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By Edouard Asselin, Guikuan Yue

"In the present study, electrochemical measurements, especially cathodic potentiodynamic polarization (CPC) and cyclic potentiodynamic polarization (CPP), have been employed to study the kinetics of ferric reduction on chalcopyrite in aqueous Fe( II )-Fe(III)-H2S04 solution at 25°C and 70 °C. Results from the calculation ofspeciation in the above solution reveal that, at both 25 °C and 70 °C, the real Fe3+/Fe2+ ratio is much lower than the nominal ratio, which leads to smaller values for the reversible potential of the ferric/ferrous couple based on the Nemst equation. Exchange current densities of the ferric/ferrous couple were obtained by extrapolating the cathodic linear Tafel line to the reversible potential and are on the order of 10-7·10-6 A/cm2 at 25°C and 10·6-10-5 A/cm2 at 70 °C, respectively. The transfer coefficients were about 0.35-0.38 at 25°C and 0.35-0.45 at 70 °C. Polarization plots of CPC and CPP under different nominal Fe3+/Fe2+ ratios are in good agreement at 25 ·c and at 70 °C. Based on the obtained exchange current densities, the rate constant k, was calculated and is on the order of 10-1 cm/s at 25 °C and 10 1 cm/s at 70 °C.IntroductionChalcopyrite is the most abundant copper mineral in nature, accounting for about 70% of copper reserves in the world [I]. In recent years, the metallurgical industry has been searching for a hydrometallurgical process as an alternative to pyrometallurgical treatment due to high emissions of S02 and capital costs associated with smelting. Activity in this area has increased recently due to some inherent advantages associated with hydrometallurgical processing, such as the possibility of treating low-grade ores (increasingly more abundant in the case of copper) and easier control of waste, with the attendant benefits to the environment [I]. Chalcopyrite is highly refractory under most hydrometallurgical conditions, owing to the formation of an anodic passivation layer on the chalcopyrite surface which renders the process kinetics very slow. Most of the currently proposed processes are based on sulfuric acid with ferric ions and/or dissolved oxygen as oxidants. Sulfuric acid is preferred over all other leaching reagents in terms of cost, environmental friendliness, and ease of its regeneration during electro-winning. Some of these processes have been piloted in attempts to implement these technologies on an industrial scale,"

Jan 1, 2012

By Hongmin Zhu, Qiuyu Wang, Shuqiang Jiao, Guojing Hu

"The equilibrium between titanium ions and metal titanium was investigated in fluoride-chloride molten salt. The electrochemical properties of titanium ions in fluoride-chloride were studied on a molybdenum electrode by cyclic voltammetry (CV) and square wave voltammetry (SWV). The equilibrium constant of the equilibrium between titanium ions and metal Ti was calculated in KCI-NaCl- 2.5wt %K2 Tif 6 at the temperature of 1073K.IntroductionTitanium, the ninth most abundant element in the earth's crust, is endowed with high strength, low density, excellent flexibility, strong spring back characteristics, high-temperature performance, corrosion resistance and biocompatibility. These characteristics make titanium eminently suitable to be used in aerospace, marine industries, and harsh chemical environments. Although it has many excellent properties, the application of titanium in industry was limited by its high-cost. Therefore, many methods have been investigated for producing high-purity titanium at low cost. Electrolysis, involving the extraction and preparation of pure metal from ore using an electrolytic process, is considered a promising method for titanium metallurgy. Many studies have focused on the electrochemical behaviour and electrodeposition of titanium in molten chloride, fluoride, and chloride-fluoride electrolytes (1-IOJ. The electroreduction mechanism of Ti3+ ions in molten alkali chlorides has previously been studied by several workers. Two reduction steps, Ti3+ -Ti2+ -Ti, have been observed in various molten alkali chlorides [IJ. One reduction step, Ti3+ -Ti, has been observed in alkali fluoride molten salts l21. The behaviour of Ti4+ in fluoride or chloride-fluoride molten salts has also been investigated in the literature; it was proposed that the reduction of Ti4+ ions in the molten salts proceeded in a two step process: Ti4+-Ti3+-Ti l3l or a three step process: Ti4+ -Ti3+ -Ti2+-Ti ri. 4l Indeed, the stability of the titanium oxidation states depends on the bath composition l5l. The valence state was Ti2+ in alkali chloride melts, which was a lower oxidation state and correspondingly, in alkali fluoride melts, the higher oxidation states ofTi4+ and Til+ were more stable.The aim of the present work is to explore the effect of F/Cl atomic ratio on the equilibrium between titanium ions and metal titanium in fluoride-chloride at the temperature of 1073K. The electrochemical properties of titanium ions in fluoride-chloride were studied on a molybdenum electrode by cyclic voltammetry (CV) and square wave voltammetry (SWV). The solubility product of the equilibrium between titanium ions and metal Ti was calculated."

Jan 1, 2012

By Jian-hua Ren, Guang-liang Wu

A lot of dust is produced in iron and steel enterprises, giving rise to serious environment pollution, with which all countries are trying to find methods to deal. The influence of relevant technological factors on dephosphorization was investigated in laboratory, and the effect laws of that were analyzed. The results demonstrate that, in the given conditions of the best slag-metal proportion for hot metal dephosphorization is 1:10, and the optimum temperature is 1350 , The phosphorus distribution ratio of dephosphorization agent containing converter dust of 30% has the maximal value, with dephosphorization rate reaching 85%. Under the optimal conditions, premelting dephosphorization agent can significantly improve the ability of dephosphorization, dephosphorization efficiency increasing to 92%. Therefore, the dust can substitute the oxidant and fixative of dephosphorization agent, be used in hot metal dephosphorization, to enhance the efficiency of utilization.

Jan 1, 2016

By Larry F. McHugh

Current sulfide ore processing methods involving mechanical sizing of ores, froth flotation, electro-winning, solvent extraction, smelting and roasting are quite effective but typically represent a significant energy and environmental cost. This paper is the subject of a recent patent application and development program involving major improvements in sulfide ore processing. This two-step ?looping oxidation? process effectively removes sulfur while producing materials of adequate purity in an energy proficient and environmentally friendly manner. The first step results in a metal sub-oxide and a highly concentrated sulfur oxide off-gas stream. This gas stream can be processed for recovery in a more effective manner regarding both energy and capital equipment costs. In the second step, this metal sub-oxide is further oxidized to efficiently generate energy that can be recovered and utilized without the typical complications of an ?acid gas? stream process. Additionally, a portion of the final fully oxidized product can be looped back to the first step as the oxidizing agent. This process will be described in detail and compared to existing technologies in the area of energy efficiency, and off-gas environment treatment energy requirements.

Jan 1, 2008

By D. Quattrini

The aim of the present work is to present the gas chromatography (GC) as an alternative method of analysis in the thermal decomposition of calcium carbonate. Therefore, a furnace/GC on-line system was employed to study the kinetics of the reaction, measuring the CO2 produced in the decomposition. One of the advantages of the GC method is the possibility to perform an in-situ characterization and quantification of the gaseous products to obtain kinetic parameters, besides the method is simple and shows a good reproducibility. The decomposition of calcium carbonate was carried out in isothermal conditions at temperatures from 655 to 715°C with nitrogen as purge gas. Several gas velocities were used to determine the adequate flow that minimizes the effect of external mass diffusion as rate controlling step. It was made a preliminary analysis of the sample size influence on the reaction rate. The activation energy of the reaction was determined by Flynn method. The value obtained was in a good agreement with other authors. On the other hand, gravimetric measurements were employed for compare GC results.

Jan 1, 2006

The physico-chemical principles of chloride hydrometallurgy are reviewed to rationalise the complex chemistry in chloride-based processes for metal sulphides in terms of the predicted Eh-log[Cl-] relationships, measured changes in activity of H+, Mz+, Cl- and solubility of Ag(I), Cu(I), Cu(II), Pb(II), Ni(II), Au(III), Sb(III) and Bi(III). These changes reflect the nature of chemical speciation, competing effect of hydration/hydrolysis and chloro-complexation,composite effect of increasing acid and/or salt concentration and decreasing water activity. Rate data for the dissolution of PbS and ZnS in HCl containing Fe(III) or Cu(II) are compared and contrasted to highlight the effect of acid and chloride concentration, water activity, and the nature of oxidant. It is shown that LiCl, NaCl and HCl influence the kinetics of oxidative PbS leaching based on their effect on solubility of PbCl2 co-precipitated with elemental sulphur on the mineral surface. Evidence for the beneficial effect of Cu(II) in sulphide leaching is discussed.

Jan 1, 2003

By James E. Simpson, Suresh V. Garimella, III de Groh

"An experimental and numerical study of the horizontal Bridgman growth of pure succinonitrile (SCN) and of a succinonitrile-1.0 mol. % acetone alloy (SCN-1.0 mol. % ACE) has been performed. Experiments at growth rates of 0, 2 and 40 µmis were investigated. The solid/liquid interface was stable (non-dendritic and non-cellular); however, it was not flat. Rather, it was significantly distorted by the influence of convection in the melt and, for the growth cases, by the moving temperature boundary conditions along the ampoule. For the alloy, the interface was determined to be unstable at growth rates greater than 2.8 µmis, but stable for the no-growth and 2 µmis growth cases. When compared to the pure SCN interface, the alloy interface forms closer to the cold zone,· indicating that the melting temperature has been suppressed by the addition of the alloying element. Two-dimensional computer simulations were performed for the no-growth case for both the pure and alloy materials. These simulations indicate that a primary longitudinal convective cell is formed in the melt. The maximum magnitude of velocity was calculated to be 1.515 mmls for pure SCN and 1. 724 mm/s for the alloy. The interface shape predicted by the computer simulation agrees well with the experimentally determined shape for the pure SCN case. In ongoing work, numerical simulations of the process during growth conditions are being performed.IntroductionIncreasingly, advanced materials used in the aerospace, automotive, optics and electronics fields require low levels of defects and high levels of solute uniformity. Directional solidification by the Bridgman process is widely used for synthesis of these high-quality materials. During Bridgman crystal growth, heat and mass transfer by both thermal and solutal gradient-driven convection and diffusion influence the shape of the solid/liquid interface and dopant segregation levels, and hence, directly determine the final crystal quality. Key process parameters include the applied furnace temperature distribution and rate of translation, ampoule properties and furnace orientation."

Jan 1, 1999

By W. L. Cornell

The processing of lead tailings for removal of the heavy metals produces concentrates upgraded in Co and Ni values. Reflected light microscopy, scanning electron microscopy, image analysis, and Vickers hardness measurements were used to identify mineral species, associations, degree of liberation, and distributions to the test products. Siegenite and bravoite were the most common species encountered, but violarite and enriched pyrite and marcasite phases were also identified. Liberation for the Co and Ni minerals contained in the tailings was 20 micrometers or less.

Jan 1, 1993

By Zhi-biao Yin

Copper smelter flue dusts often cannot be directly recycled to the smelting process and accumulate as hazardous wastes requiring environmentally acceptable disposal. Because of the limited amount of flue dust, a separate copper extraction process must be simple and require-a small plant investment. A flue dust process has been developed, consisting of the following steps: (1) roasting a pelletized mixture of hydrated lime and flue dust to fix arsenic and sulfur as insoluble calcium salts, (2) heap leaching the roasted pellets with a buffered ammonia/ammonium salt solution to extract copper as an ammine complex in a lined cell that is the final repository of the leached pellets, and (3) boiling ammonia from the lixiviant to precipitate copper. Condensed ammonia and the filtered solution are returned to leaching. Heap leaching in the final repository cell lowers the capital investment significantly compared with competing extraction processes. Chemistry with respect to arsenic, sulfur and copper is discussed.

Jan 1, 1992

By Juan Patricio Ibáñez

Separation of arsenic and copper from Cu-As-H2S04 electrolytes by electrodialysis has been investigated at room temperature. The effects of current density and pH were studied. An arsenic-free copper solution was obtained for all the tested conditions. The transport efficiency for copper ions was found to be higher than 98% after 3 hours' test. Transport of arsenic and copper through the ion exchange membranes was increased by increasing pH and current density. Solution pH was found to be a key parameter for the separation process, since it controls the speciation of the ions to be transported and the formation of unwanted precipitates which reduce the global efficiency of the electrodialysis process. The main conclusion is that electrodialysis is a promising technique to be used in separating and/or concentrating ions of interest in copper electrometallurgy.

Jan 1, 2003

By Tian Sugui

By means of the long-term aging treated, creep properties measuring and microstructure observation, an investigation has been made into the microstructure and creep behavior of the casting and rolling GH4169 superalloy after long-term aged. Results show that, after the casting and rolling GH4169 superalloy treated by long-term aged, significant amount of " phase are dispersedly precipitated within the grains of the alloy, and some of the NbC, Cr7C3 carbide are distributed along the grain boundaries. In the range of the applied stresses and temperatures, the creep activation energies and stress exponents of LTA GH4169 alloy during steady state creep are calculated to be Q=541.1kJ/mol and n=16.2, respectively. During creep, the deformation mechanism of LTA GH4169 is thought to be the twinning and dislocation slipping within the twinning regions, and the damaging mode of the alloy is the intergranular fracture, and the non-smooth crystal surface is displayed in the fracture regions of the alloy. Thereinto, the carbides film formed along the grain boundaies has a few effect on the strength between the boundaries, which is a main reason of resulting in the alloy possessing a longer creep lifetimes.

Jan 1, 2009

By P. Thapliyal

The petroleum refining industry generates over a million tons of spent catalyst per year, containing valuable metals. Currently, these materials are recycled to smelting furnaces, but the fundamental mechanisms controlling the recovery processes are poorly understood. Furthermore, submerged injection of finely divided materials is potentially a means to obtain high recoveries of pay metals. In this study, a catalyst containing 10% Ni and 1% Co was injected into 45 kg heats of matte. A copper matte was chosen so that the nickel and cobalt recoveries were measurable. It was found that the recovery ranged from 40 to 700Al, increasing with catalyst feed rate, decreasing with catalyst particle size and decreasing with the oxygen content of the carrier gas. A mathematical model was developed to account for the results, and to permit extrapolation to nickel mattes. The industrial implications are discussed.

Jan 1, 1996

By Na Wang, Chao Du, Yao Zhang Shuqiang Jiao, Hongmin Zhu

"Na2NbAlO5 was synthesized using Nb2O5 and NaAlO2 as raw materials in molten NaCl-CaCl2 by a solid reaction. With an addition of sodium into the melts, Na2NbAlO5 was subsequently reduced to form NbAl3 intermetallic compound with a particle size of 50-300nm.IntroductionThe intermetallic compounds of niobium aluminides have been a subject of research interests as high temperature materials because of their properties such as high melting temperature, large specific strength at elevated temperature, good resistance to high temperature oxidation, low density and large ductility [1,2]. They are applicable for turbine blades in aircraft engines and stationary gas turbines [3,4].In recent years, the methods of powder synthesis have been widely discussed. There are many methods to synthesis intermetallic compounds such as conventional melting and solidification [5], powder metallurgy [6,7], reaction sintering [8] and reaction sintering with prior mechanical activation [9,10]. There is a prominent weakness in such methods that they use metal to produce intermetallic compounds by the means of diffusion reaction. Although the metal can diffusion sufficiently, it is still hard to avoid maldistribution of the constituents which impairs the properties of the materials."

Jan 1, 2012

By J. Brent Hiskey, Rebecca Grace Copp

The solvent extraction of yttrium and neodymium from copper pregnant leach solutions (PLS) using Primene JM-T, a primary aliphatic amine, has been studied. Effect of contact time, pH, sulfate concentration, and extractant concentration were investigated using synthetic and actual PLS systems. Standard experimental conditions were 5 minute contact time, pH ~2.5, and 10 % v/v Primene JM-T concentration. Distribution isotherms were constructed for the pure systems and for actual copper leach solutions. Synthetic solutions contained 100 ppm Y and ~75 ppm Nd. Samples of PLS contained 2 - 10 ppm Nd and 14 - 30 ppm Y. Results showed that complete extraction of both yttrium and neodymium occurred within five minutes and at pH values greater than 1. It was also found that sulfate concentration does not inhibit extraction at any concentration. Additionally, the distribution isotherms created show that extraction for these metals can operationally take place in one stage.

Jan 1, 2016

By Joseph C. Milbourne

The selection of a suitable nitrate removal process depends on a variety of site-specific chemical and environmental issues. The dominant technologies for nitrate removal include biological denitrification and continuous countercurrent ion exchange. The decision to apply either of these technologies, or both together, depends on the nature of the waste water to be treated. Factors that affect the selection of the biological system include the feed composition and feed temperature. Ion exchange nitrate removal systems are less sensitive to the feed composition but require disposal or destruction of the concentrated pregnant eluate. The paper discusses Tetra's continuous countercurrent ion exchange technology (CCIXTM) and fixed film biological reactor, Denite°. The treatment of the ion exchange pregnant eluant is also discussed.

Jan 1, 1994

By M. Kawakami

In relation to the designing of a new-type blast furnace, the reaction of carbonaceous materials with C02 is expected to occur at as low temperature as possible. In order to get a highly reactive carbonaceous material at low temperature, the reaction kinetics was investigated by measuring such quantities as the reaction rate from weight loss, the amount of CO adsorption and specific surface area by BET method. The reaction rates were large in the order of the Bintyo char, metallurgical coke, graphite and glassy carbon. If the rate was converted to the rate per unit area, however, those of the Bintyo char was smaller than that of graphite. Thus, it is suggested that the rate of the Bintyo char is influenced by the pore diffusion of C02. The rate had a positive relation with the amount of CO adsorption, showing that the rate determining step would be the desorption of CO from the active side on the surface. The rate independent of surface area was derived, combining al\ the obtained data.

Jan 1, 2003

By J. Rastas

The recovery of lead, silver and gold from existing and potential zinc process residues using a sulfidization-flotation method was investigated on a laboratory scale. The following residues were tested: neutral leach residue, high acid leach residue, and hematite residues. The sulfidization of lead and silver is carried out at low pH by the addition of a stoichiometric amount of sulfide at a controlled rate. To increase the particle size of the sulfides, seeding with synthetic lead and silver sulfides -is employed. The flotation is carried out at pH 2-4 using low pH-collectors such as dithiophosphates and dithiophosphinates. Special attention must be paid to the role of oxygen in the conditioning stage. The effect of different parameters on both the sulfidization and the flotation has been evaluated. Recoveries of 85-90, 90-95 and about 80 % were obtained for lead, silver and gold, respectively. Typically, concentrates containing 50-60 % lead, 3-5 kg/t silver and 10-15 git gold were produced.

Jan 1, 1990

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 Merete Tangstad, Lars Klemet Jakobsson

"Slag refining is a promising refining method for boron removal from silicon as a part of a metallurgical route for production of silicon for solar cells. There is, however, limited data on the distribution of impurity elements between silicon and different types of slags. In the present study, the distribution of boron and calcium between silicon and slag were determined at 1600 °C for calcium silicate slags with a CaO/SiC>2 ratio between 0.65 and 1.3. An almost horizontal linear trend was found for the distribution of boron between silicon and slag, and the borate capacity was found to follow the relationln(CB0, ) = 30.8 + 2.96-V (1)where V\s the CaO/SiCh mass ratio within the range of the experiments.IntroductionSolar grade silicon feedstock contributes significantly to the total cost and energy required to make crystalline silicon solar cells. A less expensive and less energy requiring method of solar grade silicon production is therefore needed in order to make crystalline silicon solar cells more viable as an energy source. Silicon is an abundant element and the manufacturing cost of solar grade silicon is therefore mainly determined by costs related to purification of metallurgical grade silicon. The Siemens process is the most common process today, but it is an expensive and highly energy requiring process that gives silicon with a higher purity than is needed for crystalline silicon solar cells. A cheaper and less energy requiring method for production of solar grade silicon can either be achieved by modifying the Siemens process or by using a new production method. Purification of metallurgical grade silicon through a metallurgical route is a promising method that is already in use industrially. It has however proven to be hard to lower the boron content to 0.3 mg/kg or less, which is the requirement for most p-type crystalline silicon solar cell manufacturers. Slag refining is seen as one of the most promising approaches that can be used to bring down the boron content to the required level, but there is not much data on how boron is distributed between silicon and binary calcium silicate slags [1-4]. The distribution of boron between silicon and calcium silicate slags at 1600 °C has been studied in this work, and the obtained data has been used to calculate the borate capacity of binary calcium silicate slags."

Jan 1, 2012

By Zhang Jianliang, Zuo Haibin, Gao Bing, Wang Zhe

"As a result of the shortage of coking coal and the quality decrease of coke, it is important to know how to make better use of highly reactive cokes. The co-gasification behavior of highly and lowly reactive coke for blast furnace is investigated. The results show that: In the middle stage of reaction, the weight loss ratio of highly reactive coke reacted together with lowly reactive coke is higher than that of it reacted individually. However, the weight loss ratio of lowly reactive coke is lower. The weight loss ratio of highly and lowly reactive coke is almost the same as that of the weighted average. The scanning electron microscope analysis indicated that the reaction degree of surface and interior of lowly reactive coke is relatively uniform with the reaction time increased. And the reaction degree of surface of highly reactive coke is obviously higher than that of interior.IntroductionIn blast furnace iron making process, coke functions as heat supplier, reducing agent, carburizer and skeleton. With development of blast furnace iron making technology, the skeleton function of coke is becoming more and more important in requirements of large scale furnace and high pulverized coal injection. High reactivity coke is usually produced by cheap coal with bad quality, and is not good for blast furnace process. The reactivity of coke is mainly determined by the coals used, and the resource of good quality coking coal is limited and is non-renewable. In order to fulfill the need of blast furnace, a lot of research have been done to improve coal matching using new kinds of coal to enlarge resource, in which coking coal and fat coal are reduced, whereas low price coal with bad caking property are used to lower the cost, and this would inevitably increase the reactivity of coke [1-4] Blast furnace iron making would still be the main stream for a predicted future, and high reactivity coke would correspondingly be used more and more, so it has great importance to study how to use high reactivity coke in blast furnace."

Jan 1, 2013