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By Yasuhiro Konishi, Yoshiyuki Noda

"This paper describes a new processing of rare-earth oxide precursor, in which rare-earth carbonate powders are precipitated directly from emulsions of rare-earth loaded carboxylate solutions, using CO2 gas and water. This synthetic route of rare earth carbonate is a combined process of the stripping and precipitation stages in a conventional solvent extraction. Using this technique, lanthanum carbonate and yttrium carbonate were prepared at temperatures of 10 to 80°C and CO2 pressures of 0.1 to 3.0 MPa for 120 min. The rates of carbonate precipitation in a batch autoclave were sensitive to processing parameters such as CO2 pressure, temperature, and organic-phase composition. The particle size distributions of the carbonate powders were markedly dependent on temperature and C02 pressure.IntroductionSolvent extraction is the most appropriate commercial technology for separation and purification of rare earths. In typical commercial processes, the rare earths are stripped from loaded solvent extractants using aqueous solutions of mineral acid. After adjusting the pH of the aqueous strip solution, the rare earths are precipitated as insoluble powders of oxalates or carbonates, from which oxides can be produced by calcination. Such conventional processing can be simplified when the stripping and precipitation stages are combined by emulsifying rare-earth loaded solvent extractant with aqueous oxalic acid solution. It is likely that the single-stage precipitation stripping results in a marked decline in the consumed amounts of precipitating and neutralizing agents, thereby saving on both running and capital costs.Yoon and Doyle1) first demonstrated that oxalate powders of lanthanum and yttrium are directly precipitated from rare-earth loaded carboxylic acid solvent extractant when contacted with aqueous oxalic acid solution at ambient temperature and atmospheric pressure. Yttrium oxalate pow4ers were also prepared by precipitation stripping of di-(2 ethylhexyl) phosphoric acid. (D2EHPA) extractant using oxalic acid-hydrochloric acid solutions. 2) Moreover, neodymium oxalates were directly precipitated from organic solutions of tertiary aliphatic monocarboxylic acid and 2-ethylhexyl phosphonic acid mono-2- ethylhexyl ester using aqueous oxalic acid solutions, and powder characteristics of the resulting oxalates were compared with those of powders by the conventional solvent extraction routes. 3 • 4) Recently, attention has been directed towards the influence of processing parameters on the particle size distributions of yttrium oxalate precipitates. 5)"

Jan 1, 2000

By Luis W. Pommier

The wastes of the plating industry are generated in the process of rinsing the plated objects and during the cleaning of the plating shops. High volumes of hazardous waters are neutralized on site producing recyclable water, generating a metal rich, hazardous, filter cake. Occasionally, a complete plating bath has to be discarded which increases the metal content of the filter cakes. These filter cakes are discarded as hazardous at a cost of over $ 250 per ton. The metals found in the cakes are generally copper, nickel and chromium or zinc, lead and cadmium, assaying from 2% to 15% or even higher content of each metal The metals and their contents are highly variable. Some plating shops discard their products directly to hazardous waste sites, others, have them collected by companies which consolidate wastes from several producers prior to discarding. These wastes, richer in metal content than mine ores, need neither mining nor crushing and grinding for concentration. The commonly found impurities in the mine ores, i.e.: pyrites, arsenic, and valuable metals which are present in minute quantities, are absent in the filter cakes. The processes available to selectively recover the metals from the filter cakes, are discussed based on their technical and economic merits. The flow-sheets include leaching, solvent extraction when required, and electrolytic refining. Examples, showing the separation of copper, nickel and chromium and also of zinc and lead in pilot plants, show the technical and economic viability of the processes.

Jan 1, 1996

By Seung-Chul Lee

Transparent conducting tin(1V) oxide thin films have been studies and developed for the electrode materials of solar cell substrate. Fabrication of tin oxide thin films by sol-gel method is process development of lower cost photovoltaic solar cell system. The research is focused on the establishment of process condition and development of precursor. The precursor solution was made of tin isopropoxide dissolved in isopropyl alcohol. The hydrolysis rate was controlled by addition of triethanolamine. Dip and spin coating technique were applied to coat tin oxide on borosilicate glass. The resistivity of the thin film was lower than 0.18-cm and the transmittance is higher than 90% in a visible range.

Jan 1, 1999

By Nozomu Hasegawa

The phase diagrams and microstructures of the slags in the Mitsubishi Continuous Copper Smelting and Converting Process were studied for the prevention of the magnetite troubles such as accretion build-up on furnace hearths and launders, blockages at the melt outlet, slag viscosity increases and so on. According to the results of those studies, the silica and lime contents in the silicate slag at the smelting furnace, and the lime content in the lime-ferrite slag at the converting furnace were changed, resulting in lower and more consistent copper levels in the discard slag, with much less need for operators to clean melt outlets and launders. However, these changes may decrease the desirable amount of accretion-coating inside the furnaces and thereby reduce furnace campaign lives. Therefore, a method of estimating the magnetite level in the melts was developed, and slag compositions and temperatures have been controlled within the appropriate ranges to prolong furnace lives and also prevent magnetite troubles.

Jan 1, 2003

By Miguel Barron

Recently, a new lance design for BOF steelmaking has been proposed in the literature. This lance, in addition to six peripheral inclined supersonic nozzles, contains a vertical centered nozzle whose oxygen flow is independent from the main oxygen supply. The above authors affirm that their lance maximizes the droplet generation without causing spitting. In this work, the performance of a lance with four peripheral nozzles and one vertical centered nozzle is numerically modeled by means of Computational Fluid Dynamics software. Transient two dimensional computer simulations were carried out considering two phases, namely molten steel and gaseous oxygen. Numerical results confirm that bath agitation and droplet generation are enhanced as a result of the vertical centered nozzle, however a proper performance of this lance, related to a conventional one, strongly depends on the Mach number of the oxygen jets and the lance height.

Jan 1, 2008

By A. Elizabet Serna

The weak acid is a by product obtained in a pre-treatment of gases from a copper smelter prior to sulfuric acid manufacture and the main components of this weak acid are: sulfuric acid. copper, arsenic. antimony, bismuth and iron. Usually, this effluent is neutralized with lime and the solid residues are stored in a landfill as a hazardous waste. This work was directed at determining the optimal conditions to recover copper from weak acid using a cementation process before the neutralization of the effluent. The variables investigated are: Effluent temperature, iron scrap amount and acid concentration versus reaction time. The results of these experiments show that the cementation process of copper and the co-cementation of impurities such as arsenic, antimony and bismuth were in accord with the theory of the electrode potentials.

Jan 1, 1996

By Sui Xue

A process has been developed from laboratory-scale experiments for the aqueous processing of various lead-bearing wastes. The process exploits the limited solubility of lead in sulfate-rich solutions to effectively separate lead from other metals. The lead sulfate is then completely converted to lead carbonate using sodium carbonate and ammonium carbonate. The effectiveness of this conversion was observed to be sensitive to the solution pH and carbonate concentration. The final stage of the process uses low temperature calcination of the lead carbonate to form PbO. Yellow lead oxide (massicot) is readily formed if calcination is conducted at a temperature at or iibove 50G°C, wlule red iead oxide (iitharge) is formed at temperatures near 450°?C. A complete economical analysis of the process will be discussed.

Jan 1, 1996

By Jinrong Zhang

Fresh cyanide solution was treated by near UV light with the assistance of photocatalysts. Cyanide was oxidized mainly to cyanate. Photochemical behavior of the anatase and rutile forms of TiO2 was compared. It is found that anatase has a much higher activity than that of rutile. Bubbling of oxygen in the reactor showed no appreciable increase in cyanide oxidation, implying that the reaction is surface controlling. A very interesting finding in this study is that a natural mineral, ilmenite, can replace chemical titanium dioxide as the photocatalyst. Ilmenite without any treatment did not catalyze the oxidation of cyanide. But, after being roasted at high temperature with oxygen, the oxidation was enhanced dramatically. The mechanisms of photooxidation of cyanide and the roasting of ilmenite are proposed.

Jan 1, 1991

By Jochen Petersen

Design and operation of heap leach processes are still largely based on,operator experience and rule of thumb. Although considered a low-cost, low-tech route for mineral extraction, the underlying physical, chemical and biological processes are actually rather complex. Numerous heap leach models have been devised over time, but the majority of these tend to simplify the true process and are of limited use in practise. The modelling approach presented here combines the more conventional reaction-diffusion model with models accounting for equilibrium reactions in solution, bacterial growth kinetics, complex reactions schemes, gas flow, heat conservation, etc. One particular model application is discussed in the context of developing a novel high temperature heap leach processes using thermophile micro-organisms. The complexity of processes such as this can only be appreciated with the aid of a systematic model. For the designing engineer an accessible, personal computer based model should be an indispensable tool for the design and optimisation of efficient heap leach operations.

Jan 1, 2002

By Lei Zhang, Shining Chen, Lina Wang, Pu Liu, Benquan Fu, Jiannyang Hwang

A PFS(polymeric ferric sulfate) coagulation-photocatalytic oxidation technology was used for advanced treatment of coking wastewater from secondary biological treatment. Effects of some key factors on TOC removal rate were investigated, and the results were compared with those of the common photocatalytic oxidation technology under the operating parameters of the photocatalytic oxidation defined. Single factor experimental results showed that TOC removal rate could reach 81%, when optimal operating conditions were as follows: TiO2 loading: 4.0g/L, irradiation time: 4h, initial pH is 5.1and PFS dosage:700mg/L. PFS coagulation and photocatalytic oxidation have synergistic effect, which is meaningful for highly efficient treatment of coking wastewater

Jan 1, 2015

By Shijie Wang

In pressure oxidation leaching of copper anode slimes, than 65% of the tellurium is m' cxtraoted during decopperizing. About l0- 15% of the selenium is also dissolved simultane¬ously by severe leach conditions. Current operation for the treatment of the leachate is to constantly recirculate the leach solution through a bed of copper turnings. The tellurium and sele¬nium are precipitated from the leach liquor as copper telluride and copper selenide and sepa¬rated from the solution by filtration. In order to improve the reaction efficiency and reduce the process cost, viz, minimize the copper addition, cut retention time, and reduce the energy consumption; a chemical reducing agent is studied and the cementation process tested in the laboratory. In this paper, the test results are presented and the process chemistry is discussed.

Jan 1, 2003

By Gus Van Weert

This paper describes the results of autoclave testwork where ferric nitrate was hydrolysed in the presence of certain cations and anions and the resulting hematite analyzed for foreign constituents. For the cations Zn++, Ni++, Cu++, and AI+++, selectivity factors of over 107 were found. Magnesium gave 3.106. These factors are calculated as Me/Fe in solution over Me/Fe in the hematite; Me representing the metal in ion added. As-a result of the testwork at Delft University of Technology, BUDELCO (the Netherlands electrolytic zinc producer) ran a series of ferric nitrate hydrolysis tests in the presence of 10 additional trace elements. Impurity levels were prejudiced on Me2 EPHA extraction of iron from their zinc circuit, followed by HNO3 stripping. Good selectivity against base metals was confirmed, but trace elements forming anions (As. Sb) and sulphate were incorporated in the hematite. These BUDELCO results are also presented.

Jan 1, 1995

By A. A. Shook

The off gas from the #5 converter at BHP Copper's San Manuel smelter was analyzed continuously over a period of several weeks using an online sulfur dioxide analyzer. These data have shown that the oxygen utilization efficiency of this copper converter was somewhat lower than anticipated, and that oxygen efficiency declines significantly during the copper blow. A sharp reduction in sulfur dioxide generation was consistently observed at the end of the copper blow, which could be used by converter operators to prevent over-blowing and minimize rolling out of stack.

Jan 1, 1999

By John P. Hager

One possible approach for the recovery of mercury from acid plant blow-down sludge in smelters is the use of a vacuum retort reactor for the vaporization of the mercury with subsequent collection of metallic mercury in an attached condenser. An experimental study was undertaken to investigate the vaporization of mercury when present as a compound in the Hg-S-O and Hg-Se systems. A transpiration reactor was modified to operate under reduced pressure and with a continuous flow of inert sweep gas. A water-cooled cold finger was inserted into the exit end of the reactor to provide for the rapid quenching of the exit gases and the collection of the mercury. Rates of vaporization were measured at several temperatures for each compound and were generally found to be constant at a given temperature and reactor pressure. The results were used to determine the minimum operating temperature for 100% vaporization of the compound in 60 minutes. For Hg2SO4, HgSO4, and HgSO/2HgO the required temperatures. for a reactor pressure of 50 Torr. were determined to be 634°, 622°. and 603°C. respectively. For HgO, HgSe, and HgS the required temperatures were 557°. 451°. And 382°C. respectively. For HgS the rate of vaporization was also measured at a reactor pressure of 1 00 Torr. The rate of vaporization was found to be slower resulting in an increased vaporization temperature of 423°C. It was also determined that the mercury vapor present in the exit gas stream can back-react with the other gas species to a significant extent and can result in very little condensed metallic mercury. For the vaporization of both HgS and HgSe. the mercury vapor was found to have back-reacted to the extent that virtually none of the vaporized mercury was collected in metallic form. For the vaporization of Hg2S04? HgS04, and HgSO4*2HgO the amount of metallic mercury recovered varied from approximately 50% for HgS04*2HgO to approximately 10% for Hg2S04 and HgS04. Only for HgO was the recovered mercury in primarily elemental form. The application of the results to the operation of a vacuum retort and condenser system is discussed.

Jan 1, 2001

By P. W. Godbehere

Over the past three years the Horne Smelter has successfully introduced concentrate smelting by injection in Peirce-Smith converters, allowing definitive closure of its last operating reverberatory furnace, while commissioning a large acid plant treating off gases from its Noranda reactor. Future strategies include a major revision to present converter practices to permit further significant reductions in sulphur and dust emissions. This paper gives an overview of the status of these and other technical and operating developments which will further contribute to ensuring the Horne's position as an efficient custom smelter of primary and secondary feeds.

Jan 1, 1993

By Meghan McGrath

Third generation advance high strength steels with microstructures of acicular ferrite and retained austenite were investigated and meet mechanical property goals. A good combination of strength and ductility were achieved with duplex ferrite and austenite microstructures where cementite formation was suppressed. Transformation induced plasticity (TRIP) behavior produced rapid work hardening. The mechanical properties of two hot-rolled steels with duplex microstructures were compared and had the following compositions: (1) Fe-0.14C-13.87Mn-1.42Si-3.51Al; and (2) Fe-0.06C-14.2Mn-1.85Si-2.38Al. These steels were cast, homogenized, and hot rolled at 900ºC to obtain a refined microstructure with ultimate tensile strengths and elongations to failure of 865 MPa and 39% and 1,217 MPa and 28%, respectively. The amount of metastable austenite in both compositions decreased after tensile testing from 58% and 28% to 6% and 0%, respectively. Microstructures were characterized using optical microscopy, scanning electron microscopy (SEM), and x-ray diffraction.

Jan 1, 2010

By A. W. Bryson, S. P. Fox, S. A. Godorr

"This work is an extension of a previous investigation on the development of surface roughness during electrodeposition of copper. A comprehensive model based on diffusion and migration in a force field together with surface diffusion and sticking probabilities is used to generate profiles which are compared to those produced experimentally. The roughness is characterized by using the technique of fractal geometry which is shown to describe both qualitatively and 9uantitatively the development of surface morphology during electrodeposition.The work is extended to the deposition of copper in the presence of various concentrations of thiourea. The development of roughness is observed experimentally on the edge of a thin copper disc mounted between two glass plates. This enables photographs to be taken at various stages during growth. The surface outline is digitized using an image analyzer which enables the fractal dimension to be determined as growth proceeds. As expected, the presence of thiourea at low concentrations produces a fractal dimension which is closer to unity (i.e. the surface becomes smoother).IntroductionThe development of surface morphology during electrodeposition has far-reaching implications for copper plating in the electrowinning and electrorefining processes. Short circuits as the cathode surface grows unevenly require operator intervention in a dangerous environment and imply processing delays, and the inclusion of electrolyte in small gaps in the plated cathode have implications in downstream processing of the cathode. Higher current densities are obviously desirable, as they result in greater production rates, but as shown by Ettel et. al.(l), Harvey et. al.(2), Cook (3), and Harvey et. al.(4), it is not possible to operate near the projected economically optimum conditions because the electrodeposition of copper from sulphate and acid solutions is a mass transfer controlled process. It has been shown (Ettel et. al.(l), Harvey et. al.(2)) that the closer a system operates to mass transfer limiting conditions, the poorer the resulting cathode quality. One solution is to use agitation techniques to increase the limiting current density. Another is to add surface active additives to the electrolyte which has been shown by Ettel et. al.(l), Harveyet. al.(2) and Afifi et. a1.(5) to allow higher rates of production without decreasing cathode quality. The second proposed solution is of interest in this work, since there is very little knowledge of the conditions under which these additives operate effectively, and little fundamental understanding of the mechanism by which they operate. The current work seeks to contribute to this field by correlating a simulation model with experimental results to describe the development of surface morphology in the electrodeposition process."

Jan 1, 1997

By Timothy W. Ellis

This paper presents the basic theory of operation, physical chemistry and phase equilibria which allow the development of liquid-liquid extraction circuits based on metallic solvents. The incorporation of reduction and reduction/diffusion processes into the process 'scheme is discussed and a detailed description of ,several liquid-liquid extraction schemes are developed. A synopsis of experimental results obtained using this: method to separate rare earth and other metal based materials will be given.

Jan 1, 1996

By James R. Craig

The slags generated during gasification of petroleum coke are heterogeneous and con-sist of many different phases. These phases are important because their physical properties affect the operability of gasifiers and because they concentrate many elements that are present in the petroleum coke feed in only minor to trace quantities. An understanding of the chemistry and physical nature of these slag phases is necessary to predict behavior in the gasifier and in considering the ultimate use or disposal of the materials. Slags typically consist of silicate glasses, calcium-silicates, free iron-nickel metallic phases, iron sulfides, and aluminum oxide spinels enriched in iron, chromium, and vanadium. The partitioning of elements among these phases has been analyzed and will be discussed.

Jan 1, 1989

By Micheal McCarter, Biswadeep Saha, Meenakshisundaram Ramanathan, Chai Ren, Sivaraman Guruswamy

"Three-point bend test was used to study the effect of electrochemically charged hydrogen and magnetic field on the embrittlement behavior of AISI 4340 steel in this work. Acoustic emission signals were collected during the test and analyzed to gain an understanding of the crack growth process. Cathodic hydrogen charging in AISI 4340 steel resulted in drastic reduction of ductility and strength. Hydrogen embrittlement was characterized by a change in fracture surface from dimpled ductile surface to quasi cleavage type fracture. No significant effect was observed in the presence of magnetic field. The acoustic emission signals collected during the test provided an indication of the extent of energy released during the crack growth process.*Support of this work by NSF through the award DMR-0854166 is gratefully acknowledgedIntroductionGrowing interest in hydrogen as a clean fuel and use of steel and other iron based alloys for storage and transport of hydrogen has led to extensive study of the influence of hydrogen on the mechanical properties of these alloys. Hydrogen interaction with materials may result in degradation of mechanical properties. Embrittlement, either ductile or brittle, can be described as a condition which decreases the toughness of the material or increases the ease of crack growth. Hydrogen present even in few parts per million is sufficient to embrittle steels at room temperature [1]. In most cases, hydrogen exposure is through an electrochemical process in aqueous corroding environments. In such cases, they are prone to be exposed simultaneously to electrically induced magnetic fields, which are also believed to affect the hydrogen embrittlement susceptibility of these alloys. So it is also important to study the effect of magnetic field on the hydrogen embrittlement susceptibility. Hydrogen solubility by electrochemical process in aqueous solution is proportional to square root of current density for iron. [2,3]"

Jan 1, 2012