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By E. James Quinn

Solvent extraction technology using EHEHPA (2-ethylhexyl phosphonic acid, 2-ethyhexyl mono ester) is the norm for industrial separations of rare earth elements. This process has some shortcomings, including a large number of stages compared to most SX processes and high acid requirement for stripping of the heavy rare earths. In this work, we examine a number of alternative mixed solvent extraction systems: (i) Mixtures of organophosphonic and phosphinic acids such as EHEHPA/Cyanex 272 or Cyanex 572; (ii) Ionic liquid mixtures of EHEHPA with quaternary ammonium chloride (Aliquat 336); and (iii) Mixtures of carboxylic acids for yttrium/lanthanide separations. We discuss and compare the efficacy of these systems with reference to the Nd/Sm separation, which is of industrial significance. Based on the extraction chemistry and the use of modelling tools to define the counter-current solvent extraction circuit, we present a techno-economic analysis of a separation plant and discuss the impact of various solvent systems on the capital expenditure (CAPEX) and operating costs (OPEX).

In low carbon TRIP steels, the formation of carbide-free bainitic ferrite is crucial for the stabilization of austenite. Based on experimental investigations modeling the bainite reaction is examined adopting diffusional and displacive mechanisms, as well as the semi-empirical JMAK approach. Transformation tests were carried out to study the isothermal austenite decomposition into bainitic ferrite for a model steel containing 0.6wt%C, 1.5wt%Mm and 1.5wt%Si which replicates the composition of remaining austenite at the start of the bainite reaction in a classical C-Mn-Si TRIP steel. In the diffusional approach, classical nucleation theory is employed and subsequent growth of bainite plates is modeled using the Zener-Hillert theory. In the displacive approach, the autocatalytic nucleation of bairtite plates is assumed to be rate controlling. The predictive capability of all models is evaluated for temperature ranges where different morphologies of bainitic ferrite have been detected, The shortcomings and inherent challenges associated with either of these modeling approaches will be delineated.

Jan 1, 2003

By Mikiya Tanaka, Mikio Kobayashi, Mansour A. S. A1Ghamdi, Kenji Tatsumi, Yukinori Saiki, Hirotaka Senba

"In order to recover nickel ion in a spent electroless nickel - phosphorus alloy plating bath and, at the same time, to remove impurities such as iron and zinc, the applicability of solvent extraction with LlX84I as the extractant has been investigated using actual spent solution. Although the extraction efficiency of nickel from the spent solution is considerably lower than that from the nickel sulfate-nitrate solution, nickel in the spent solution is selectively extracted with high efficiency at the pH of 6 - 7. The extracted nickel is effectively stripped by sulfuric acid at a pH of less .than· 3. On the basis of these results, a· flowsheet for recovering nickel from the spent solution is proposed Chemical equilibrium calculations of the spent solution has shown that the complex formations of nickel with anions such as lactate and phosphonate ions become predominant in the pH range between 2 and 6. This results in the depression of nickel extraction efficiency from the spent solution as compared with that from the .nickel sulfate-nitrate solution. By combining these aqueous equilibrium calculations with the· extraction model considering the extraction stoichiometry and the aggregation of the extractant in the organic phase, the extraction behavior of nickel is quantitatively predicted.IntroductionElectroless plating is indispensable for the recent advanced industries such as the electronic and mechanical industries. Electroless plating baths are repeatedly used by supplying the metal salts; however, the accumulation of the counter anions of the metal ions, the components formed by the oxidation of the reducing reagents in the plating baths, and the metal ions as impurities dissolved from the surface of the objective materials degrades the· quality of the plating. Thus, the baths are finally treated by a precipitation method to form a large amount of metal sludge, which is disposed in dumping sites. Therefore, from the standpoints of environmental protection and resource preservation, it is highly desired to establish a recycling process of the plating baths with minimum emission. Solvent extraction seems to be one of the 'suitable methods to recover metals from the spent electroless plating baths, because the concentration of the metal ion in the baths is relatively high, which is advantageous to solvent extraction as compared with the ion-exchange and adsorption methods. Some studies about the application of solvent extraction have already been carried out using simulated spe11t electroless plating baths [1-3]."

Jan 1, 2000

By R. W. Harnmack

Hydrogen sulfide generated by the anaerobic respiration of sulfate-reducing bacteria was used to treat pH 2.2 water from the abandoned Rio Tinto copper mine in Nevada. The untreated water contained 550 mg/L Fe, 140 mg/L Al, 90 mg/L Cu, 80 mg/L Mn, 60 mg/L Zn, 4 mg/L Co, and 2 mg/L Ni. The bench-scale treatment system examined consisted of a bioreactor for H2S generation and three precipitator/clarifier units for metal sulfide precipitation and recovery. The treatment system reduced the concentrations of all metals except Mn to less than 0.1 mg/L. Manganese concentrations were reduced by 96 percent to 3.3 mg/L. A CUS/SO concentrate (33 pct Cu) and a ZnS/5° concentrate (28 pct Zn) were produced that may be suitable for metal recovery at existing smelters

Jan 1, 1994

By R. A. Roberti

Most copper refineries use conventional wheel systems to cast anodes. over a period of time the copper moulds that are used become warped and cracks develop. To control mould warpage, the mould's are either rejected after a certain warpage is reached, or the shape is restored by mechanical means. The cracks, unless they are very severe, are repaired by a peening process. Even with regular maintenance to control warpage and cracks, the moulds have a limited useful life. If warpage and cracks are not controlled, anode quality deteriorates and tankhouse operations are seriously affected. -An intensive study was initiated to develop means of controlling mould warpage which culminated in the d?evelopment of technology to control mould warpage to within ±1. 5 mm, and at the same time effectively contr0l: cracking and significantly increase the mould life-. The warpage control has been achieved by using a unique mould design. Mould cavities are present on both sides of the mould and periodic inverting controls the wa-rpage in the cavities. The mould casting procedure has been developed and all production wheels have been converted to the new mould design. The performance characteristics of these moulds will be detailed. 21

Jan 1, 1987

By T. C. Goel, A. Venna, R. G. Mendiratta

"Processing of ferrites has gained tremendous importance in recent times to meet the high performance demands on ferrites in keeping with the fast emerging· technologies. The quality of ferrite powders has strong influence on ·the performance of final device. Fabrication· of high performing ferrite components requires starting ferrite powders of precise stoichiometry, purity and microstructure. It is difficult to obtain these attributes by the conventional ceramic method. The key to obtaining quality powders lies in the· solution techniques. With this in view soft ferrites have been prepared by a wet chemical process, known as the citrate precursor method, which involves the formation of citrate complexes of the constituent cations. The advantages of this process are the ease of preparation and close control of composition, homogeneity, purity and particle size. Electrical and magnetic measurements on lithium ferrites have shown resistivity higher by more than two orders of magnitude compared to that observed for samples prepared by the conventional ceramic method, and low magnetic losses, making the ferrites specially suitable for high frequency applications.IntroductionProperties of ferrites are known to be sensitive to .their processing technique. A small deviation in the compositional stoichiometry of the ferrite affects its properties greatly. Soft ferrites such as Ni-Zn, Mn-Zn and Mg-Mn. are well known ferrites covering wide-ranging applications [1,2]. Lithiiim ferrites have also assumed technological importance for microwave applications and are potential substitutes for the expensive garnets [3]. Lithium ferrites are often doped with zinc to tailor the saturation magnetization required at high frequencies. Lithium and lithium-zinc ferrites, however, present difficulty to processing due to the volatile nature of both the cation components, namely Li and Zn. These ions are volatile at temperatures > 1000°C which makes their processing difficult. One of the main considerations of high frequency performance of ferrites is the high eddy current losses which prevent the interaction of the magnetic field with the ferrite component and hence impair device performance. These losses can be reduced by having a material of high resistivity. Electrical conductivity in lithium ferrite has been attributed to electron hopping [4] between the two vaience states of iron, Fe2+ <=> Fe3+, on octahedral sites. Maintaining the + 3 valence state of otahedral- Fe ions is thus a prerequisite for achieving high resistivity. The resistivity of ferrites is normally found to be low when processed by the conventional solid-state or the ceramic method [5]. This is attributed to (a) extensive ball-milling employed in the method to mix the component oxides results in non-stoichiometric compositions due to introduction of additional Fe ions on abrasion of steel balls during milling, (b) high processing temperatures involved which result in significant volatilization of Li and Zn ions creating thereby oxygen non-stoichiometry which results in reduction of Fe3 + to Fe2 +, (c) large and non-uniform grain sizes. In the present work, preparation of Li and Li-Zn ferrites by a non-conventional method known as a citrate precursor method [6, 7] which requires lower processing temperatures and duration is reported. The method gives stoichiometric compositions on account of homogeneous atomic-scale mixing of the constituent cations via the formation of metal-citrate complexes mixed in solution state. The method is also capable of giving small grain size which aids the oxidation ofFe2+ ions."

Jan 1, 2000

By Upali Siriwardane, Tushar V. Kudale, Naidu V. Seetala

"Cellulose acetate (CA) membranes with 25% triethyl citrate (TEC) as plasticizer were prepared with varying thickness for CO2 gas separation from water-gas-shift (WGS) reaction products. The AFM analysis of the CA membrane showed that the uniform coating had fewer and smaller pores as the film thickness increased, and corroborated by gas permeability studies. The CO2 permeability has decreased faster than CO permeability with the CA/TEC membrane thickness, and findings support that the CA membrane could be used to entrap CO2. Several CA/TEC membranes were also staked to increase the separation efficiency. Positron Annihilation Lifetime Spectroscopy (PALS) was used to estimate the nano-porosity (pore size and concentration) changes of CA/TEC films. PALS results show a decrease in pore size with increasing CA-TEC concentration in acetone, while the pore concentration increases. The PALS results are correlated with the CO2/CO permeability variations as the CA-TEC concentration change.IntroductionHydrogen is one of the main energy sources available for the future advancement of clean fuel technologies especially for fuel cells. Generation of hydrogen and CO2 from Water Gas Shift (WGS) reaction mixtures of CO and H2O is of interest to many researchers since it allows a large scale production of hydrogen [1, 2]. Once hydrogen is produced using the WGS reaction, the output products contain mixture of CO, CO2, H2, and water vapor. Metallic membranes have been used as hydrogen separation membranes [3-6]. As H2 is separated from the mixture using the metal membranes, we need to separate CO2, and find ways of sequestration of CO2 to avoid environmental problems by greenhouse gasses. Polymeric Membranes have been used for CO2 separation [7]. Plasticizer can control the micro-structural properties such as pore size and concentration of polymer membranes [8], which influence the size/molecular weight dependent diffusion rates of the gas molecules. We have used cellulose acetate with triethyl citrate as plasticizer to separate CO2 from the WGS reaction products. Positron annihilation lifetime spectroscopy (PALS) is very sensitive and able to identify different kinds of defects and their agglomerates such as vacancies, vacancy loops, and voids [9, 10]. PALS has been successful in determining the free volume in polymers that influence the properties of the polymers [11, 12]. Microscopic properties of the free volume obtained from PALS have been correlated to macroscopic properties [13, 14]. We used PALS to study the nanoporosity (pore size and concentration) and fractional free volume changes of CA/TEC films, and used to understand the variations observed in the CO2/CO permeability as the CA-TEC concentration in the membranes change."

Jan 1, 2014

By H. C. Roland Kammel

Stannous sulfate electrolytes are widely used nowadays in electrolytic tin production. Characteristic features of this electrolysis process are that dense cathode deposits can only be obtained by additions of organic additives and that so called ?black mud is formed on the anode surface which leads to an increase in cell-voltage. In order to prevent excessive cell-voltages or oxygen evolution the black mud has to be removed periodically. Studies in laboratory scale have been performed about the effect of different organic additives on electrolytic tin deposition and the formation of surface layers on pure and industrial tin anodes. Results reveal that organic addition agents are effective in reducing cathode roughening as well as extending the covering time of the anode ?by black muds.

Jan 1, 1985

By H. A. F. de Souza, Dana S. Mills, P. E. Burgener

"ICP-MS has moved from a laboratory curiosity to a functional analytical tool. This paper discusses how ICP-MS has been used to solve difficult analytical problems encountered when analyzing various mine materials. Comparisons between analytical techniques applied to the analysis of gold and the platinum group metals illustrate the advantages and problems of ICPMS when. applied to trace levels of some metals iri the presence of ore grade metals. Interferences and matrix effects are compared to ICP, AA and Neutron Activation. The necessity to select chemical extractions which are compatible with ICP-MS are also discussed.The ICP-MS techniques explained in the examples on Au and precious group elements (PGE) have validity in analytical problems encountered in testing of trace metals in the presence of major elements found in mine materials. Exploration and environmental testing are other areas that require the same analytical approach to quantify trace levels in the presence of major interfering elements normally associated with mining environments."

Jan 1, 1999

By E. Daniel Baker

"The term ""oxide disseminated gold deposits"" refers to near surface, gold-bearing veins, faults, and shear zones that typically contain appreciable amounts of oxidized ore or gossanous material, resulting from oxidation of sulphides.The concept of oxide gold deposits underwent a dramatic change after the discovery of the Carlin gold mine in north-central Nevada in the early 1960's. Now the term implies large tonnage, low-grade bulk minable deposits that are processed by milling and/or heap leach methods.Oxide gold deposits may now be classified into two types: (1) primacy ores derived directly from the effects of hydrothermal alteration on host rocks, and (2) secondary oxide ores derived from the supergene oxidizing effects of circulating post-mineral meteoric waters on gold-bearing sulphides. Each type of deposit has unique diagnostic mineralogic and metallurgical characteristics that must be addressed to achieve successful exploration strategies and viable metallurgical exploitation.The author would like to thank the management of Newmont Metallurgical Services and Newmont Mining Company for allowing presentation of this paper. Thanks are due Sevkett Acar, Donald M. Hausen, Jerry R. Odekirk, and D. Erik Spiller for their critical review of the manuscript. Also, thanks are extended to all those cited and uncited whose hard work and dedication have led to the discovery and exploitation of near-surface oxide gold deposits. Our knowledge would be greatly limited without the dedication and research of many others."

Jan 1, 1997

By M. K. Mohan

During the processing of metals like Cu, Ni, Co, large quantities of solutions, which contain co- products such as Sb, Cd, Pb etc. are generated. These solutions if processed to recover the metals help in conservation of metals as well as environment preservation. The present study was taken up to recover antimony from process solutions using zeolites. The effect of pH of the solution, time and type of zeolite viz., chabazite, mordenite, erionite and clinoptilolite on the sorption of antimony was investigated. Rate of sorption increases with pH and about 77-pct. antimony sorption was observed with chabazite at a pH of 6. Optimal conditions were established for the maximum recovery of antimony fiom process solutions. The mechanism of sorption for Sb was proposed in terms of adsorption and intraparticle diffusion. The calculated adsorption constants from Langmuir and Freundlich equations indicated that the adsorption of antimony on chabazite was strong.

Jan 1, 1999

By S. K. Wu, Ray Y. Lin, Sunil Annaji

Infrared joining of TiAI using aluminum foils as the filler material was investigated at temperatures between 1050 °C and 1350 °C in a flowing argon environment for times varying between 15 and 60 seconds. Using aluminum foils, the attempt was to form the Al3Ti phase in the joint as a result of reaction between Al and TiAI at temperatures above the melting point of Al. It has been found based on X-ray diffraction and TEM analysis that, Al3Ti, indeed is the product of infrared joining of TiAI using Al as the joining alloy. Al3 Ti was detected even in the joint processed at 1050 °C for only 15 seconds. Since the aluminum foil used in this study contains 27 at% Si, the t 2 phase in the Ti-Al-Si ternary system is believed to have also formed at the joint/base TiAI interface. Cross sectional studies on the joined specimens have shown different degrees of reaction depending on the temperature and time of joining. Micro hardness evaluations across the joint show that the hardness near the center of the joint is typically smaller than that near the joint edge next to the base material. However, as the joining temperature and time increase, the increment of the hardness at the center of the joint is faster than that around the periphery of the joint.

Jan 1, 1996

By T. R. A. Davey

A simple model for metal solution behaviour may be derived, on the basis of dilute solution solubilities (where? log concentration of solute varies linearly with reciprocal temperature) and not-so-dilute region solubilities (where the log of the alpha-function at saturation frequently varies linearly with reciprocal temperature) and assuming activity to vary according to the quadratic formalism in between. Matte binary systems usually exhibit regular .solution behaviour when the constituent species are chosen appropriately. In many recent papers, metal solubilities in .slags are expressed as the sum of several different and supposedly independant molecular species (e.g. oxides, sulfides, chlorides), Such a view is untenable because of the now proven ionic nature of slags. Some possible reasons for the great effect of sulfur on copper solubilities in slags are discussed.

Jan 1, 1985

By W. W. Albrecht

I. Introduction Refractory metals like tungsten, molybdenum, rhenium, tantalum and niobium and their compounds are essential ingredients of our modern technology. Especially in purified form, they are used in special alloys, electronics, optics and ceramics. The processing route from raw material to high purity refractory metals and their compounds includes, as a prime option, the following steps: - dissolution of raw materials. - liquid liquid extraction. - precipitation of high purity intermediate compounds. - calcination/reduction to high purity oxides/metals. Especially in the first three steps, major amounts of chemicals like acids or sodium hydroxide are used and, as by-products, substantial quantities of residues and effluents are generated. The impact of environmental regulations on these by-products and the attempt to reduce or minimize the amount of residues and effluents produced will be discussed in this presentation using Ta/Nb chemistry as the example. The basis of our considerations will be the way these by-products are handled at HCST, a major, and in some cases, the biggest producer of refractory metals (tungsten, molybdenum, rhenium, tantalum, and niobium).

Jan 1, 1992

By A. A. el-Geassy

High-grade iron ore fines rejected from the DRl plants (>96%Fe20) were isothermally reduced in 30-60%COIH2 gas mixtures at 973-1273K. The freshly reduced reaction products were then subsequently carburised in either H2/CO or H2/CO/S mixtures at 823-1073K for 30-120 min. The thermogarvimetric technique was used to follow up both of reduction and carburisation reactions as a function of time. The carburised samples were characterized by X-ray and Mossbauer techniques. Chemical and carbon analyses were also applied. The influence of temperature and gas composition on the reduction behavior was investigated. The calculated values of apparent activation energy, application of gas-solid mathematical formulations were correlated with the microstructures to predict the reduction mechanism, The influence of carburization time, temperature, CO contents in H2/CO or H2/CO/S were investigated. A conversion extent of Fe to Fe3C was taken as a measurable index for the efficiency of carburization reaction under the different experimental conditions.

Jan 1, 2003

By Gaballah Djona M.

Spent hydrorefining catalysts contain about 5 % of CoO and/or NiO, 12 % of MoO3 and up to 10 % of V205. They are generally supported by alumina and contain up to 25 percent of C, S and hydrocarbons. Such materials are potentially hazardous to the soil and to water resources. Selective chlorination of raw unroasted samples with Cl2 + air gas mixture had been investigated. At temperatures lower than 600 °C, it was possible to recover more than 90 % of nickel and cobalt chlorides, about 99 % of the molybdenum and up to 75 % of vanadium chlorinated compounds. CoCl2 and Ni/Cl2 were extracted from the chlorination residues by their dissolution with acidified water. Molybdenum and vanadium chlorinated compounds were recovered by selective condensation from the vapor phase. The chlorination of Al2O3 could be limited to less than 6 %. The scale up of this treatment was successful and a flow-sheet is proposed.

Jan 1, 1995

By Steven R. Izatt

IBC Advanced Technologies, Inc. (IBC) has developed a mercury selective product, which can be used by sulfuric acid producers as either a polisher, or as the primary technology for mercury removal from sulfuric acid. The Molecular Recognition Technology (MRT) separations material selectively binds Hg2+, and to a lesser extent Hg+, out of concentrated sulfuric acid. Mercury output levels of less than 0.1 ppm can be attained by the MRT system. Pilot plant tests have been successfully conducted at base metal smelting operations. A large-scale commercial plant is due for commissioning in 2003. Results from these projects will be discussed.

Jan 1, 2003

By N. Kanari

One of the criteria to define the market value of chromite concentrate is its chromium to iron ratio. Changing this ratio for a definite chromite mineral is impossible by physical processing. This study investigated the possibility of increasing this ratio through the carbochlorination and the oxychlorination of chromite concentrates. Experiments are carried out up to 1000 °C. The characteristics of samples and reaction products are determined by SEM, XRD and chemical analysis. The carbochlorination of a chromite concentrate at about 600 °C leads to the . selective partial elimination of iron allowing a higher Cr/Fe ratio of the treated concentrate. Selective extraction of iron could also be achieved at about 950 °C by oxychlorination. In this case, a part of chromium contained in the concentrate is recovered as chromium oxychloride. The obtained residue had high content of Cr, Mg and A1 oxides. Such material has probably better chemical and thermal properties that may. be useful for foundary and refractory applications. Two flow-sheets for the beneficiation of the chromite concentrates using carho- and oxychlorination are suggested.

Jan 1, 1997

By J. G. Zafiratos

The leaching of a Greek low-grade manganese dioxide ore, not amenable to conventional mineral processing operations, was studied using a mixed culture of Thiobacillus sp. bacteria. The experiments were carried out in specially designed continuously aerated and stirred tank reactors arranged in two-tank series. The first tank of each series was loaded with an elemental sulfur culture suspension while the second was loaded with a manganese ore high density slurry. The bacterial culture had been previously adapted to grow on elemental sulfur and also in the presence of manganese ore and dissolved manganous ion. A two level full factorial design was constructed in order to study the effects of the ferric ion concentration in the leach solution, the "elemental sulfu weight to ore weight" ratio, the ore pulp density and the composition of the dispersed gas. The responses which were investigated included percentage manganese recovery, co-dissolution of iron and manganese dissolution rate. Parameters with constant values throughout the experiments were the leach solution pH, the nutrient medium composition, the dilution rate and the ore and sulfur grain sizes. It was found that the ferric ion concentration was the most significant factor and had a positive effect on the final percentage extraction of manganese from the ore and also on the rate of manganese solubilization from the ore. The effects of the other factors studied are discussed in detail.

Jan 1, 1997

By A. E. Torma

In recent years the copper industry has gained considerable economic stability. An essential part of this industrial wealth is attributable to the successful application of bio-mediated heap and dump leaching techniques in the recovery of copper from low-grade resources. This study evaluated the leachability of a chalcopyrite conlentrate using naturally occurring mixed culture of predominantly Thiobacillusferrooxidans and Thiobacillus thiooxidans. For the effects-of pulp density, the overall reaction rate constant (k) and the order of reaction (n) have been determined to be 1.93 h-1 and 1.36, respectively. Cyclic voltammetric measurements revealed that intermediate reactions are involved in the chalcopyrite oxidation. Using the Price approach, it was shown that the dissolution of chalcopyrite is solid state diffusion controlled.

Jan 1, 1992