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By G. B. Harris

Much has been written over the past decade concerning the disposal of arsenic from metallurgical processes. In Canada, there are proposed regulations which would classify arsenic in the Primary Group of twenty one persistent, toxic pollutants to be banned or phased out. Since many nickel and cobalt ores, not to mention those of copper, gold and uranium, contain significant amounts of arsenic, it is pertinent to assess the current state-of-the-art of its disposal. The literature is reviewed, and it is demonstrated that from a purely chemical point of view, the family of ferric arsenates largely immobilize arsenic. There is clear evidence from laboratory studies that both crystalline ferric arsenate (scorodite) and amorphous ferric arsenates in which the molar Fe/As ratio is at least three (Fe/As = 3) have very low arsenic solubility; plant data are given to support this. The debate over the long term stability of these compounds continues however; the evidence presented for long term stability and for compound breakdown is critically reviewed in the light? of the recent structural studies, and the role of base metals in these compounds evaluated. Finally, conclusions are drawn as to the viability of a purely chemical process for the long term disposal of arsenic from metallurgical processes.

Jan 1, 1993

Roasting treatments were investigated to remove arsenic from a nickel concentrate. The main arsenic minerals and their proportions in the concentrate were niccolite (NiAs)-50%, gersdorffite (NiAsS)-40% and arsenopyrite (FeAsS)-10%. Thermal analysis showed that gersdorffite and niccolite began decomposing when heated above 640 and 830°C respectively. The maximum roasting temperature was limited by agglomeration of the concentrate above 900°C. A small vibrated bed reactor was used to investigate the effects of temperature and gas flowrate, the latter to sweep away evolved arsenic. At 900°C, 24% of the original arsenic remained in the concentrate. SEM examination of the calcine showed that the residual arsenic was associated with the calcium in the gangue minerals. Additions of sulphur (either as elemental sulphur or from pyrite) facilitated the decomposition of the arsenic-containing minerals, decreased reaction with calcium in the gangue and produced calcine containing 4-6% of the original arsenic. Treatment with chlorine during roasting was effective in reducing the arsenic content to similar levels. Generation of chlorine in the bed by sulphation of CaC12 also produced encouraging results. Arsenic, Nickel Concentrate, Roasting, Chlorine, Sulphur, Gersdorffite, Niccolite

Jan 1, 2005

By Alan James Parker

Chalcopyrite can be converted to pure copper by the following five steps. An exothermic sulfation roast of chalcopyrite; leaching of cupric sulfate from the calcine with dilute acid; precipitation of Chevreul's salt and or other copper sulfites with ammonium sulfite or precipitation of crude copper by autoclaving ammonium sulfite and cupric sulfate at 150°C; dissolution of Chevreul's salt, or the crude copper, as cuprous sulfate, using acidic cupric sulfate in an acetonitrile-water solution as oxidant; precipitation of pure copper by thermal disproportionation of the cuprous sulfate solution. Acetonitrile and acidic cupric sulfate solution recycle. Advantages over conventional processes include lower cost, lower energy consumption as waste heat, sulfur removal as ammonium sulfate or gypsum, rather than as sulfur dioxide and rapid throughput. The net reaction is: 2 CuFeS2 + 4H20 + 15/2 02 + 8 NH3?2Cu + 4 (NR4)2 SO4 + Fe2O3

Jan 1, 1976

By C. D. Adams, R. T. Tuenge, C. N. King, J. A. Samuels, B. F. Espinoza, R. C. Dye, C. F. Schaus, D. C. Smith, N. M. Peachey

"Recently, doped calcium thiogallate (CaGa2S4) phosphors have been investigated for use in electroluminescent flat panel displays. The current technique used for the deposition of thin film calcium thiogallate is sputtering. Unfortunately, this requires a high temperature annealing process to provide the desired crystallinity of the phosphor. Recent efforts have focused on the possible use of metal-organic chemical vapor deposition (MOCVD) to produce the CaGa2S4 layer. The use of MOCVD provides an attractive alternative to sputtering since it does not require heating above the strain point temperatures of the glass substrates used for the display panels. To accomplish this, the deposition of both Ga2S3 and CaS is investigated as these compounds are intermediate steps in the development of the phosphor deposition. Uniform, crystalline films of both Ga2S3 and CaS were deposited and the process shows promise for successful deposition of the CaGa2S4 phosphor.IntroductionThe lack of a satisfactory blue phosphor having sufficiently high luminances at low power has hampered the development of high resolution flat panel displays. Recently, a new series of blue emitting materials have been investigated for use in thin film electroluminescent (TFEL) devices. l ,2,3 These phosphors are based on a series of alkaline earth thiogallate host materials of the form MGa2S4:RE where M can be either calcium, strontium, zinc, or barium and RE is a rare earth ion. A full-color VGA TFEL panel using CaGa2S4:Ce as the blue phosphor has recently been fabricated and tested. l This FPD provided a luminance of 10 cdlm2 at 60 Hz. The enhanced blue in this display allowed its color capabilities to approach those of the conventional CRT.The method of depositing the phosphor onto the display panels in these test devices has been sputtering. Unfortunately the phosphor as deposited does not possess the crystalline properties required for optimum luminance. The crystalline structure is achieved by subsequent annealing of the deposited material. Although this post deposition anneal provides the desired crystal structure, it occurs above the strain point temperature of ordinary glass. Consequently, the implementation of these phosphors requires the use of glasses capable of withstanding high temperatures, adding to the cost of the final display unit."

Jan 1, 1994

By Mikiya Tanaka, Mikio Kobayashi, Kazuya Koyama, Yoshihiro Nishisu

Preparation of multicomponent powders are very useful and important for producing the materials with complicated and homogeneous structure. Therefore multicomponent powders have a lot of attention in the field of advanced value-added materials. The aqueous processing in hydrometallurgy has a broad potential for producing multicomponent homogeneous precipitates. Furthermore the aqueous processing has a future potential for integrating the separation, precipitation and synthesis processes. In this presentation the precipitation from homogeneous solution including rare-earths and/or common metals is presented. These precipitates probably consist of almost monodispersed, multicomponent and spherical particles by precisely controlling several reaction factors, reaction temperature, concentrations of starting materials, pH and so on. The separation of the nucleation stage and the growth stage of the particles is very important and how to control the reaction factors to realize enough separation is discussed. In this presentation the systems of Y-Eu-0, Y-Fe-0 and Y-Al-0 are mainly presented. In addition the precipitation-stripping method from organic phase is presented focusing the synthesis of multicomponent powders of Ni-La-0 system. These precipitates have multicomponents homogeneously and so they are converted to multicomponent ceramic powders by calcination. They are important compounds as phosphor, opto-magnetic materials, optical materials, hydrogen storage alloy or as the related precursors. In this presentation some characterization of these particulate materials is included.

Jan 1, 1998

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 J. J. Kim

In a study of buildup in a green-feed reverberatory furnace, it was determined that approximately half of the crucible area has a moderate buildup of 25 in. or less, and that the area extending 45 f t from the burner end of the furnace has only a slight buildup. The false bottom, averaging 6 in. in thickness, was found to cover the entire crucible area. The stratification of Cr2O3, A12O3, and SiO2 occurs throughout the slag layer; this phenomenon is the principal reason for the formation of the false bottom in the green-feed reverberatory furnace. The false bottom is caused primarily by the settling of FeO*(A1,Cr),03 aggregates, which are derived mainly from returned converter slag. The false bottom can be transformed to a solid permanent buildup in the furnace, particularly when the matte is completely withdrawn. From the material balance of Al2O3 and Cr2O3 around the furnace, It is estimated that the average rate of aluminum chromite accumulation is approximately 0.3 ton per day or less.

Jan 1, 1976

By D. C. Foguel, J. L. R. Bravo

For several years, Caraiba Metais S.A. (CMSA) had to stock the arsenic sludge generated from the electrolyte purification process of its tankhouse. The amount stocked · reached approximately 3,500 tonnes, as the effects of its recycling during the smelting process and consequently in the sulfuric acid plant were unknown. Besides, it had as limiting factors the high content of arsenic in the copper concentrates supplied by foreign countries as well as the reduced capacity of the tankhouse's purification plant. The choice for selling the mentioned residue, which generally contains more than 50% of Cu, was attractive, but the environmental policies and regulations had not allowed this option. Other alternatives, such as the production of bicupric arsenic by means of a solvent extraction process or arsenic trioxide, were considered but the economic feasibility was not attractive due to the absence of a domestic market and a poor international market. After a study of the arsenic partition in the metallurgical process, it was verified that the residue could be recycled without causing any operational problems or damage to the environment. To make this possible, the capacity of the purification plant was increased and the way of removing the arsenic sludge from the cells was modified from manual to mechanical, therefore avoiding the direct contact of the workers with this poisonous substance. Moreover, procedures for recycling in the smelter were established and tolerance limits were set for both the smelter and the sulfuric acid plant. The main amount of arsenic to be recycled is released with the smelting furnace off-gas, which is washed during the purification stage of the sulfuric acid plant. The acid water, rich in arsenic, is then treated in the waste plant and the arsenic, in its stabilized condition, is confined in an appropriate area.

Jan 1, 2000

By Manuel Alvarado, David Nemir, Jan Beck

"Thermoelectric generation using special N-doped and P-doped semiconductors is well known as a means for direct heat energy to electrical energy conversion without the need for moving parts. The technology is used today in niche markets for low level electricity production and has been proposed as a scalable means for capturing large scale energy from waste heat streams. The choice of geometry of the thermoelements and conductors is critical to the successful implementation of a waste heat recovery system in order to manage losses due to Joule heating and diffusive heat flows. This paper describes a simulation study to define the performance impact of different aspect ratios for the active thermoelements and the electrical interconnect. The use of a finite element model that incorporates the intercoupled heat and electrical energy flows highlights some of the issues impacting scalability.IntroductionThermoelectric phenomena arise out of the intercoupled electrical and thermal currents in a material. A two-element thermoelectric generator is depicted in Figure 1. It is constructed by connecting an N-type thermoelement and a P-type thermoelement in electrical series, with both elements in thermal parallel between a heat source and a heat sink. The electrical series connection is made by attaching conductors as shown. Ideally, these series connection elements will be both good thermal conductors and good electrical conductors.The two element generator in Figure 1 is disposed between two thermal reservoirs: the heat source, which furnishes heat energy; and the heat sink, which absorbs heat energy. Heat energy flux Q, flows from the heat source to the heat sink, driven by the temperature difference between the source and the sink. As depicted in Figure 1, when a resistive load, R, is attached, electrical current, I, may be extracted from the thermoelectric generator and furnished to the load. The N-type and P-type thermoelements, are the active portions that do the actual conversion of heat energy to electrical energy. Although thermoelements may be built using conductors such as bismuth and antimony, higher efficiency thermoelectrics are built using heavily doped semiconductors. Thermoelectric devices are generally formed by connecting many pairs (couples) of N and P type thermoelements in electrical series and in thermal parallel. A commercially available module having 127 couples (254 elements) is shown in Figure 2."

Jan 1, 2011

By Husamuddin Ahmadzai

A survey of regulations and state of the art control technologies is presented relating to the smelting of primary aluminium, copper and recycling of residues. Some costs associated with the alternatives and trends for the coming decade in this. sector are identified.

Jan 1, 1992

By Yukio Ishikawa

Sumitomo Metal Mining Co,. Ltd. (SMM) has been producing 22,000 t/y of electrolytic nickel at Niihama by nickel matte electrorefining process since 1970. Although the matte electrorefining is an established process and the productivity has been greatly improved in the last 20 years, SMM has intensively developed the chloride process for the nickel production since 1970's. The nickel and cobalt refining process involving solvent extraction and electrowinning from the chloride solution has been successfully developed for the treatment of the mixed sulphide in 1975. The first application of chlorine leach to the anode slime has been succeeded since 1986. Based on those technology, the matte chlorine leach electrowinning process (MCLE) has been developed as an alternation to the relatively old technology of matte electrorefining. The new process offers significant cost down and excellent quality of the product. In 1986, the feasibility of MCLE was confirmed by the test work using the integlated pilot plant. The innovation of the chlorine leach process has been undertaken by this work. The new refining process can be divided into three stages including chlorine leach stage, purification stage and electrowinning stage. More than 99 % of nickel was extracted in atmospheric chlorine leach. Although copper ion was used for electron carrier in the chlorine leach, the excess copper from the feed matte is bled off from the leach circuit by de copperizing electrolysis. The copper ion of the pregnant solution is fixed on nickel matte by the cementation reaction. The nickel matte containing copper is processed in the chlorine leach. In the purification circuit, cobalt, iron and other impurities were removed from the nickel chloride solution. The nickel chloride solution is then fed into the electrowinning cell. Based on the process established, the new plant with a capacity of 330 t/M electrolytic nickel was commissioned in order to obtain the engineering data for design of the full scale plant in 1989. The performance of the plant was fully satisfied and the new process demonstrated the potential application of modern process control.

Jan 1, 1992

By Mitsuru Tanahashi

In order to develop an effective process for the production of from metallurgical-grade one (MG-Si), the oxidation removal of boron from molten MG-Si was investigated at a solar-grade silicon (SOG-Si) 1773K by the following two CaO-saturated CaO-CaF2 flux treatment processes. I) Boron removal by flux addition onto the molten M6-8 followed by oxygen gas injection into the melt (Two-stage connecting process). II) Boron removal by simultaneous injection of flux powders and oxygen gas into the molten MG-Si (Simultaneous injection process). These processes can establish the special condition of both high basicity of the flux and the high oxygen partial pressure at the boron removal reaction sites. Through these processes, especially by the simultaneous injection Process using a flux powder injection equipment, the boron content in MG-Si can be efficiently reduced. The obtained results clarified that both processes should be conducted for a time period as short as possible by using as much flux as possible. By repeating the simultaneous injection process for 60 s three times under the optimum operating conditions determined in the present study, the boron content in MG-Si can be reduced from 14 to 4.7 mass ppm.

Jan 1, 2003

By James A. Voigt

"The efficient separation of metal species from aqueous streams by precipitation techniques requires a fundamental understanding of the various processes that occur during precipitation. These processes include particle nucleation, particle growth by solute deposition, agglomerate formation, and agglomerate break-up. The application of the population balance approach has been used to develop a kinetic model that accounts for these competing kinetic processes. The usefulness of the model is illustrated through its application to the precipitation of yttrium hydroxynitrate, YHN. The kinetic parameters calculated from the model equations and system specific solution chemistry are used to describe several aspects of the effect of pH on the precipitation of the YHN. Implications with respect to the simultaneous precipitation of more than one cation type are also discussed through use of example systems. The effects of solution chemistry, precipitator design, and solvent choice are considered.IntroductionThe application of precipitation technologies to the separation of metals from solution is widely used. Regardless of its application, be it in such diverse areas as the preparation of metal oxide powders for use in commercial products or as a unit operation in the removal of trace metals during wastewater clean up, the fundamental processes involved are the same. These processes include: nucleation from solution, either homogeneous or heterogeneous; growth from solution with chemical reaction either in solution or at the precipitate/solution interface; growth by particle agglomeration; and particle break-up by collisional or shear forces. The effectiveness of the operation and the properties of the precipitate formed, or ""quality"" of the product, are determined by the competing kinetics of the different processes. The kinetics of the processes, in tum, are determined by system-specific solution chemistries and the conditions used to carry out the precipitation operation. For example, generally, when system conditions are such that the supersaturation driving force for precipitation is very high, growth species normally do not have the time to organize themselves with a high degree of crystallographic order and the precipitate is amorphous. In this case nucleation rates are invariably extremely high and the primary mechanism for growth is the agglomeration of nuclei. Conversely, when the supersaturation levels for the same system are reduced, the kinetics of the nucleation and growth processes also are greatly reduced, and a crystalline precipitate can be formed, since the growth species have time to order on particle surfaces."

Jan 1, 1996

By Miroslav Raudensky, Kallol Bera, Jaroslav Horsky, Jee G. Chang, Ampere A. Tseng

"A combined experimental and finite element approach to study the local heat transfer coefficient is presented in this paper. The heat transfer coefficients at different cooling regimes in a roll are quantified by an inverse heat conduction technique; the heat transfer phenomena involved are then discussed. A discussion of the application of the heat transfer information found in the present study for better design of a roll cooling system is also included. Finally, an identification of areas where further work is needed is presented.IntroductionIn metal rolling processes, the roll is used as a tool to deform the workpiece at very high speeds. As shown in Fig. 1, the heat transfer phenomena involved in the process are complicated by the interaction between the roll and the strip, mainly including 1) the heat transferred from the workpiece to rolls in the contact regions, 2) the heat created in the interface due to the deformation of the workpiece and the friction between the workpiece and roll, and 3) the heat removed by watercooling as well as the ambient air. All of these transport phenomena occur at extremely high pressure, high speed, and high heat flux; these make the control of the roll temperatures an extremely challenging problem.In hot rolling, proper cooling of rolls can lead not only to improve the roll shape quality by controlling the thermal crown of the roll, but also to extend the roll life by minimizing the thermally induced stresses [1,2]. Also, knowledge of roll temperatures can contribute to insights about the roll/workpiece interfacellubricant behavior, and lead to the desired surface condition of the workpiece. Therefore, adequate roll cooling or control of roll temperatures is of critical concern to mill designers and process engineers. In order to have proper operation of the process, a good understanding of the influence of cooling practices on the roll is essential [3]."

Jan 1, 1994

By A. H. Rhoades

The modern polarizing microscope with such accessories as cameras, infrared devices, reflectance and/or transmission photometers, indention hardness, and heating stage is used to characterize coal, coke, and other carbon forms. It allows characterization of coke by-products, such as tars and pitches and their insoluble residues. A useful product of the microscopic approach is the coal petrographic analysis which permits the prediction of coke strength carbonization pressure and volume change. Carbonization tests are expensive, time-consuming and require large amounts of coal. Tests on the coke show it to be strong or weak but give no indication of why. Petrographic analysis requires grams of coal and yields data that indicates why the coal produces coke of a given quality. Small samples from drill cores are sufficient for petrographic analysis. These data are also used to optimize blends for coke production. When coke-plant problems occur, ~he microscope can be used to check the coal blend proportions, as well as for weathered coal. Microscopy is useful in spore correlation work which may be a prerequisite to sound coal reserve estimates. Dispersed vitrinoid reflectance studies are used to determine the degree of organic metamorphism which serves to establish oil and gas deadlines. Tars and pitches are examined microscopically for the amount of normal solids as well as the size of undesirable carry-over solids resulting from pollution abatement practices in coke works. The microscope is also used to study coals for gasification and liquefaction.

Jan 1, 1981

By Tom W. Gonzales

Magma Metals Company commissioned a 3000 tpd Outokumpu flash smelting furnace in July 1988. Through September 1992 the PSP has smelted a first campaign record 4.1 million tons of concentrate. This paper discusses modifications made to the original process equipment to overcome design flaws as well as future design changes currently under consideration.

Jan 1, 1993

The 15m high Inco flash furnace uptake was designed as a reaction chamber with the objective of destroying the H2S contained in the furnace off-gas by combustion with oxygen at about 1300°C. Until recently, the oxygen required for this purpose was injected through afterburners located at the bottom of the uptake. An undesirable side effect of this practice was the formation of build up accretions on the inside walls of the uptake. This buildup had a negative impact on both the furnace on line time and the control of the flash smelting process. In late 200 I, the afterburners were relocated to the roof of the uptake. As a result, about 80% of the uptake accretion buildup disappeared with obvious beneficial effects for the operation of the furnace. This paper discusses key flash smelting aspects that affect the operation of the flash furnace uptake such as the dusting rate, the formation of H2S in the freeboard of the furnace, and the impact of using coke to supply some of the heat required by the process. The mechanism of buildup formation and its dependence 'on uptake afterburners location are also examined. Prof. Yazawa's sulfide smelting thermodynamic relationships proved instrumental in understanding the conditions that influence the formation and the elimination of H2S and uptake buildup.

Jan 1, 2003

By John W. Graydon

Incineration is an attractive alternative to the disposal of MSW in landfill sites. However, the process of incineration generates fly ash which contains significant levels of leachable heavy metals - particularly cadmium, lead, and zinc - and it is essential to manage this fly ash in an environmentally sound manner. The compositions, phases, textures, morphologies and size of fly ash particles have been studied by light microscopy, scanning electron microscopy, X-ray microanalysis, and X-ray diffraction. The detailed spatial relationships and speciation of the environmentally significant constituents have received particular emphasis. The information obtained is useful in understanding how fly ash is formed during incineration, in understanding the leaching behavior of untreated fly ash if it is disposed of in a landfill and, most importantly, in guiding the development of the best treatment strategies for fly asti to mitigate its environmental impact.

Jan 1, 1992

By Tim J. A. Smith

Fundicion Refimet S.A. has operated a custom copper smelter at La Negra, near Antofagasta in northern Chile since 1993. From an initial operation based on Reverb smelting and Peirce-Smith, converting, the plant was expanded from 90 000 t/y to 160 000 t/y copper production in early 1997, by conversion to oxy-fuel smelting and use of concentrate injection on Converters. As part of this expansion a novel reverb gas cooling and cleaning system was developed and designed by Kilborn SNC-Lavalin Europe, the London, UK-based mining and metals; Office of Canada's SNC-Lavalin group. The reverb gas cooler needed to satisfy several very specific requirements including low cost, flexibility, robustness and simplicity of operation. Of particular importance was the requirement to cool and clean the ,oxy-fuel reverb gases and render them suitable for subsequent treatment in a conventional sulphuric acid plant. It was also important to avoid accretion or dust handling problems. This paper describes the key design features and subsequent successful installation, commissioning and operation of the unit.

Jan 1, 1998

By Tamas Kekesi

Anion exchange in HCl media is considered an efficient alternative to the combination of the conventional purification methods. Anion-exchange distribution functions have been determined for cobalt and the main impurity elements by the technique of batch equilibration. Results were confirmed by spectrophotometric investigations and elution tests. Based on the new and the available distribution functions, combined with the assessment of thermodynamic stability, a procedure of anion exchange separation has been devised to eliminate virtually all the impurities from the cobalt-chloride solution. Separation of copper has been enhanced by the introduction of a preliminary step under reduced conditions. The rest of the impurities are eliminated in a second anion-exchange step applying rinsing and elution stages under oxidized conditions. The optimum parameters of the procedure have been determined according to performance characteristics (purification ratios, yields and volume efficiencies) derived from the analysis of elution curves obtained with laboratory scale ion-exchange columns. Special computer programs have been developed to facilitate thermodynamic simulation, analytical correction and data processing.

Jan 1, 2003