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By Chu Yong Cheng

Manganese is one of the main impurities in the recovery of base metals from their ores. This is especially true when laterite ores are processed using the pressure acid leach (PAL) process. The use of intermediate precipitation, solids/liquid separation and re-leach in the three Western Australian nickel laterite plants to separate nickel and cobalt from manganese and other impurities makes these processes complicated and costly in capital and operation. The research work carried out by the solvent extraction (SX) group at the A J Parker Cooperative Research Centre for Hydrometallurgy (CSIRO Minerals) has led to the development of direct solvent extraction processes to separate nickel and cobalt from manganese and other impurities. The simplicity of the process flowsheets and the expected savings in capital and operating costs are the major advantages of the new direct solvent extraction processes over the existing processes. By using a new synergistic organic system, Versatic 10 / dccyl-4-pyridinccarboxylatc ester, with a pilot plant leach solution from BHP¬Billiton (after iron precipitation), the metal values (Ni and Co) together with zinc and copper were separated from manganese and other major impurities (Mg, Ca and Cl) in the first SX circuit. The co-extracted manganese, magnesium and calcium were easily scrubbed out. The extraction and stripping kinetics of the metals with the new synergistic organic system were very fast and the synergistic system was found to be chemically stable. pH-extraction isotherms of metals with D2EHPA showed that the extraction order as a function of pH50 was Zn2+ > Ca2+ > Mn2+ > Cu2+ > Co2+> Ni2+> Mg2+. Semi-continuous test work with a cobalt pilot plant leach solution from Peko Rehabilitation Project Pty Ltd and a synthetic solution to simulate a concentrated laterite leach solution from BHP-Billiton showed that manganese, together with calcium, copper and zinc can be separated from nickel, cobalt and magnesium. This led to the development of another direct solvent extraction process to separate manganese and other impurities from nickel and cobalt and to recover nickel and cobalt from leach solutions. A project was initiated by HiTec Energy Ltd to recover manganese from waste laterite leach solutions using SX technology and to further purify it to produce high purity electrolytic manganese dioxide (EMD) for the high quality alkaline battery industry. Batch tests were conducted to select a suitable organic system for the extraction of manganese in terms of selectivity and extraction and stripping kinetics. A total of eight organic systems were tested using waste laterite processing solutions. A Versatie 10 / synergist system showed very promising results. By using the synergistic system, high manganese recovery would be obtained, fewer SX stages would be required and a higher A:O ratio could be used in extraction, resulting in a smaller organic inventory and lower capital costs. The risk of gypsum formation is also minimised with the synergistic system. Keywords: Solvent Extraction, Manganese, Laterite, Synergist

Jan 1, 2004

By Emil B. Milosavljevic

The photochemical reactions of cyanide ion induced by light were investigated in the presence or absence of a titanium(IV) oxide semiconductor photocatalyst. The light sources employed were the sun and arrays of either mercury or fluorescent (cool white) lamps. The results obtained verify that cyanide decomposes much faster when TiO2 is present in the solution and that it is first oxidized to cyanate. However, contrary to the previous studies, it is established that cyanide is subsequently further oxidized via nitrite all the way to nitrate irrespective of the light source. As expected, the rates of the oxidation processes decrease with the illumination source utilized in the following order: Hg-lamps > sunlight > fluorescent lamps. As nitrate is a significantly less hazardous contaminant than cyanide, complete photocatalytic oxidation of cyanide to nitrate may be a viable method for decontamination of cyanide wastes. Contrary to previous claims, we find that cyanide is slowly photochemically decomposed even in the absence of TiO2. For example, with the mercury lamps as the light source, in two hours, cyanide concentration decreases to essentially zero; up to 7% was converted to cyanate and the remainder to unidentified products.

Jan 1, 1992

By Rui Mao, Ke-Xin Nao, Jian-Liang Zhang, Xiang-Nan Xu, Meng-Fang Wei

"In this research, fundamental characteristics of dust and sludge containing iron from the dusting system of sintering process, blast furnace, oxygen converter and rolling process in steel enterprise were studied by chemical analysis, X-ray diffraction analysis, optical microscope analysis, scanning electron microscopy analysis, particle size analysis and other analysis means. Development direction of resource utilization for dust and sludge containing iron from steel enterprise was put forward on the basis of above study.IntroductionDust and sludge containing iron for steel enterprise mainly come from the dusting system of sintering process, pelletizing process, blast furnace, oxygen converter, rolling process and other related process. Iron content of dust and sludge is between 30% and 70%, and they also contain certain content of carbon, calcium oxide, magnesium oxide and harmful elements [1-3]. Output of dust and sludge is determined by raw materials conditions, technological processes, equipment configuration and management level. Dust output in sintering process accounts for about 2% to 3% of the sinter production, while dust and sludge from iron making and steel making process respectively take up 3% to 4% of hot metal and crude steel production, and the solid waste from rolling process accounts for about 0.8% to 1.5% of the output of rolled products [4,5]. Dust and sludge contains Fe, CaO, MgO, C and other valuable resources, it will not only result in the waste of resources, but also cause serious pollution to environment ifthe dust and sludge are not recycled. China's crude steel production in 2012 is about 700 million tons and output of dust and sludge containing iron is nearly 60 million tons, so, it is of great significance to have a resource recycling for dust and sludge containing iron from steel enterprise."

Jan 1, 2014

By J. A. Sekhar

Solidification processing/casting is increasingly being adopted as the preferred manufacturing technique for the fabrication of net shaped complex geometry components. Modeling of solidification processes is important both for design purposes as well as for understanding the physics of morphological evolution of the solidification microstructure. A fundamental aspect of such modeling involves the precise understanding? of heat transfer through the two phase solid/liquid region. A scheme to do this will be presented where the nonlinearity of the fraction liquid with change in temperature can be incorporated into the numerical calculations. The importance of properly accounting for the non-linear mushy zone will be discussed. Typical processes like squeeze casting and electromagnetic stirring will be discussed to illustrate how precise modeling of the solid/liquid region can aid in the calculation of accurate heat transfer coefficients for these processes.

Jan 1, 1990

By Keiji Okumura, Jiayi Shan, Jian Yang, Masamichi Sano

"A new method of deoxidation and desulfurization of molten iron with magnesium vapor has been developed. An immersion tube, which was filled with pellets of the mixture of magnesia and carbon powders, was put into the molten iron. Magnesium vapor produced by carbothermic reduction of magnesia inside the tube was injected directly into the molten iron with argon carrier gas. The effects of temperature and carrier gas flow rate on deoxidation and desulfurization were investigated. A mathematical model of the reactions was developed. The rates of deoxidation and desulfurization were controlled by mass transfers of magnesium vapor in the gas-phase and oxygen and sulfur in the liquid-phase. This method may offer high efficiency for magnesium deoxidation and desulfurization of molten iron.IntroductionMagnesium is a strong refining agent in steel-making processes1 • At steelmaking temperatures, magnesium has a very low solubility in liquid iron, and a very high vapour pressure2 • Deoxidation and desulfurization with magnesium take place essentially through the interaction of magnesium vapor with oxygen and sulfur dissolved in molten iron, and magnesium can change chemical composition of nonmetallic inclusions3 • However, addition of magnesium to the steel bath is dangerous and does not give high efficiency in the refining process4 • Furthermore, as a refining agent, the price of magnesium is higher than aluminium and CaO fluxes. In the present study, a new method of the deoxidation and desulfurization of molten iron was developed using magnesium vapour in-situ produced by carbothermic reduction of magnesium oxide. Pellets made of mixture of magnesia and carbon powders were charged into an immersion tube, which was made of alumina or graphite. The magnesium vapor was injected directly into the melt. The effects of pellet mass, experimental temperature and carrier gas flow rate were studied on the refining rate. A mathematical model of the refining reaction was proposed on the basis of the experimental results."

Jan 1, 2000

By D. A. Milligan

Ammonia leaching of copper sulfide concentrates, matte, scrap or other sources of copper yields copper amnine sulfate solutions which are converted to metal in a two-stage process involving precipitation of inter- mediate sulfites and their thermal decomposition to copper powder of high purity. Processing details and results are given. Considerable simplification in circuitry and cost savings are indicated. Energy requirements are reduced by substitution of copper powder precipitation and ammonium sulfate crystallization for solvent extraction, electrowinning and lime boil.

Jan 1, 1976

By Dietmar Eifler, Marcus Klein, Hendrik Kramer

Conventional methods to characterize the fatigue behavior of metallic materials are very time and cost consuming. That is why the new short-time procedure PHYBALCHT was developed at the Institute of Materials Science and Engineering at the University of Kaiserslautern. This innovative method requires only a planar material surface to perform cyclic force-controlled hardness indentation tests. To characterize the cyclic elastic-plastic behavior of the test material the change of the force-indentation-depth-hysteresis is plotted versus the number of indentation cycles. In accordance to the plastic strain amplitude the indentation-depth width of the hysteresis loop is measured at half minimum force and is called plastic indentation-depth amplitude. Its change as a function of the number of cycles of indentation can be described by power-laws. One of these power-laws contains the hardening-exponentCHT eII, which correlates very well with the amount of cyclic hardening in conventional constant amplitude fatigue tests. To identify heat-treatment-parameters and SAE 52100 TRIP-alloys with high hardening rates as well as their damage tolerance the PHYBALCHT- and PHYBALLIT-method were used. One modified SAE 52100 TRIP-alloy was investigated in detail. The fatigue behavior and the cyclic hardening of the selected SAE 52100 TRIP-alloy was investigated and compared with conventional SAE 52100. Conventional stress-controlled fatigue tests were performed on a servo-hydraulic test system with a frequency of 5 Hz and a load ratio of R = -1. Different rates of cyclic hardening were identified. The size of the nonmetallic inclusions leading to crack initiation and the number of cycles to failure were used to evaluate differences in the damage tolerance capability.

Jan 1, 2015

By I. Gaballah

Decontamination of synthetic solutions of copper acetate, chloride, nitrate and sulfate containing 10, 100 and 1000 ppm of copper, using chemically treated barks has been studied. Metal percent removal from solutions depends on the pH and the initial concentration and to some extent on the salt used. It varies from 40 to 99 % of the solution initial metallic ion's content. The maximum retention capacity of the treated bark varies from 31 to 43 mg of Cu per gram of dry modified bark. Bark loaded with copper had been analysed by Scanning Electron Microscopy and lnfra Red spectroscopy. Cu is uniformally distributed in the bulk of the bark. No copper segregation is observed. It seems that copper is bound to the acidic sites of the bark. Anions are not detected on the copper loaded bark neither with the SEM or with the IR spectroscopy.

Jan 1, 1993

By . Menad Gaballah I

Three samples of solid wastes generated by the non ferrous metallurgy were characterized. These residues contain up to 42 % of valuable metal compounds ( Cu, Pb and Zn ) and 23 %of toxic compounds t As, Hg, Cd and Se ). These sample were subjected to thermal treatments between 200 DC and 800 °C in controlled oxidizing. reducing and chlorinating atmospheres. Up to 99 % of As, Cd, Hg and Se were eliminated from these industrial wastes. Cu, Pb, and Zn compounds were concentrated in the treatments' residues of these samples. A Global Decontamination Factor' GDF ' was defined to measure the efficiency of the elimination of toxic elements and the recovery of valuable elements for a specific sample submitted to a given treatment. It seems that the thermal treatment in a reducing atmosphere was the most efficient in decontaminating these solids and the concentration of valuable elements. a.

Jan 1, 1995

By J. J. Moore

The application of plasma technology to process metallurgy is briefly discussed. Experiments involving in-flight reduction of minerals (taconite, chromite, in particular) with a solid-based carbon reductant are described. The resultant metallic and slag product analysis is discussed with respect to thermodynamic and kinetic considerations.

Jan 1, 1985

By Katsutoshi Inoue

The sulfuric acid leaching of spent hydrodesulfurization catalysts yields an acidic solution rich in rare metals such as molybdenum, vanadium, cobalt, and nickel in addition to aluminum. For the purpose of separating and recovering the rare metals from the solution, basic solvent extraction characteristics of the metals involved with commercially available acidic organophosphorus reagents like TR-83, PC-88A, PIA-8 and CYANEX 272 as well as aliphatic alpha-hydroxyoxime LIX 63 from sulfuric acid media were investigated in the present work. It was demonstrated that CYANEX 272, PIA-8 and LIX 63 possessed excellent selectivity for molybdenum and vanadium over the other metals at comparatively low pH. Further, recovery of molybdenum and vanadium from the total leach liquor by the selected extractants was discussed. Additionally, in order to achieve preferential separation and recovery of cobalt and nickel over an appreciable amount of aluminum from the raffinate obtained after recovering molybdenum and vanadium, a systematic investigation was conducted on synergistic extraction behaviors of the mixed solvents of LIX 63 in combination with a series of acidic extractants such as CYANEX 272, PIA-8, PC-88A, D2EHPA, TR-83 and OPEHPA for cobalt, nickel and aluminum. It was elucidated that all of these mixtures could exhibit a good synergistic effect for extraction of cobalt and nickel, and that the lower the pKa of the acidic extractants, the greater the synergism. Contrarily, the extraction of aluminum, was considerably suppressed by LIX 63. Effective extraction of cobalt and nickel away from aluminum was accomplished from the sulfate solution at low pH (1.0 - 2.5) with the mixtures. In particular, the mixtures consisting of LIX 63 and CYANEX 272 or PIA-8 appeared to be the most feasible and economic from an industrial point of view, yielding acceptable separation efficiency for cobalt and nickel over aluminum and .a low acidity requirement for stripping cobalt and nickel as well as negligible degradation of LIX 63. Aluminum can be readily recovered as sulfate salt from the raffinate obtained after recovering molybdenum, vanadium, cobalt and nickel as outlined above by conventional crystallization method.

Jan 1, 1995

By N. J. Themelis

The basic chemical, thermal and transport principles that underlie sulfide smelting of. copper, nickel and lead are reviewed. Two basic types of modern smelting processes are distinguished?: flash-smelting, where the predominant reactions occur between oxygen-bearing gas and concentrate particles dispersed therein; and bath-smelting where the concentrate is enveloped and reacted in a turbulent bath of matte, slag and gas. The controlling heat and mass transfer phenomena are discussed, and appropriate correlations are proposed.

Jan 1, 1983

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 M. T. Thomas

Sufficient development of the X-Ray Photoelectron Spectroscopy (XPS), the Auger Electron Spectroscopy (AES), and the Secondary Ion Mass pectroscopy (SIMS) has made these instruments ideal for solving problems related to mineral processing -particularly gold ore processing. XPS can determine both the surface composition and chemistry of ores and tailings, and the various phases within either of them. AES can also determine surface composition with the further advantage of having greater spatial resolution so the surface chemistry associated with specific minerals in the ore can be identified. This identification helps to clarify why some minerals pass through a chemical process unaffected, while others can be successfully treated. SIMS has an elemental sensitivity from one to four orders of magnitude greater than XPS or AES which makes it useful for detecting the presence of some elements in very low concentration (parts per million).

Jan 1, 1981

By A. Kontopoulos

The Olympias Mine in Northern Greece is producing an extremely refractory gold-bearing arsenical pyrite concentrate, containing on the average 41 3 S, 40 3 Fe, 10-12 3 As, 25 ppm Au and 35 ppm Ag. During the process selection stage, more than a dozen alternative technologies? were considered and an in-depth analysis was prepared for the three most promising, ie roasting, pressure oxidation and biological oxidation. Detailed capital and operating cost estimates were prepared, based, where appropriate, on laboratory and pilot-plant tests. A number of criteria was used for process evaluation and selection, including capital and operating costs; environmental impact, gold' recovery, stage of development, etc. Based on the above evaluation, the Sherritt Pressure Oxidation Process was finally selected. A detailed description of the process selection stage, supported with laboratory and pilot-plant test results on many of the processes considered, will be? presented.

Jan 1, 1989

By I. C. Howard, E. J. Palmiere

"Heat transfer and friction in hot flat rolling have traditionally been characterised by an average heat transfer coefficient (h) and an average friction coefficient (p.). However, the presence of oxide scales and asperities at the interface question the use of such averages. The apparent irregularity and lack of pattern of interactions at the interface has prompted this present investigation to move away from averaged h and 11 values, and to study their local evolution based on probabilistic rules. The approach is based on the probability of finding the workpiece surface in a specific configuration at a particular instance of time in the roll gap. These rules are based on observations of surface phenomena such as scale behaviour during hot rolling. The model is implemented using user-subroutines integrated with the commercially available finite element program ABAQUS™. The results show the strong dependence of h and u on the local scale interactions. In particular, the effect of scale thickness, material behaviour and processing conditions on the evolution of hand 11 are discussed. Finally, the development of a Cellular Automata based Finite Element (CAFE) model is proposed to model the combined interfacial phenomenon of friction and heat transfer at the tool-work piece interface.IntroductionIntricate interactions between process variables in hot rolling of steels make it a challenge to the modelling community. For a given material and geometry combination, reducing interfacial power losses can increase the efficiency of the rolling process. The roll-strip interface, therefore, forms the critical zone and is currently the domain of intense investigation, especially to characterize interfacial frictionl • 2 and heat transfer3 • 4 . These interfacial phenomena are inter-related and cannot be studied in isolation. However, very few mathematical models4 • 5 combine an analysis of friction and heat transfer and deformation of the strip-roll interface taking into account the role of asperities and oxide scales."

Jan 1, 2001

By Akira Yazawa

Experimental results for the distribution ratios of various elements between the slag, matte and/or copper in the silica-saturated copper smelting system were summarized. The experiments were carried out under an oxidative smelting condition with S02 gas flow, and also a reductive smelting condition equilibrating with metallic copper or iron. To evaluate the results thermodynamically, the availability of one atom cation base expression for the constituent compounds is emphasized from both of theoretical and practical standpoints. Both of oxidic and sulfidic dissolutions in slag are postulated for some elements such as copper, nickel and lead., and the experimental results are reasonably explained thermo-dynamically. The results for the mutual solubility between matte and ferrite slag and the distribution of minor elements between liquid copper and ferrite slag are also discussed.

Jan 1, 1983

By Kenneth P. Michalek, James E. Kelly, Jonathan A. Dantzig

"Many investigations have been reported regarding the simulation of continuous casting with emphasis on in-mold heat transfer. These analyses have been limited, however, because they require either estimation or measurement of the characteristic heat transfer between the ingot and the mold. In this paper, a self-consistent model 'is presented for calculating the heat transfer between a solidifying continuous casting and the mold, in the context of the continuous casting of steel. Using both thermal and stress analyses, the air gap formed during continuous casting is calculated and used to compute the heat transfer coefficients. Iteration between the thermal and stress analyses is used to determine a self-consistent solution. IntroductionThe continuous casting process for steel is illustrated schematically in Fig. 1. Molten steel is tapped into a tundish from which it flows at a controlled rate into the continuous casting mold. The initial shell of the casting forms in the mold by transfer of heat from the metal through the mold wall to the cooling water. The remainder of the casting is solidified by application of water sprays, and/or radiation cooling below the mold.Heat transfer in the mold portion of the process is important because it controls the formation of various defects which are deleterious to subsequent processing. Examples of defects formed in this region are surface irregularities, such as cold folding and oscillation marks, and more serious defects, such as longitudinal or transverse cracks. A more catastrophic problem which may occur is a breakout, in which the shell ruptures and molten steel is discharged in an uncontrolled way."

Jan 1, 1986

By T. M. Dreher

The difficulties associated with the operation of a classical rhodium refining process have prompted many attempts to develop a viable solvent extraction flowsheet for rhodium. Recent investigations at McGill University have involved the activation of rhodium prior to its solvent extraction. The role of activation is to convert the aquochloro complexes of rhodium to a form extractable by conventional solvent extraction reagents. In the novel separation scheme identified, chloro complexes of rhodium are converted to bromo complexes, which undergo aquation to a lesser extent, making them more easily extracted. Rhodium is then extracted using Kelex 100, and stripping is achieved by use of a concentrated chloride based solution. Separation of rhodium from iridium is achieved by either prior reduction of Ir(IV) to Ir(III), as the latter is not extracted, or via co-extraction and differential stripping. A conceptual flowsheet for the refining of rhodium using this method is proposed.

Jan 1, 1998

By G. Van Weert, A. van Sandwijk, O. W. J. S. Rutten

"Cathodic and anodic reactions in an acidic nitrate medium were studied in reference to the production of electrolytic manganese dioxide from pyrolusite' (Mn02) ores by reductive leaching. Two USA ores were investigated. The reductant for the pyrolusite ore is produced cathodically in an electrolytic cell and can either be nitrous acid (HN02) or nitric oxide gas (NO). In this work emphasis was placed on the nitrous acid leach. In a high-temperature leach in a nitrous/nitric acid medium, manganese and silver are solubilized and iron is not. Anodic electrowinning of manganese dioxide from the acidic manganese nitrate electrolyte yields flaky y-Mn02, similar to that produced from sulfate and chloride electrolytes. Cathodic regeneration of nitrorts acid was studied in a membrane cell in 1.0 M nitric acid and 0.0 to 0.1 M nitrous acid on a' platinized titanium cathode. At cathode potentials ranging from +950 to +700 mV (SHE), cathodic reduction to nitrous acid takes place, at cathode potentials < +700 mV, cathodic reduction of nitrous acid to nitric oxide takes place. A conceptual process is presented and discussed.IntroductionManganiferous-silver oresLarge reserves of manganiferous-silver ores are present in the Southwestern United States and Latin America. These ores are generally refractory to hydrometallurgical methods of treatment, due to the insolubility of the higher oxides of manganese (Mn 4+) in all common lixiviants such as cyanide solutions, dilute sulfuric acid, nitric acid, ammonia, salt solution, thiosulfates, etc. The silver is either bound by the insoluble manganese, or is rendered inaccessible to cyanide leach solution by the surrounding manganese mineralization.Higher oxides of manganese will dissolve if they are first reduced pyrometallurgically to manganous oxide (Mn2+). This is a widely used pretreatment for manganese dioxide ores and subsequent dissolution in sulfuric acid is common. In order to avoid the pyrometallurgical pretreatment with its large energy requirements and gaseous emissions, fully hydrometallurgical processes have been proposed. These processes are based on the presence of a reductant in solution, in order to reduce the insoluble higher oxides of manganese to soluble lower oxides. Aqueous S02 has been proposed and tested on industrial scale by the U.S. Bureau of Mines. After washing, silver could be extracted by cyanidation. The neutralization of the pulp prior to cyanidation however causes problems in filtration and the reagent consumptions are high [1]. More recently, acidified thiourea and bacteria were proposed for the solubilization of both manganese and silver in a single leach step. High extractions were obtained, but drawbacks of these methods are high reagent consumption or slow kinetics [2,3]. For the options of manganese recovery from the leach filtrate, precipitation with persulfate or ammonium carbonate and ion exchange have been proposed. The proposed options for silver reclaim are precipitation with either zinc or Na2S and adsorption onto activated carbon."

Jan 1, 1997