants. As such, these methods represent a major contribution to environmental protection as well as a solution to problems relating to the diffusion of heavy metals and dioxins from cement plants.1. IntroductionWaste generation levels have risen rapidly in recent years. in both the consumer and industrial sectors and today, the need for effective, efficient waste management is one of the most pressing and serious problem of today's society.The Japanese cement industry has reacted to the increase in waste generation by using certain materials as alternative raw inputs or fuels for cement production, in an effort to contribute to society and conserve energy resources.These wastes often contain non-negligible levels of chlorine and heavy metals, however, both of which are unsuitable for cement production. Depending on the element content, Heavy metals have a particularly negative effect -on cement quality; in addition, they can be released into the environment. Chlorine, on the other hand, is contained in large amounts in incinerated ash from household wastes as well as in certain plastics. Both substances are considered impediments in cement-production, not only because they reduce the quality of the cement produced but also because they impair operating safety on cement production lines.To address this problem, two practical technologies have been established for separation and recovery of chlorine components during cement pre-processing and production. This paper introduces the application of these technologies with a special focus on incinerated ash from urban wastes, a representative form of waste material having notably high concentrations of chlorine, heavy metals, and dioxins. We also outline the technologies enabling this material to be used as an alternative input to cement production."

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, 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 I. Gaballah

The chalcopyrite ore's anodic and cathodic electrodissolution are studied using a Porous Pulsed Percolated Electrode (3PE) reactor. Stationary solid electrode experiments are also performed to explore the mechanism of electrochemical dissolution of chalcopyrite. Experiments with a low - grade natural ore have been carried out at 25 "C in solutions containing 1 M NaCl and 1 M HCl. Galvanostatic and potentiostatic conditions are employed. The influences of current and potential on selectivity of the chalcopyrite ore dissolution are assessed. Anodic oxidation of this ore leads to a preferential dissolution of iron bearing minerals, whereas cathodic reduction is more selective with respect to chalcopyrite. However, in both cases the electrochemical dissolution is incomplete and the current efficiency is low. Design of the actual reactor has to be modified to increase the bed conductivity and to allow continuous experimentations.

Jan 1, 1994

By A. P. Paiva

Studies focused on the recovery of precious metals by solvent extraction have recently increased. either to devise suitable solvents or to clarify the involved extraction mechanisms and kinetics. In this work, a comparison of the performance exhibited by triphenylphosphine (TPP), bis-(penty1thio)-ethane (BPTE) and triisobutylphosphine sulfide CI"I'BPS) in the extraction of silver from acidic chloride media is carried out. Extraction and stripping isotherms involving the three extractants are presented together with the results obtained on the selectivity of silver extraction against high contents of iron, copper and lead. Attempts to clarify the mechanism of silver extraction by TIBPS were performed by studying the distribution coefficient dependence on ligand and chloride concentrations. The effect of temperature on extraction and stripping is also considered. The interfacial tension for the system, measured with different concentrations of extractant in the organic phase, is analysed.

Jan 1, 1994

By Senlin Xie, Wanlin Wang, Lejun Zhou

"The innovative development of multiphase slag in hot-metal treatment has attracted considerable attention due to the reduction of CaO consumption and minimal environmental emission. In order to improve the efficiency of dephosphorization and to reutilize the waste-slag as an alternative source of phosphate ores, it is important to increase the distribution ratio of P2Os between the solid solution (2CaO· SiO2-3CaO· P2O 5) and liquid slag. An investigation was carried out to study the effects ofNa2O and B2O3 on the distribution ratio of P2Os, the results indicated that the increase ofNa2O would enhance the distribution ratio of P2Os with the formation of solid solution (2CaO·SiO2-Na2O·2CaO·P2Os), while B2O3 has the opposite function, and changes the morphology of solid solution. The study would provide an instructive way for the design of multiphase slag and re-utilization of waste-slag.IntroductionIn order to meet the increasing demand for high quality low-phosphorus steel, it requires a high efficient hot metal dephosphorization process. The current slag system for hot metal treatment contains large amount of solid CaO dispersed in liquid slag, which introduced a large amount of CaO consumption due to its low solubility, especially when CaF2 was restricted due to the environmental concerns. Therefore, new refming method to improve the utilization efficiency of CaO by using a solid/liquid coexisting multiphase slag was proposed, and the studies regarding to solid solution formation mechanism, mass transfer behavior of phosphorus and the phase relationship for multi-phase slag have been conducted. [1-6]Normally, hot metal dephosphorization slag consists of CaO--SiOz-FeO--P2O 5, and it has been approved that 2CaO·SiO2 forms a solid solution with 3CaO·P2Os at the hot metal treatment temperature over a wide range of compositions. [7] Kitamura et al [8] pointed out that the (2CaO·SiO2-3CaO·P2O 5) solid solution plays an important role in dephosphorization, and it has been regarded as an absorbents for phosphorus to lower the phosphorus content in liquid phase, which makes it more capable for future dephosphorization. l Besides, the multiphase slag has the potential to be recycled as a source of phosphorus, if the (2CaO· SiO2-3CaO· P2O 5) solid solution could contain high phosphorus content, and it can be separated from FeiO matrix 8hase due to the large difference of their magnetic properties under the strong magnetic field. [10, 11]"

Jan 1, 2014

By D. B. Dreisinger, V. van der Pas

Zinc sulphate electrolyte used for zinc electrowinning must be purified for cObalt ions. The cobalt is removed in a cementation stage by the addition of zinc dust. Copper arid antimony are frequently used additives which enhance the cementation of cobalt. This paper aims at a better understanding of how copper and antimony promote the removal of cobalt. Initial experiments were done in a batch cementation reactor. Copper and antimony precipitated in the early stages of cementation indicating that a preferential substrate was formed. The individual role of copper and antimony was further investigated in an electrochemical cell. On a microsca1e, the , growth process, morphology and the composition of the precipitates were examined with SEM and XRD. It was found that cobalt could not be deposited in its pure form but as a cobalt-zinc alloy with zinc as the prime constituent. Copper increases the cathodic surface area of zinc dust by precipitating as numerous dendrites. Antimony acts as a cathodic surface onto which a cobalt-zinc alloy with an increased cobalt content is deposited.

Jan 1, 1997

By Nathanael Hudson, Ruel A. Overfelt, Sushil H. Bhavnani

"In the aerospace and automotive industries, complex shapes exist which require casting. The problem with these cast parts is the empiricism required to develop the casting process and the accompanying time and expense to develop that process.There has been an interest in using fluidized beds to allow molding sand to better encapsulate the complicated surface geometries of lost foam patterns. Fluidization coupled with a mixing jet helps to homogenize the sand through stirring and may improve the integrity of the casting.At issue is the hydrodynamics of the sand and air around the foam pattern. The commercial package PHOENlCSTM is used to simulate the flow around the pre-casting foam geometry. Employing a two fluid approach, each component is considered a fluid that interpenetrates the other phase. To this end, the kinetic theory of granular 'flow for the sand phase was incorporated into the re-compilable PHOENlCSTM code.The results of this study consist of time-averaged void fraction patterns, with voidage being defined as the fraction of air in the mixture, around the foam pattern submerged in a two-dimensional fluidized bed. The model was benchmarked against past fluidized bed experiments. In order to better understand the dependence of the void fraction pattern around the lost foam pattern, certain physical parameters are varied and the resultant void fraction maps are predicted with the model. Physical parameters such as the aspect ratio of length to width, the placement of the mixing jet, and different mixing jet velocities are varied to illustrate the dependence of the time-averaged void fraction on those variables.Results consistently indicate the presence of channeling around the lost foam pattern, with the extent of the channeling and void formation reliant to a greater degree upon the placement of the mixing jet, and to a lesser degree on mixing jet velocity and aspect ratio.The increase in radial position of the mixing jet from the bed centerline had the desirable effect of granting the churning benefits of a penetrating jet, while at the same time minimizing the formation of excess void fraction at the top of the pattern."

Jan 1, 2001

By D. Doungdeethaveeratana

The extraction kinetics in a novel solvent extraction process have been investigated. In this process, the liquid-liquid emulsion is generated by bottom gas injection into countercurrently flowing aqueous and organic phases. This process has a number of advantages over the mixer-settler unit or the spray column in terms of simple equipment configuration, without any mechanical moving parts, and the ease of cleaning and process control, while providing a sufficiently large interfacial area for rapid mass transfer. The overall rate increased with increasing gas injection rate and height of the aqueous phase but decreased with increasing injector diameter at the same gas injection rate. The variation of the overall rate constant was correlated against a set of dimensionless numbers, representing the operating conditions. Extraction rates and efficiencies comparable to those in a mechanically generated emulsion were attained in this new process.

Jan 1, 1998

By F. D. S. Marquis

An investigation of the mechanisms of formation of two types of porosity-primary and secondary-their characterization, evolution during processing, and effects on the mechanical behavior (fracture, fatigue, and failure) of 7X50 and 2X24 alloys has been conducted. The mechanisms of formation of three forms of primary or cast porosity were investigated, and each form was characterized: (a) macroscopic shrinkage porosity-MSP); (b) microscopic interdendritic porosity (MIP); and (c) hydrogen gas porosity (HGP) or primary hydrogen porosity (PHP). The mechanisms of formation of four forms of secondary or thermal/thermomechanical porosity were investigated, and each form of porosity was characterized: (a) high temperature oxidation (HTO). internal hydrogen precipitation (IHP), or secondary hydrogen precipitation (SHP); (b) preheating blistering porosity (PBP); (c) eutectic melting porosity (EMP);and, (d) dissolution micro void formation (DMF). The evolution and interactions of the primary and secondary types of porosity (w.ith special emphasis on PHP and SHP) during industrial and laboratory processing and their effects on the fracture and failure behavior of both types of alloys (with special focus on fatigue crack initiation and propagation) were investigated.

Jan 1, 1996

By Y. K. Rao

In the carbonyl process for the refining of crude nickel CO(g) reacts with nickel in the 310-370K range producing nickel tetracarbonyl, Ni(C0)4(g). Iron and cobalt impurities also form gaseous carbonyls but their partial pressures are low. The carbonyl is led to a decomposer plant wherein the gas disproportionates in the 500-600K range depositing pure metal on nickel pellets that move countercurrent to the gas-flow. This system serves to illustrate the fundamental principles involved in the vapor phase mass transport of elements, against temperature-gradient, under the influence of chemical potential gradient. Unlike in the crystal growth, the source is at a lower temperature (say 350K) whereas the seed is in the hot-zone (say 550K) of the closed ampoule-type reactor. By assuming virtual gas-solid equilibria in the end zones, with diffusion of gaseous species between them acting as a slight perturbation, the quasi-steady- state mass-transport rates are computed for a range of CO-pressures and temperatures.

Jan 1, 1993

By V. A. Luganav

The behavior of arsenopyrite under heating has been studied by many scientists. It has been already established that under heating at more than 650°c and without air access the arsenopyrite dissociates with the formation of one atom arsenic. Under vacuum the dissociation process begins at 5500C with the formation of elemental arsenic. The residue of dissociation process contains pyrrhotite and throilite. In the presence of pyrite, arsenopyrite dissociates under lower temperature and with a higher velocity than without it. The industrial realization of fool scale processing of arsenic bearing raw materials is possible only by the use of standard equipment and oxygen containing blast. In this view the paper presents the results of the study on the effect of oxygen in the gaseous phase and its addition into the charge of pyrite in the process of arsenopyrite decomposition. Thermodynamic analyses showed that under thermal processing of arsenopyrite in the presence of pyrite and limited quantities of oxygen in the gaseous phase the formation of arsenic sulfides is possible according to the following reactions:

Jan 1, 2003

By A. Lakschevitz

The Amazon region offers a large potential for gold extraction but its peculiar characteristics such as heavy rains, lacking of roads and general infra-structure, nature of the ore deposits, etc.. do require special care in plant design. REMETÁLICA has developed a know-how is designing leaching plants which have been demonstrated to be profitable under those tropical weather conditions. The solutions adopted are related to general process route, leach liquor distribution and flow pattern, conditioning of solids and effluent treatment. These plants, now operating in South America countries, demonstrate the success for the technology developed. A tipical plant with 800 t/day ore processing capacity, may require an investment of US$ 1.200.000,00, arid have? a pay back period of a few months, depending on ore grade.

Jan 1, 1989

By D. J. Murdock

Cominco Ltd. has developed a number of innovative technologies for electrowinning. The paper discusses the application of these technologies to the copper industry. Tankhouse and cell design will be discussed in addition to anode cleaning and cathode handling. Specific examples of the application of this technology to the copper industry are cited.

Jan 1, 1987

By C. A. Young, J. D. Miller

Adsorption isotherms previously determined by in-situ Fourier transform infrared/internal reflection spectroscopy (FT-IR/IRS) for oleate adsorption at calcite and fluorite surfaces near pH 9 and at various temperatures are compared. Results indicate that, at both mineral surfaces, chemisorption occurs at equilibrium concentrations below approximately l x l0-5 M oleate while calcium dioleate surface precipitation occurs at higher equilibrium oleate concentrations. The extent of chemisorption at the calcite surface is 3 to 5 times less than that at the fluorite surface while the extent of calcium dioleate surface precipitation on calcite is nearly a magnitude larger than that on fluorite. However, for both minerals, surface precipitation decreases with increasing chemisorption. Contact angle measurements and flotation recoveries show the hydrophobicity of fluorite to be greater than that of calcite at each of the temperatures and oleate concentrations studied. Significant differences are noted only in the chemisorption region. Unlike calcite, the hydrophobicity of fluorite was sensitive to the presence of oxygen in the system. Multichannel Laser Raman Spectroscopy (MLRS) showed this behavior was caused by the double-bond reactivity of adjacent chemisorbed oleate molecules and subsequent formation of an epoxide/polyether complex at the fluorite surface. Such a reaction product could not be detected at the calcite surface. These differences in adsorption density, hydrophobicity, and polymerization behavior are discussed in terms of the intrinsic surface properties of the minerals.

Jan 1, 1999

By Heimo Thalhammer

During the refining of lead, copper or other metals the furnaces used in the process · often produce waste gases. This paper illustrates how these waste gases can be successfully treated and destroyed by CTP 2-bed or multi-bed compact systems, modified for the additional reduction of dioxins and furans. The CTP regenerative thermal oxidizer also destroys voes (organic compounds and odours) using ceramic blocks as a heat exchanging media. The raw gas is forced through the ceramic beds where it is heated up to the oxidation temperature level. The voes, dioxins and furans are destroyed in the combustion chamber, subsequently generating water, eo2 and heat. The hot purified gas heats up a second ceramic bed, which is used to preheat the raw gas after the valves have been switched. This process does not produce any secondary waste such as contaminated water, polluted air or any other products that have to be disposed of.

Jan 1, 2000

By Guy Xueyi

The environmental impact assessment of the Imperial Smelting Process for metallic zinc and lead production in Shaoguan Smelter, China, was carried out by the life cycle assessment method. The detailed inventory analysis of the Input/Output in the process during 1998-2000 was conducted and the allocation was done among the main products of zinc, lead and sulfuric acid, according to the system expansion and substitution principle, The environmental impacts were assessed by using the following five Eco-indicators: Gross Energy Requirement (GER), Global Warming Potential (GWP), Acidification Potential (AP), Heavy Metal Toxicity' (HMT) and Solid Waste Burden (SWB). The results from this study are useful to address the environmental situation of the technology practice in this smelter, and provide a scientific basis for the further improvement.

Jan 1, 2003

By Jing Lin, Yuan Xu, Qingcai Liu, Dengfu Cheng

"Smelting reduction technology has been developed greatly in recent years. But one of the key problems for this technology is about the refractory that used as lining material in the molten bath. Investigation and test shown that corrosion rate of refractory was much higher and the corrosion mechanism was much more complexity in the molten bath of smelting reduction with iron bath than that of the blast furnace and rotary furnace technology [l-5]. The corrosion behavior and corrosion rate of Al2OrC-ZrO2 series refractory in the melt of smelting reduction with iron bath have been studied by rotary immersion and quasi-static immersion test in this paper. The major factors that affect the interaction between the melt and refractory were investigated. The test results shown that the corrosion rate of AI2O 3-C-ZrO2 series refractory decreased with the ZrO2 increasing when ZrO2 content was from 3% to 10%. Ferrous oxides content, relative moving speed between the melt and refractory and temperature of the molten bath were the important factors that affect the corrosion rate. But the ferrous oxides concentration was the most important one. The corrosion rate was increased as a linear relation with the rising of ferrous oxides content of the melt. The corrosion rate in the quasi-static immersion was much less than that of the dynamic immersion (rotary immersion) for the Al2O 3-CZrO2 series refractory in the same testing condition. The corrosion mechanism of Al2OrC-ZrO2 series refractory is: graphite oxidized in advance, then interaction between the constituents of refractory and melt taken place and deteriorate layer of refractory and new compounds were formed, the properties of refractory was changed.IntroductionSmelting reduction with iron bath is a typical technology [3, 4, 6]. The obvious features of the melt for smelting reduction technology with iron bath are much higher ferrous oxides and much more complexity melt composition and structure than that of the blast furnace technology [2, 5-8]. The properties of the melt were changed dynamicilly and constantly in reduction process. On the other hand, the behavior of the melt depends on the activity and the reduction rate of ferrous oxides in the molten bath[9]. Because of the high concentration of ferrous oxides in slag and high reduction rate in the molten bath, the corrosion behavior and corrosion mechanism of the refractory lining by melt are an important factor in development of the technology of smelting reduction with iron bath. Up to now, improving refractory quality to anti-corrosion of melt and developing high quality and long term refractory used as the lining refractory materials in the molten bath of the final reduction furnace are also the most important questions for developing smelting reduction technology."

Jan 1, 2000

The cleaning of copper containing fayalite slag using a CuFe alloy was studied under an oxygen pressure ranging from 10-7 to 5 X 10-11 atm at 1200º c. The reduction of copper from fayalite slags by Cu-Fe alloys was found to be very effective. For example, at a P 02 of 10-7 atm, the copper content in the slag was reduced from 4.1 to 0.402 wt. percent after 90 min. of reaction time using a Cu- 5.27 wt. percent Fe alloy. The copper reduction rates were found to be independent of P02 in the gas phase when using Cu-Fe alloys which exhibit an iron activity of greater than 0.4. A mechanism for slag c1eaning is proposed based on the concept that the Cu-Fe alloy lowers the oxygen potential of the slag according to Eq.1 1, fol1owed by the reduction of cuprous oxide by wustite as shown in Eq.2. Here X represents element X in the alloy phase while (X) represents the element in the slag phase. The copper and iron transfer behaviour obtained in this study are explained by a ?Stepwise equilibrium model.

Jan 1, 1985

By Andre L. De Vegt

Hydrogen sulfide is an expensive chemical used in nickel, zinc and copper mining and metallurgical operations for selective recovery and concentration of metals, from leach water streams, acid plant blow down streams, refinery electrolyte bleeds and precious metal, plant bleeds. Hydrogen sulfide is either produced on site by catalytic reduction of elemental sulfur or transported to the site as liquefied hydrogen sulfide (H2S) or as a sodium sulfide solution (NaHS) Biologically produced hydrogen sulfide has economically very interesting, application possibilities in the mining and metallurgical industry. Converting sulfates from waste streams into usable hydrogen sulfide by biological reduction results in operational cost savings in existing lime treatment systems. H2S can be produced biologically for less-than $500/ton S. For the past ten years Paques has been engaged in the development and installation of treatment systems based on biotechnological processes to remove sulfur compounds from water, air and gaseous streams. Paques has designed and installed a groundwater treatment system for the Budelco zinc refinery in the Netherlands to remove sulfate and heavy metals. The hydrogen sulfide produced is used for recovery of metals,, mainly zinc, from the ground water stream. The system has been operating since May 1992 treating a flow of 5000 m3/d. At Kennecott's Bingham Canyon Utah copper mine, a pilot plant started operation in November 1995 to develop the process for selective recovery of copper from leach water using biologically produced hydrogen sulfide from sulfate containing groundwater. Other pilot plants are operated at DOE's Pittsburgh Research Center and at Cominco Research focusing on selective recovery of metals.

Jan 1, 1998