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By I. Gaballah

About forty percent of the SOx emissions are generated during the processing of metal sulfides of Cu, Pb, Zn, Ni, etc. Although new technologies for metal sulfide's smelting allow the production of H2S04 with a reasonable cost and decrease the emissions of sulfur oxides, the generated quantity of SOx is considered as a serious threat to environment. This paper suggests alternatives for low temperature processing of complex sulfide ores or concentrates 'CSO or CSC' under neutral, reducing and chlorinating atmospheres or their combination. At T > 400 "C, The neutral and reducing treatments allow the decomposition of pyrite and the partial recovery of sulfur as So and H2S. At 300 "C, the chlorinating treatment of CSC is fast, exothermic and allows the separation of FeC13 from the valuable elements' chlorides. It also generates SyCIx that can be either reduced by H2 or hydrolyzed in presence of sodium sulfide. The recovery rate of elemental sulfur with respect to the sulfur input exceeds 90 %.

Jan 1, 1999

By Junfu Chen, Jiann-Yang Hwang, Yong Zhou, Lijun Lu, Likun Lia, Jixiong Liu

The sheet-like NiS-ZnS heterostructured composites were prepared by the microwave hydrothermal. The fabrication of the heterojunctions broadened the range of light response of ZnS. The photoexcited electrons of ZnS migrated to the redox potential of NiS/Ni2S under visible light irradiation, which can facilitate the effective separation of photogenerated electrons and holes in space. The visible photocatalytic activity towards hydrogen production for NiS/ZnS nanosheet heterostructed composites without co-catalyst achieved 0.28 mmol h–1, and the quantum efficiency was up to 18.6% under the wavelength with 420 nm visible light irradiation.

Jan 1, 2015

By Frederick T. Wallenberger

"Laser assisted chemical vapor deposition (LCVD) is a new containerless fiber process whereby growth of small diameter fibers or microstructures (microsprings, microsolenoids) occurs directly from the vapor phase. The laser beam has a focal point adjusted to coincide with the tip of the growing fiber inside the reaction chamber. Since the growing fiber is not in contact with reactor walls or foreign materials, it is chemically pure, and suitable for optical uses and uses requiring high structural uniformity. Continuous fibers and multifilament yams are possible. The use -of high reaction chamber pressures (1-10 bar) and a small wavelength Nd-YAG laser made it possible to fabricate small diameter fibers at growth rates >1 mm/s. This paper describes the synthesis of single crystal, polycrystalline and amorphous fibers by LCVD, and provides a comprehensive analysis of phase transformations occurring during their fabrication.IntroductionLaser assisted chemical vapor deposition (LCVD) is a new containerless fiber process [1-10] whereby growth of small diameter fibers or microstructures occurs directly from the vapor phase. The laser beam has a focal point adjusted to coincide with the tip of the growing fiber in the reaction chamber (Figure 1). The diameter of the growing fiber corresponds to that of the laser focus. Depending primarily on the laser energy (Le., the temperature at the growing fiber tip), it is possible to obtain single crystal, poly crystalline or amorphous fibers by this method.Since the growing fiber is not in contact with reactor walls or foreign materials, it is chemically pure, and suitable for optical uses and uses requiring high structural uniformity. Laser assisted CVD is a potentially continuous process; continuous fibers and multifilament yams are possible."

Jan 1, 1994

By Serdar Aksu, Fiona M. Doyle

"CMP will be an essential process in the production of integrated circuits containing copper interconnects. This study aims to improve our mechanistic understanding of the role that organic chelating agents might play in the reactive slurries used in copper CMP. Copper dissolution behavior in EDTA arid glycine was first examined by producing potential-pH diagrams for the copper-water-EDTA and copper-water-glycine 'systems. The results of potentiodynamic polarization experiments were then considered in light of these diagrams. . In-situ polarization experiments were conducted to gain insight into the electrochemistry of copper during dynamic polishing in slurries prepared from EDT A and glycine.IntroductionCopper has recently started to replace aluminum as the interconnect metal in integrated circuits. Copper interconnection offers faster and more reliable integrated circuits due to its higher electrical conductivity and superior electromigration resistance (1). The damascene method is used to form multilevel interconnects in the manufacture of integrated circuit devices with copper metallization (2, 3). Copper is deposited by CVD or electroplating into vias and trenches etched in the interlayer dielectric (IDL), over a diffusion barrier usually made from titanium, tantalum or their nitrides. Chemical mechanical planarization (CMP) then prepares the wafer for the next deposition step, by removing excess copper and planarizing the surface. During CMP, the wafer is rotated and pressed against a rotating platen covered with a polishing pad. Chemically active slurries containing submicron size abrasive particles (Si02, Al20 3, ceria, diamond, etc.) are applied. Both the mechanical action of the abrasive particles and the chemical action of slurry constituents remove material from the wafer surface. Planarization results because material is removed faster from protruding regions on the surface than from recessed regions. Since CMP can globally planarize .the entire wafer, it has become one of the key technologies for producing integrated circuits with copper metallization."

Jan 1, 2000

By Katsuyoshi Tatenuma

"In order to mitigate the effect of global warming by preventing the accumulation of atmospheric CO2, a permanent fixation method of surplus CO2 as an insoluble mineral onto the sea bottom is proposed. As the proposed reduction method of atmospheric CO2, the concrete concept of this method is to form an insoluble carbonate mineral (CaCO3) by direct electrolysis of the seawater; Ca2++2HCO3 -+OH- ? ?CaCO3(insoluble)+CO3 2- (soluble)+H++H2O <not as coral reef reaction>, are directly disposed of itself onto the sea bottom. By this treatment, a concentration of carbonate is reduced in the section of superficial seawater, and therefore the absorption capacity of atmospheric CO2 increases depending upon the shift of chemical carbon equilibrium between the mass of superficial seawater and the atmosphere. As no additives are required, or no secondary waste are produced, the proposed method assuming as green-orientated, has possibility to resolve fundamentally the problem of global warming in a green orientate manner.IntroductionRecently, the amount of atmospheric CO2 has been exponentially increasing and it is a main greenhouse effect gas causing the global warming [1, 2]. The concentration of atmospheric CO2 has increased more than 30% (370ppm in 2001) during only last two centuries, therefore approximately 750 Gton-C of CO2 currently exist in the atmosphere, in which 180 Gton-C of CO2 are accounted for the increment during two centuries [1, 3, 4]. In order to avoid the progressive increase of CO2 global abundance, 3 Gton-C of the incrementing amount per year [4], have to be removed annually from the atmosphere."

Jan 1, 2008

By Zdzistaw MiGzkowski

At KGHM Polska Miedi S.A. a direct flash smelting process is used for smelting of chalcocite concentrate for the production of blister copper. The paper presents a model of complex oxidation process of single concentrate grains smelted at KGHM. The description covers main chemical reactions, phenomena of heat and mass ex-change inside the grains and between a grain and the surrounding space. In the model, two zones describing the course of process inside the grain were distinguished: ? The first one, which moves faster towards the centre of a grain, both organic and carbonate carbon are freed. The process takes place without the presence of oxygen and results in an increase of the temperature in the core of the particle. ? The second zone moves slower into the grain and the rate of the movement is deter-mined by the presence of oxygen. In that zone the sulphur is eliminated and the oxidation of the organic compounds vapours moving from deeper layers of a grain takes place. Based on the results of laboratory tests, the coefficients that describe the oxygen transportation into the grain and decide the progress in the chemical reaction were determined. The paper contains the results of model calculations for single grains reacting in environment of various content of oxygen as well as the results of model calculations for the laboratory reactor system.

Jan 1, 2003

By Dong Joon Min, Joo Hyun Park, Mi Sun Choi, Jae Hong Shin

Sublimation of ZrCl4 is important for the production of nuclear grade metallic Zr in Kroll’s process. The sublimation kinetics of ZrCl4 was investigated by TGA under both isothermal and non-isothermal conditions. The sublimation rate of ZrCl4 increased with increasing temperature under isothermal conditions. ZrCl4 sublimation was confirmed to be a zero-order process under isothermal conditions, whereas it was first-order kinetics under non-isothermal conditions. The activation energy of ZrCl4 sublimation under isothermal conditions was 21.7 kJ/mol. The activation energy for non-isothermal sublimation was 101.4 kJ/mol and 108.1 kJ/mol with the Kissinger method and Flynn- Wall-Ozawa method, respectively. These non-isothermal activation energies were very close to the heat of sublimation (103.3 kJ/mol). Sublimation occurs by two elementary steps: surface reaction and desorption. Therefore, the overall activation energy of ZrCl4 sublimation is 104.8(±3.4) kJ/mol. The activation energy of the surface reaction and desorption steps are proposed to be 83.1 kJ/mol and 21.7 kJ/mol, respectively.

Jan 1, 2014

By L. Yin, R. B. Haber, N. Sobh, D. A. Tortorelli, R. W. Hyland Jr.

"We optimize continuous quench process parameters to produce a desired precipitate distribution in aluminum alloy extrudates. To perform this task, an optimization problem is defined and solved using a standard nonlinear programming algorithm. Ingredients of this algorithm include a cost function, constraint functions and their sensitivities with respect to the process parameters. These functions are dependent on the temperature and precipitate size which are obtained by balancing energy to determine the temperature distribution and by using a reaction-rate theory to determine a discrete precipitate particle size distribution. Both the temperature and the precipitate models are solved via the finite element method. Since we use a discrete particle size model, there are as many as 105 degrees-of-freedom per finite element node. After we compute the temperature and precipitate size distributions, we must also compute their sensitivities. This seemingly intractable computational task is resolved by using an element-by-element discontinuous Galerkin finite element formulation and a direct differentiation sensitivity analysis which allows us to perform all of the computations on a PC.1 IntroductionThis work addresses the need for an integrated design capability that links microstructure evolution to the process parameters. It is motivated by the manufacture of lightweight aluminum-alloy extrusions for use in automotive structures. Aluminum alloys offer obvious benefits, however, care must be taken to manufacture favorable microstructures that ensure acceptable structural performance. For example, the manufacturing process for 6000-series components involves hot extrusion of cast aluminum billets followed by either an air or water quench process. The bill~t's initial grain structure is dramatically altered during extrusion by massive mechanical deformations and recrystallization processes. The microstructure continues to evolve during the quench, as complex chemical processes determine the formation of precipitates. The control of the precipit'ate size distribution is vital. Indeed, large precipitates located on grain boundaries serve as crack initiation sites which adversely effect structural crash· worthiness."

Jan 1, 2000

By T. J. A. Smith

This paper provides an overview of some of the key issues in design of smelter gas handling systems, with particular reference to smelter smelting plants. In both primary smelting and converting, gas handling and treatment systems often represent the major capital cost component. There is also ample evidence that poor system design can be a major cause of smelter down time, lost production and unforeseen high maintenance costs. The paper discusses these issues and offers guidance for improved design.

Jan 1, 1992

By Lenny Winkel

With the aim to develop a solar-driven process for the extraction of copper from sulfide concentrates research on the decomposition of copper sulfides under inert atmospheres has been initiated. Thermogravimetric measurements on chalcocite (CuzS) revealed that copper is formed already at 1823 K. Chalcopyrite (CuFeS2) also disintegrates at this temperature, although at a lower rate. Copper and iron have been identified in the solid residue. The results confirm the feasibility of copper extraction by direct decomposition of sulfides under atmospheric pressure. The decomposition under inert atmosphere prevents generation of SO2, it also alters the behavior of volatile impurities during decomposition of copper sulfide concentrates. Chemical eqUilibrium calculations for chalcopyrite contaminated with enargite (Cu3AsS4) have shown that the absence of an oxidic slag allows for a complete evaporation of arsenic and subsequent separation from intermediate sulfides. The need to better assess the potential of direct sulfide decomposition has prompted the development of an experimental setup for studying the decomposition reactions. The experiment has been devised such that data on the decomposition kinetics and on impurity removal can be obtained at temperatures up to 2500 K.

Jan 1, 2003

By Zdzislaw Miczkowski

At KGHM Polska Miedz S.A, a direct flash smelting process is used for smelting of chalcocite concentrate for the production of blister copper. The paper presents a model of complex oxidation process of single concentrate grains smelted at KGHM. The description covers main chemical reactions, phenomena of heat and mass exchange inside the grains and between a grain and the surrounding space. In the model, two zones describing the course of process inside the grain were distinguished: ? The first one, which moves faster towards the centre of a grain, both organic and carbonate carbon are freed, The process takes place without the presence of oxygen and results in an increase of the temperature in the core of the particle. ?The second zone moves slower into the grain and the rate of the movement is determined by the presence of oxygen, In that zone the sulphur is eliminated and the oxidation of the organic compounds vapours moving from deeper layers of a grain takes place. Based on the results of laboratory tests, the coefficients that describe the oxygen transportation into the grain and decide the progress in the chemical reaction were determined, The paper contains the results of model calculations for single grains reacting in environment of various content of oxygen as well as the results of model calculations for the laboratory reactor system.

Jan 1, 2003

By William E. Torres

The Southern Peru Limited smelter, in Ilo, operates two reverberatory furnaces, seven Peirce-Smith converters, one Teniente Converter, two casting wheels and a single contact acid plant. The Teniente Converter was commissioned in August 1995 and was designed to smelt 744 dry metric tons (820 dry short tons) of concentrate per day. The process off-gas is collected in a water-cooled hood, cooled in a spray chamber, and cleaned in a Joy electrostatic precipitator for further treatment in the Acid Plant. This paper presents the current Teniente Converter operating practices and control philosophy. Relevant improvements and modifications to achieve a 379 day campaign without tuyere replacement and a daily average smelting rate of 862 dry metric tons (940 dry short tons) of concentrate are discussed.

Jan 1, 1998

By Derek J. Fray

"In order to extend the application of fused salts in\the electrowinning and electrorefining of metals, it is necessary to maximise the current density, minimise the voltage drop and greatly increase the area of electrode surface so as to compete with the space-time yield of pyrometallurgical reactions. The various designs of electrowinning cell are reviewed and it is shown that by the application of a modest centrifugal field it is possible to reduce the anode to cathode interelectrode spacing to 4 mm whilst still maintaining a current efficiency of 85-90%.The thermodynamic potential for electrorefining is far less than for electrowinning yet fused salt electrorefining is only applied in limited cases. The reasons for this are discussed and the important design parameters evaluated. It is concluded that by using packed bed electrodes, separated by a diaphragm, the possibility of electrorefining with very low energy consumption can be achieved. Carbothermically-produced metals are always cheaper than those produced by electrolysis but suffer from the disadvantage of low purity. It is proposed that fused salt electrorefining may offer an energy efficient way of upgrading the metal. IntroductionThe majority of metals can be deposited from fused salts (1,2) but as commercial production is restricted to the more reactive elements, it is worthwhile considering the advantages and disadvantages of fused salt electrolysis as' compared to smelting and aqueous electrolysis. The advantages over aqueous extraction are as follows:1) the much higher conductivities and diffusivities result in much lower IR losses and higher current densities can be achieved at modest voltages;2) the elevated temperatures of operation result in larger exchange currents which give rapid kinetics and lower activation polarisation for the electrode reactions;3) the absence of water as a solvent means that it is not necessary to consider the evolution of hydrogen as a competing cathodic reaction. Furthermore, alkali halide salts, often used as solvents in fused salt electrolytes, have high deposition potentials;4) molten salts generally are mutually soluble and, therefore, concentration polarisation effects are minimised."

Jan 1, 1988

By Xiang-ning Meng, Miao-yong Zhu

"A three-dimensional finite-element heat-transfer model is conducted to predict temperature of hot copper plate in a slab continuous casting mold and the effect of casting speed on temperature difference between copper plate and solidifying shell is simulated in combination with process data. The results show that centre temperature of hot copper surface at casting speed 1.8 m·min-1 and 2.0 m·min-1 are higher than that of 1.6 m·min-1 casting speed 4.7-5.2 °C and 11.2-12.2 °C respectively and temperature is not increased linearly with casting speed. Temperature difference in meniscus between mold and shell is influenced obviously by casting speed and increased 4.0- 6.0 °C with increment of casting speed 0.2 m·min-1• Fluctuation of temperature difference in meniscus is a main reason to deteriorate casting quality as increasing casting speed.IntroductionIn conventional continuous casting of steel, a large amount of sensible and latent heat of molten steel dissipates in primary cooling zone and mold becomes a critical component of caster to govern steel quality, meanwhile, thermal load on mold is increased constantly and environment is also more abominable since high productivity and quality are required and high-effective technologies are applied. So, an in-depth understanding of thermal behavior of mold at high casting speed is essential to design cooling structure and maintain casting stability. Many studies have been carried out to shed light on thermal behavior in mold. Chow et al. [l] applied a mathematical model to heat transfer in billet mold at a high casting speed to give a new taper in order to minimize mold-strand interaction. Thomas et al. [2] researched relation between mold geometry and temperature distribution based on a finite-element heat-transfer model. Lu et al. [3] indicated that slab mold temperature are mainly affected by thickness of copper plate and nickel layer by a heat transfer model. Samarasekera et al. [4, 5] researched temperature of copper plates for both billet and slab molds and effect of a large number of factors ranging from water quality to casting speed. Park and Thomas et al. [6, 7] developed a finite-element thermal-stress model to determine temperature and thermal distortion and stress in both thin and slab molds and O'Connor et al. [8] applied an elastic-plastic-creep finite-element model in a funnel shaped mold to achieve same goals. Cicutti et al. [9] evaluated heat transfer and temperature fluctuation in a slab mold and proposed an expression to predict global heat flux as a function of process parameters and an index to quantify thermal instability. All mentioned above shown that thermal behavior is not only important to casting stability, it is also premise to further understand mechanical behavior in mold."

Jan 1, 2011

By Raj P. Singh

Two design-of-experiments studies were carried out to investigate the leaching of technical grade molybdenum tri-oxide (TGM) in the presence of hydrochloric acid and the mother liquor of ammonium di-molybdate crystallization used as an ammonia source. Results indicated that leaching of TGM in HCl is possible only when used at about 1N concentration. In high concentrations of HCl, technical grade MoO3 had very high solubility (7.5 to 40 g/L Mo). The most suitable conditions for HCl leaching of TGM were obtained at a slightly elevated temperature of 80°C. Using about 1N HCl at 80°C, potassium in the leached solids (TGM) decreased to about 110 ppm, a value typically obtained in TGM leached in HNO3 - NH4NO3media (3.5 - 4.0 moles /L HNO3 + 0.5 ? 1.0 moles/L NH4NO3). Mo losses under these conditions were 0.8-0.9 g/L Mo. The HCl-leach method, presented here-in, has a significant advantage in chemical cost and environmental benefits over HNO3 ? NH4NO3 purification method.

Jan 1, 2006

By S. L. Pohlman

Physical characteristics of possible importance in the acid leaching of Chrysocolla have been evaluated. Surface area studies and pore size distribution indicate: 1) a large surface area (350 m /gm); 2) an average pore size of 13 or 16 Å , depending upon use of the adsorption, or desorption, branch of the Type IV isotherm in the evaluation; ) the presence of a significant fraction of pores of size less than 15 Å determined by the accumulation surface area method. The initial structure is micro- crystalline on the basis of x-ray powder patterns; the silica leach residue is amorphous and has only 24 m2 /gm surface area, and loses integrity when dry. However, readsorption of copper onto the wet leach residue gives a product with integrity and 100 m2 /gm surface area. Visual observation of the leach residues supports evidence of a non-protective diffusion mechanism of leaching which is well correlated by the shrinking core model previously presented.

Jan 1, 1976

By R. J. St. Eloi

The Kidd Creek Copper Smelter has been expanded from its original design of 59,000 tonnes of copper per year to over 120,000 tonnes per year .. Modifications to the process gas handling system and acid plant have been made to accommodate this higher production rate and to .generally optimize the operation. The gas handling system associated with the continuous smelting process is discussed in terms of boiler accretions and modifications to minimize their impact on operations; design changes to effect reductions in high pressure drop duct configurations; material changes to overcome corrosion and plant additions to &apos;improve gas cleaning capability. The acid plant is reviewed with references to changes made to accommodate the increased S02 gas strength resulting from the higher smelting rates;

Jan 1, 1992

By B. C. Blakey

Unlike most hydrometallurgical slurries, those containing significant concentrations of goethite are typically highly viscous and shear-thinning, even at solid volume fractions below 5%. The viscosity may also depend upon time. These characteristics must be taken into consideration in slurry transport and heating. The technical literature is replete with apparent contradictions regarding the viscous behavior of these slurries, which may be due, in part, to variations in viscosity-measuring techniques. We present techniques that yield consistent results suitable for use in process design. A striking degree of time-dependent behavior is demonstrated for a laterite slurry. Reliable methods to design and analyze tubular transport and heating systems for time-independent slurries are summarized. Rules of thumb are then offered to account for the effects of time-dependency.

Jan 1, 2000

By E. Fregeau-Wu

The mineralogy and grain size distribution of phases in a steelmaking slag and experimental products from the heating of the slag under various conditions were determined to explore the possibility of recycling of the iron and manganese to the blast furnace. The steelmaking slags consisted of three major phases: dicalcium silicate, dicalcium ferrite, and Mg-Mn-wustite. Most of the phosphorus was contained in the dicalcium silicate and to lesser extent in the dicalcium ferrite. Due to the fine grain size of the dicalcium silicate, grinding and magnetic separation required pretreatment to increase the grain size and hence the liberation. Experiments on a steelmaking slag were conducted by heating the slag to 1633-1748°K( and slow-cooling in an inert atmosphere at various rates with or without the addition of fluorspar (CaF2) as a flux. Grain size distribution analyses of the starting material and the slow-cooled products were performed using the SEM-IPP area scan method and the QEM*SEM linear scan method. Comparable and reproducible results were obtained on the same sample using both methods. A size versus volume percent plot showed the increased grain growth most effectively. Examples of the grain size distributions obtained were used to show that a higher soaking temperature prior to slow-cooling, a slower cooling rate, and the addition of fluorspar to the slag promoted grain growth.

Jan 1, 1989

By Roger Altman

The solubility of copper in primary spinel crystals encountered in reverberatory slag samples has been determined by electron microprobe analysis. These spinels, which ranged in composition from 22% A12O3 to pure magnetite, contained small quantities of dissolved copper (0-0.4%). Based on literature data it was estimated that the solubility limit of copper in solid magnetite is no greater than about 1% at 1200°C and about 2% at 1250°C. However, it was found that practically every spinel crystal examined contained significant amounts of matte inclusions. Further examination of converter slag revealed large quantities of irregularly shaped precipitated magnetite crystals which contained a large proportion of copper inclusions. Additional experimentation showed that the total copper content in reverberatory slag samples was greater than the sum of the estimated en- trained plus dissolved matte in the slag. This difference is believed to be significant and is due to the presence of matte inclusions in the spinel crystals. In the present reverberatory slag samples these inclusions accounted for about 1/2 of the amount of sulfide directly entrained in the slag.

Jan 1, 1976