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By Daoxin Wu

In this paper, the rutile TiO2 were prepared under air, Ar and H2 calcination atmosphere by low temperature hydrolysis using Tetrabutyl titanate (C16H36O4Ti) as raw material. Powers were characterized by X-ray diffraction, UV-vis diffuse reflectance and X-ray photoelectron spectroscopy. The influence of the calcination atmosphere on the photocatalytic reactivity of rutile TiO2 for oxygen production was investigated. The photocatalytic reactivity of rutile TiO2 prepared under air, Ar and H2 atmosphere was compared under ultraviolet and visible light radiation with Fe3+ (c=8.0mmol.L-1) as electron acceptor. The results showed that rutile TiO2 prepared under Ar and H2 atmosphere had higher photocatalytic activity for oxygen production than that prepared under air atmosphere. The oxygen production rates under ultraviolet irradiation were 427.5, 378.2 and 357.0µmol.l-1h-1 respectively when rutile TiO2 was prepared under Ar, H2 and air atmosphere. The oxygen production rates under visible light irradiation were 78.2, 52.2 and 13.5µmol.l-1h-1 respectively when rutile TiO2 was prepared under Ar, H2 and air atmosphere.

Jan 1, 2008

By M. Wenzel, Dang Thanh Tung, Nguyen Anh Duc, Nguyen Huu Luong, Dang Van Sy, N. Kelly, K. Gloe, K. Kretschmer, Phuc Nguyen Le, K. Schnaars, S. Robles M, L. Götzke, J. J. Weigand

The recovery of rare earth metals from secondary sources has attracted much attention due to their ever expanding demand in the high-tech industry. The studies reported here focus on the hydrometallurgical recovery of lanthanum and cerium from spent fluid catalytic cracking (FCC) catalysts in a two-step process: leaching with nitric acid and solvent extraction by tri-n-butyl phosphate (TBP) and di(2-ethylhexyl)phosphoric acid (D2EHPA). The experiments show a high dissolution yield of about 93% lanthanum and 42% cerium in a single leaching step with 2 M (126 g/L) HNO3 at 80 °C; only 11% aluminum has been dissolved simultaneously. In the subsequent solvent extraction step the best results for this leach liquor could be achieved using a 1:1 mixture of 25% (v/v) TBP (0.92 M) and 25% (v/v) D2EHPA (0.76 M) in n-decane without the need for any pH adjustment. In that case La(III) and Ce(III) can be extracted with 60% and 74% yield respectively in one stage from the majority of accompanying matrix elements. In particular no extraction of Al(III) could be observed under these conditions.

Jan 1, 2016

By Zhao Hengxian

We studied the phase diagram of Na3AlFe-ZrO system, reduction of ZrO2 by aluminium and electrochemical behaviours of ZrO2 in the system. The results show that Na3ALF6-ZrO2 system is a simle eutectic one, that the velocity of reduction of ZrO2 in the system is rapid al 960'C and that the Zr content in the alloy abtained can reach as high as 2.5wt%. Potential scanning shows that there exist new current peaks on the potential scanning plats except for the cuurent peaks corresponding to the oxidation of aluminium. The method of making Al-Zr alloy in our paper has advantages over the traditional method of mixing metals.

Jan 1, 1992

By J. W. Perez

Raw coal will often break intragranularly in either a completely random way or in a differential mode where one species will have a different rate of breakage than another. Locked coal-ash and coal-pyrite particles can also break by the preferential detachment of one species from another along zones of inherent weakness in locked particle assemblages. The mode. cf breakage is largely a function of the nature of the feed, but it is also influenced by the comminution device and the operating variables. Evidence of breakage of particles in the various modes is seen in the crushing of raw coal and middlings particles with a rotary beaker, jaw crusher, rolls, hammer mill and rod mill. Evidence from the literature indicates the detachment mode is often important for coal, ores and metallurgical products. Further confirmation comes from the crushing of a specially prepared 'ore' of sized magnetite in plaster of Paris.

Jan 1, 1988

By Derek J. Fray

"A need exists for fast and accurate analysis of species in various phases at elevated temperatures. Although modern analytical techniques are very efficient, the equipment is usually situated some distance from the industrial operation and time is spent taking the sample and sending it to the analytical facility. Several minutes can easily lapse and, during this time, heat must be supplied in order to keep the system molten and, if the composition is changing rapidly due to a refining process or reaction with the environment, the information may only be of retrospective use. Perhaps more important reasons for the use of on-line sensors are that instantaneous analysis gives better control, process optimisation and the minimisation of energy losses and pollution. To date oxygen has been the only element which is measured widely using solid electrolytes. However, the analysis of many more elements is required and possible electrolytes for other species are discussed. For some elements, ~here is no suitable conducting electrolyte and, therefore, a different approach is adopted where the electrolyte, in which one species is mobile, comes to equilibrium with another species. IntroductionThere is an ever increasing demand for the development of sensors for on-line measurements in most areas of technology and, in particular, metal processing. This is especially relevant in situations where greater control can be achieved by monitoring the chemical composition of the melt during processing and where a minor constituent in the melt can have a major effect on the properties of the finished alloy. Although modern analytical techniques are fast and reliable, the equipment due to its complexity, is frequently situated away from the process area and valuable time may be spent in sampling and transportation. During this period, heat may have to be supplied to prevent solidification and the refining reactions may be continuing, and, therefore, the analytical information may not be of direct use."

Jan 1, 1988

By P. Henry

A novel electrochemical cell has been developed for the recovery of MnO2 from residue of pyrolusite ore leading loaded with Fe, Al Ni, Co and Si impurities, This new process can be considered as an alternative to the traditional methods : S02, H2O2 or bioleaching. It has been observed to proceed fairly rapidly and could prove to be a more economically viable process, as well as being more environmentally acceptable. Electrochemical characterization and kinetic studies have shown that MnO2 is effectively leached by electrogenerated ferrous ions at high current density from a pulp containing less than 5 g8 Fe. The chemical reactions are : Cathode (inox) : 2F23+ + 2e ? 2 Fe2+ Bulk: MnO2 + 2 fe2+ 4H+ ? Mn2+ + 2 Fe3+ + 2 H2O Anode (Pb-Ag) : H2O ? ½ O2 + 2H+ + 2e Global: MnO2 +2H+ Fe2+ = Mn2+ + H2O + 1/2 O2 The catholyte (MnO2 pulp) circulates upward in the expanded mesh cathode separated from the sulfuric acid solution anolyte by a separator which shows high mechanical resistance, low porosity, low potential drop, and reasonable cost. Laboratory and mini-pilot tests have led to the construction of an OT crating pilot plant (100 kg/hr) able to leach more than 95% of Mn, Ni, Co at 1000-1200 A/m2, 50°C with high faradic yield (> 95 %) and low power consumption (3.2 kWh/kg kWh/kg &4D). New applications like the treatment of spent Zn-Mn batteries, polluted soils, spent catalysts and oxide ore (cobalt, nickel) with electrogenerated redox species are now investigated at a laboratory and mini-pilot scale.

Jan 1, 2000

By D. E. Woolley

The rate of reduction of iron oxide from calcia-silica-alumina slag by carbon in liquid iron has been measured over the temperature range 1400-1600°C by monitoring the rate of carbon monoxide (CO) evolution. Slags containing ferric iron have been used in order to study the reduction of both ferric and ferrous cations. Results show that ferric iron is reduced before ferrous iron, so that the ferrous iron concentration increases initially. It is also shown that the rate constant, k, decreases at low reaction rates, or, equivalently, at low concentrations. The authors conclude that the reaction occurs in two periods. During the first period, ferric iron is reduced to ferrous iron. During the second period, ferrous iron is reduced to metallic iron, and the rate-limiting step during the second period is the mass transfer of ferrous cations in the slag phase to the slag-metal interface.

Jan 1, 1998

By Kuniaki Murase, Tetsuji Hirato, Koji Nitta, Yasuhiro Awakura

"The redox behavior of copper species in an ""ammonium imide"" room temperature molten salt was examined in order to clarify the applicability of the salt to the electroplating media of various metals. Trimethyl-n-hexylammonium bis(trifluoromethanesulfonyl)- amide (TMHA-Tf2N), having an electrochemical window of 5.6 V (50 °C), and corresponding copper(II) salt were synthesized. In TMHA-Tf2N media monovalent copper ion, Cu(I), was stable and Cu metal was oxidized, or corroded, in the presence of Cu(II) species. Cathodic electrodeposition of copper metal and anodic dissolution of it were, thus, one-electron reaction and their current efficiencies were almost 100%.IntroductionElectrodeposition of metals from aqueous solutions is an important soft process for manufacturing thin-film materials, surface finishing, and extractive metallurgy. However, the electrodeposition of base metals, such as zinc, chromium, and nickel, from aqueous media inevitably accompanies hydrogen evolution, which lowers the cathodic current efficiency of metal deposition. Since the electrodeposition of aluminium, titanium, and rare earths from aqueous media is actually impossible due to their largely negative redox potentials, nonaqueous media such as aprotic organic solvent and high-temperature molten salts have been employed for the electrodeposition of these metals. Room temperature molten salts (RTMS),1, 2) or room temperature ionic liquids, have also been developed as a promising electrolytes for the electrodeposition of base metals. In this field, chloroaluminates of alkylpyridinium or alkylimidazolium cation have been well investigated for aluminium3) or alluminium-alloy4-5) electroplating media. On the other hand, in order to avoid high hygroscopicity arising from the use of aluminium chloride, attempts have been made to combine the alkylimidazolium cations with fluorine-containing hydrophobic anions, e.g. BF4-,6) CF3SO3- (TfO-),7) (CF3SO2)2N- (Tf2N-),8) and H(HF)n-ions,9) and investigated for electrodeposition media.'°) Recently, a new series of RTMS consisting of tetraalkylammonium cations and Tf2N- anion, sometimes abbreviated as TFSI- anion, was found independently by MacFarlane et al.11, 12) and Matsumoto et al. 13) This type of RTMS, which is commonly named ""ammoniumimide"" salt, has a wide electrochemical window of ca. 5 V and, thus, the RTMS seems to be suited for practical application as a solvent for the electrodeposition process. In this paper, we report the electrochemical behavior of copper species in an ammoniumimide RTMS, trimethyl-n-hexylammonium bis(trifluoromethanesulfonyl)amide (TMHA-Tf2N)."

Jan 1, 2000

By T. Ueno

Naoshima Smelter & Refinery of Mitsubishi Materials Crop. commissioned a new Mitsubishi continuous copper smelter in May 1991. Process offgas volume of the conventional reverberatory furnace line, one of the previous smelters having been shut down, was very large and thus two acid plants had been operated. It was expected that the offgas volume would, be reduced at the new smelter to about a half of the sum of those from previous two smelters and the sulfur dioxide strength would be increased. So various alternatives were studied to minimize the operation cost. And it was decided to utilize both of the plants with minor modifications by diluting the gas either with air or with dilute gases. The acid plants now receive off gases from the new copper smelter, a sintering machine of a lead smelter and a decomposer of waste acid. The paper discusses plant design, operation, improvements and modifications realized in relation with the retrofitting of the copper smelter.

Jan 1, 1992

By Makoto Ohlsuka

The ternary Ni2MnGa intermetallic compound is an intelligent material which has both a ferromagnetic property and a shape memory effect (SME). The use of the shape memory alloy films for an actuator of micro-machines is very attractive because of its large recovery force. The purpose of the present study is to investigate the effects of fabrication conditions and to clarify the relationships between these properties and fabrication conditions of the Ni-Mn-Ga films. The Ni-Mn-Ga films with a thickness of nearly 5 um were deposited with a radio-frequency magnetron sputtering apparatus using a Ni50Mn25Ga25 or Ni52Mn24Ga24 target. They were heat-treated at various temperatures between 873 and 1273 K for homogenization and ordering and then cooled in a furnace. The composition of the films depended on the sputtering power. The as-deposited films were crystalline and had columnar grains. After the heat treatment the grains widened and the grain boundary became indistinct with the increasing heat treatment temperature. The martensitic transformation temperature of the heat-treated films increased with increasing nickel content. Furthermore the effect of plastic deformation and constraint aging on SME is also investigated. After plastic deformation, the two-way SME was shown through the martensitie transformation and its reversion, The intensity of X-ray diffraction peaks from stress-induced martensitie phase was found. The constraint-aged films also showed the two-way 3ME by thermal cycling.

Jan 1, 2003

By Lamar S. Todd

The direct production of metal from a sphalerite concentrate is an attractive route for primary zinc. A series of operations and conditions have been selected to efficiently cause the following overall exothermic reaction. The process uses a continuous circulation of molten copper for material and energy transfer between the unit operations. Sulfide concentrate is reduced with an excess of superheated copper to make a copper alloy and white metal. The alloy is stripped of volatile metals under vacuum and some metals can be separately condensed. The residual copper and the white metal are fed into a copper converter to be blown with oxygen for desulfurizing and the superheated copper is recycled. The paper will include a detailed material flow sheet for the process, discussion of the operating conditions of the individual units, behavior of minor elements, and zinc quality.

Jan 1, 1999

By Liow Jong-Leng

A survey of the interactions of large gas bubbles formed from top and bottom injection of gases into melts was carried out. Spherical cap bubbles were found not to produce much splash when they break through the bath free surface except for that formed by plunging of the-spout at its edges. In contrast, the bursting of balloons produces cavities which give rise to liquid jets being ejected from the bath free surface. The position of the balloons relative to the bath free surface is an important parameter in the formation of the liquid jet. It is found that the interactions of multiple bubbles close to the free surface is important in determining the splash behaviour of gas injected systems.

Jan 1, 1996

By Robert Mensah-Biney

The loading characteristics of gold-tetrabromide species onto a weak-base resin, PAZ-4, were evaluated using a completely mixed batch reaction system. The time. to attain equilibrium loading was substantial, on the order of several days. However, abnormally high loading capacity values of 15 to 20 meq Au/g dry resin (1000 to 1300 kgAu/tonne) were attainable in 24 hours. The loading of gold-bromo species by P AZ-4 was visualized as consisting of two processes: (i) the rapid adsorption of [AuBr4r species by simple ion exchange mechanisms and (ii) reduction of [AuBr4r to metallic gold by an electron exchange mechanism. Elution of gold from loaded resin was feasible provided the resin had not been loaded to high capacity values. If loading is carried to high levels, complete elution becomes impractical and the gold may be recovered by ashing the loaded resin. For the high loading capacities observed this option would appear to be cost effective.

Jan 1, 1991

By Takeshi Nagano

"Prior to discussing future trends of non-ferrous metals smelting and refining, the past developments are looked back. Social and economic environments in Japan over the past two decades are reviewed. Technological developments to comply with these environments are explained, taking for examples the cases of the Mitsubishi continuous smelting and converting process and Onahama's jumbo tank system for copper tankhouse. After considering the factors which will influence the improvements in non-ferrous processing, future trends are forecasted generally for copper, zinc, lead, aluminum and rare earth metals. Recent development works in Japan for the future are also introduced. In the discussed area, it appears that the emergence of new innovative processes would be difficult. The progress will be made rather toward the sophistication of the existing technologies, utilizing the advancement of the related technologies such as computers, electronics, etc. IntroductionThis paper discusses the future trends of non-ferrous metals smelting and refining on the occasion of the international symposium, ""The Metallurgical Processes for the Year 2000 and Beyond"".It is considered that the improvement of technology is greatly influenced by the social and economic environments which surround it. From this standpoint, review was made of Japanese case over the past two decades. Various new technologies were developed also in the non-ferrous metal world to comply with the requirements under the above environments. The examples are described in the cases of the Mitsubishi continuous smelting and converting process and Onahama's jumbo tank system for copper electro-refining.After foreseeing the major factors which will affect the technological developments in the future, the trends are forecasted for copper, zinc, lead, aluminum and rare earth metals generally. Some development works in Japan, which will give suggestions for future trends, are also introduced in some detail."

Jan 1, 1988

By A. Treverrow, G. A. Brooks, H. K. Worner

"The work by H.K Worner and co-workers at CRA in the 1960s, and early 1970s, established that molten metals could be refined continuously utilising counter current flow of metal and slag. Womer also demonstrated that counter current refining could produce highly refined metal products. These developments coincided with the advent of high intensity metallurgical reactors in both the ferrous and non-ferrous industries (e.g. BOS, Q-BOP and later Sirosmelt) that utilised high levels of gas injection to produce rapid stirring and very fast reaction. These new generation of high intensity metallurgical reactors allowed high tonnage rates through relatively small volume vessels.Whilst, it is well known that the counter current flow of reacting phases offers the potential of efficient mass transfer and high purity products, the application of counter current reactors to molten metal/slag systems has been criticized on the basis that they suffer from either low intensity or, alternately, from poor refining due to excessive dispersion. These criticisms relate to the balance between intensity and the refining capacity of a reactor. That is, whilst high levels of mixing transversely to the direction of flow promotes high mass transfer, longitudinal mixing (dispersion) is detrimental to refining. Of course, mixing in one direction invariably leads to mixing in other directions, thus creating a playoff between high mass transfer and excessive dispersion.This balance between intensity and refining has been the subject of recent studies overseas, and at"" the University of Wollongong, using cold modelling techniques to evaluate the effect of mixing on dispersion in a counter current refining launder. These studies have shown that for a given geometry and mixing regime, dispersion decreases with increasing flow of liquid phases. This means that whilst high mass transfer cannot be achieved in a refining launder without sacrificing the degree of refinement, there is no impediment to achieving high productivity through such a system, in fact, high through puts may favour good refining. Thus, it may be possible to match a high productivity smelting operation with a equally productive counter current refining stage."

Jan 1, 1996

By Jana Dobrovska

Solidification and cooling of a continuously cast slab and simultaneous heating of a mould is a very complicated problem of transient heat and mass transfer. Nowadays, the solving of such a problem is impossible without numerical models of the temperature field not only of the slab itself, while it is being processed through the whole concasting machine (Caster), but of the mould as well. Two original numerical models have been developed and used in the investigation of a continuously cast steel slab. The first (one of two) 3D model of the temperature field of a concasting is capable of simulating the temperature field of a caster. Experimental research and data acquisition have to be conducted simultaneously with the numerical computation-not only to confront it with the actual numerical model, but also to make it more accurate throughout the process. After computation, it is possible to obtain the temperatures al each node of the network, and at each time of the process. The utilization of the numerical model of solidification and cooling of a concasting plays an indispensable role in practice. The potential change of technology-on the basis of computation-is constantly guided by the effort to optimize, i.e. to maximize the quality of the process. The user can therefore choose any appropriate longitudinal or cross-section of a slab and display or print the temperature field in a 3D or 20 graph whenever necessary. The second numerical model of dendritic segregation of elements assesses critical points of slabs from the viewpoint of their increased susceptibility to crack and fissure. In order to apply this model, it is necessary to analyze the heterogeneity of samples of the constituent elements (Mn, Si and others) and impurities (P, S and others) in characteristic places of the solidifying slab. The numerical model, based on measurement results obtained by an electron micro-probe, generates distribution curves showing the dendritic segregation of the analyzed element, together with the distribution coefficients of the elements between the liquid and solid states. The combination of both models enables the prediction of cracks and fissures in critical points of the continuously cast carbon-steel slab. Both models had been applied in the industrial investigation of a cast low-carbon-steel slab.

Jan 1, 2003

By W. S. Kirk

World cobalt production in 1987 was estimated to be about 26,600 metric tons (MT) of which Market Economy Country (MEC) production was estimated to be about 22,000 MT. Zaire and Zambia produce about 80 percent of the primary cobalt produced among Market Economy Countries (MEC). Production cutbacks. lowering cobalt grades and mining curtailments in Finland and Zambia in 1987, resulted in lower production than that of 1986. The trend is expected to continue through 1988. Cobalt production from Canadian ores and from Botswana is expected to increase significantly in 1988 as a result of increased nickel production. MEC production in 1988 is estimated to be 22,100 MT, only slightly higher than that of 1987. There are currently no primary cobalt mines. Virtually all cobalt is recovered as a byproduct of copper and/or nickel mining. Zaire, which produces cobalt as a byproduct of copper, is the worlds largest cobalt producer, with over 50 percent of total estimated world cobalt production and nearly 65 percent of MEC production. Zambia follows with about 14 percent and 17 percent, respectively. Zambia's cobalt production also results from copper production.

Jan 1, 1988

By N. Menad

Thermal treatments of five different types of non-ferrous metallurgical wastes, under controlled atmosphere, were carried out at temperatures lower than 800 °C. The aim of these treatments was to reduce the toxic elements content and to increase that of valuable metals in the residue. <Best results were obtained by their treatments in air or hydrogen or successively both of them. Simple treatments using air or hydrogen of three samples allowed the elimination of more than? 95 % of their toxic elements and&apos; almost doubled their valuable metals&apos; concentration. For the rest two samples, combined treatment was necessary for their efficient decontamination and the concentration of valuable metals, in the treatments residue, to a reasonable value. Most of the solids issued from these treatments can be recycled in .the current non-ferrous metallurgical processes.

Jan 1, 1995

By Joseph Goodwill

1. PURPOSE The objective of this paper is to summarize a study undertaken by the EPRI Center for Metals Production (CMP). The overall purpose of the study was to identify electrolytic opportunities that might merit consideration for joint development by industry and EPRI. 2. SCOPE The electrolytic technologies of interest to this study include: Electrorefining, Electrowinning, and Fused-salt electrolysis. Recovery from primary, secondary, and waste materials were included in this effort; however, we excluded from consideration: Plating and coating operations, such as electrogalvanizing; Mining and milling operations in which electric energy is predominantly used for comminution; Electrothermal processes in which submerged-arc, open electric-arc, and plasma-based smelting processes use electric energy largely to provide a melting or refining ("heating") capability; and Aluminum electrotechnologies since these were the subject of a separate study (CMP 86-2). We recognize that there may be some "gray areas" between these excluded areas and the electrolytic sectors of interest. For this reason, a secondary criterium was used, namely, if the major use of electric energy was to extract or refine the

Jan 1, 1990

By B. C. Jena

Activities of carbon, cobalt and nickel were evaluated in the ternary systems iron-carbon-cobalt and iron-carbon-nickel for the temperature range 1300-1600°C for cobalt and 1300-1700°C for nickel. The carbon activities were determined from the knowledge of activities (1) in the binary system iron-carbon, (2) in the dilute ternary systems and (3) from the knowledge of carbon saturation data. The activities were mathematically expressed with the Taylor series expansion of Wagner&apos;s interaction parameter formalism modified to suit concentrated solutions. The cobalt and nickel activities were determined from the knowledge of carbon activities by applying the Gibbs-Schuhmann integration and from cobalt and nickel activities in the binary systems iron-cobalt and iron-nickel. Partial molar enthalpies of mixing were determined based on the temperature behaviour of the activity coefficients.

Jan 1, 1992