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By George P. Demopoulos

In this paper the production and stability of crystalline scorodite (FeAsO4·2H2O) is discussed both on the basis of previously published work as well as recent work performed in our laboratory. The production of scorodite, especially from arsenic-rich and iron-deficient sulphate solutions offers a number of operational advantages such as high arsenic content, stoichiometriciron demand, and excellent dewatering characteristics. In addition to hydrothermal production of scorodite the work done over the last 10 years in our laboratory has determined that it is feasible to produce scorodite by step-wise lime neutralization at 90°C. The atmospheric scorodite possesses the same structural and solubility characteristics with the hydrothermally produced scorodite. Long term equilibration tests (up to 66 weeks) in the pH range 5 to 9 and temperatures from 22 °C to 75 °C revealed scorodite to undergo slow incongruent dissolutionyielding a highly metastable nano-sized 2-line ferrihydrite phase. The equilibrium arsenic concentration with this phase was 0.35, 0.96 and 5.87 mg/L at pH 5, 6, and 7 respectively at 22°C. In the presence of gypsum slightly lower concentrations were measured, this being more pronounced at pH>7. It was tentatively deduced that a Fe-Ca-AsO4 association (in the form of a phase resembling the mineral yukonite) contributes to the lowering of As concentration. Finally thermodynamic calculations determined that scorodite is stable in the presence of ferrihydriteunder oxic conditions up to pH 6.75 at 22 °C or higher pH at lower temperature and gypsum-saturated solutions. Keywords: Scorodite, Crystallization, Arsenic, Solubility, Stability, Precipitation, Disposal, Extraction, Processing, Metals, and Environment.

Jan 1, 2005

By Koji Matsubara, Yoshiaki Iguchi, Shoji Hayashi

Iron ore particles of a limonite iron ore were reduced completely with H2 at 1023K to 1273K in a fluidized bed. Then, at 973K, the formed iron was exposed to HrH2S mixtures (sulfur activity, as=0.5) for 3.6ks and carbidized with CO-H2-H2S· mixtures at 0.1 MPa. During the carbidization, the particles of about 150mg were sampled at every 600s interval. The sampled particles were analyzed by XRD and chemical analysis for C and S to evaluate the content of Fe3C, Fe5C2, Fe and free carbon. The reaction extent is defined as fo=Xfc3C +xFc5c2; x is the molar fraction of Fe in Fe3C. The carbidization curves can be fitted very well to -ln(l-f0)=g(pb T)t; g(p; T) is the carbidization rate, i.e. the carburization rate on the pore surface of reduced iron. The rate is found to be nearly proportional to the specific surface area of reduced iron, a P 0 , which decreases with increasing the reduction temperature. The value of a P 0 does not change by the carbidization and the stability of the iron carbide product in the atmosphere increases with the temperature.

Jan 1, 2000

By Rajesh Kumar Mishra

About 500,000 troy ounces of Platinum Group Metals (PGM) will be available for recycling each year from spent automobile catalytic converters in North America alone. Platinum Group Metals? from spent catalyst can be extracted by Hydrometallurgical, Pyrometallurgical or Gas Phase volatilization processes. This paper is a review and comparative study of various processes investigated for PGM extraction. A number of processes described in this paper have already been commercialized. The technical and environmental aspects of the important processes are discussed.

Jan 1, 1989

By J. Phillip Mackey

A whole new group of non-ferrous pyrometallurgical processes with the ability to utilize tonnage oxygen and capture sulphur dioxide were developed and commercialized over the period 1940s–1980s. Many of these earlier process developments were undertaken with limited knowledge of the process chemistry and influence of key process variables; in many cases, piloting helped provide much new physico-chemical data, but gaps remained. The second generation versions of these technologies of today provide all the primary copper, nickel and lead produced worldwide by pyro-metallurgical smelting. Further, process development has continued and a new generation of copper and lead smelting technologies have also been developed in China since the 1990s. The older reverberatory and blast furnaces have been progressively replaced by the newer technologies—a good example being the introduction in 1992 of the copper IsaSmelt technology at the Mt. Isa smelter in Australia where the former fluid bed roaster and reverberatory furnaces were replaced by a single new smelting unit, together with an acid plant for sulphur dioxide collection. The development of these new technologies was made possible by investment in fundamental and applied research. The lesson for the future is, in order to sustain these improvements, continued investment in research and development capability is required—to do otherwise is to risk obsolescence and lack of competiveness in the world market. Dr. Peter Hayes at The University of Queensland is one of the many researchers and process engineers who have contributed to the fundamental understanding of metallurgical processes over this period of rapid change in technologies. The present paper briefly outlines some of the many contributions Peter Hayes has made to the understanding of kinetics, mechanisms and phase equilibria in metallurgical systems, and metallurgical process development.

By C. Coetzee

Additives are commonly used in copper electrowinning to improve cathode morphology. Polysaccharides such as guar are generally favoured as additives due to their compatibility with solvent extraction. Polyacrylamides are, however, being considered as possible alternatives. Understanding the influence of the structural chemistry of additives on electrowinning performance is critical to utilise them efficiently. This paper investigated polyacrylamide additives which are structurally different; their effects on copper electrodeposition were characterized and compared to that of guar. Electrochemical impedance spectroscopy (EIS) were used to characterize the effects of molecular weight and ionic charge of the polyacrylamides on electrodeposition. The findings were compared against results obtained with an industrially used guar product. Equivalent circuit modelling of EIS data indicated that an increase in polyacrylamide concentration and a decrease in additive molecular weight increased the overall system resistance.

By Brajendra Mishra

Molten Salt electrolytic processes offer unique opportunities to extract and refine metals where gaseous or metallothemlic reduction, hydrometallurgical extraction and aqueous electrolytic methods are thermodynamically constrained. Production of aluminum and magnesium by molten salt electrolysis are well known commercial processes. Several other reactive metals, such as lanthanides and actinides, as well as beryllium and calcium, make use of molten salt processing for extraction and refining. This presentation describes the science of molten salt chemistry and electrochemistry for winning and refining of several metals. In addition, recovery of metals from waste process salts by molten salt reduction as well as oxidation have been discussed. Material issues in design of molten salt reactors have been included. Various applications have been presented through case studies. Experimental data have been included to justify the suitability as well as limitations of these specific processes.

Jan 1, 2003

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).

By Mingming Zhang, Marshall S. Coe, Marcelo W. Andrade

To supply iron units and flux burden in blast furnaces, sinter basicity is one of the vital parameters for sinter plants. The sinter basicity also plays an important role in sinter quality since it imparts the formation of different mineral phases in sinter. Pot-grate sintering tests were carried out with low and high basicity to investigate the effects of sinter basicity on sinter mineralogy, properties and productivity. It was found that with an increase in sinter basicity, both sinter productivity and reducibility (RI) increased. Tumbler index (TI) and low temperature degradation index (LTD) of high basicity sinter were comparable to low basicity sinter. Softening and melting tests showed that sinter with 3.5 C/S basicity had slightly higher softening temperature comparing to lower basicity sinter with C/S 2.6, acid and fluxed pellets. XRD analyses confirmed the formation of silico-ferrite of calcium and alumina (SFCA) and calcium ferrite (CF) in the tested sinter samples.

Jan 1, 2015

By Hiroyuki T. Takeshita

Ca-Ni based alloys were investigated on structures, hydrogenation properties and the effect of additive elements on hydrogenation properties. CaNi, samples were decomposed to form a new hydride with a CsCl-type structure on the constituent metal atoms at high temperatures such as 673K in a hydrogen atmosphere. The candidate of the third element which was added to stabilize the original compound was investigated by using the Miedema's semi- empirical model and, as a result, Pd was chosen. The hydrogenation of CaPd was conducted with a Sieverts' type apparatus and the synthesis of Ca-Ni-Pd ternary alloys was performed by high frequency heating.

Jan 1, 2002

By Marion Dattilo

The search for an improved anode for the electrowinning of lead from fluosi1icic acid medium has led the U.S. Bureau of Mines to investigate composites. Polymer bonded metal oxide powders which may contain catalyst additions were prepared by pressing. These composites display an improved activity toward the oxygen evolution reaction over electrodeposited lead dioxide on titanium, carbon, and nickel substrates. These composite electrodes contain 5 to 10 wt. " binding polymer, with the balance being metal oxides. Lowered anodic potentials achieved using the compnsite anodes resulted in lower levels of lead dioxide deposition during electrowinning.

Jan 1, 1995

By T. V. Swaminathan

Monazite sand is normally processed by, the caustic soda route to produce mixed rare earths chloride, thorium hydroxide and trisodium phosphate. Bulk of the mixed rare earths chloride is used for the preparation of FC catalysts. Recently some of the catalyst producers have shown preference to cerium depleted (lanthanum enriched) rare earths chloride rather than the natural rare earths chloride obtained from monazite. Therefore, a process for producing cerium depleted rare earths chloride, cerium p thorium and uranium from Rare earths + thorium hydroxide obtained by treating monazite based on stepwise hydrochloric acid extraction, was developed in our laboratory. The process involves drying of the mixed rare earths-thorium hydroxide cake obtained by monazite-caustic soda process followed by stepwise extraction of the dried cake with hydrochloric acid under specified conditions.

Jan 1, 1989

By Wang Zhi

High-Mg-content concentrates are usually treated in Jinchuan flash smelting Furnace. Because the viscosities of high-Mg-content slag is very high, the operation of flash smelting becomes very difficult. To solve this problem, the viscosities of the semi-synthesized FeO-MgO-Si02 slag of different compositions were measured. The results showed that when in the slag the weight percentage of MgO [m(Mgo)] is 6-10%, the ratio of the weight percentage of iron to that of Si02, m(Fe)/m(SiO2) is 1.1-1.4 and the temperatures are within 1473?1773K, the slag viscosities increased with the increase of m(Mgo) and m(Fe)/m(sio,). When m(Mgo)<6%, the smelting temperature should be controlled at I 300°C in order to to keep the smooth operation. When m(Mgo» 10%, the temperature should be kept above 1633K. When the content of MgO is higher, a lower viscosity slag ean be produced by decreasing the ratio of m(Fe)/m(sio,). The appropriate ratio of m(Fe)/m(sio,) for Jinchuan flash smelting furnace is about 1.2.

Jan 1, 2003

By John W. Cash

The mineralogy and textures of cyclone dust, sludge, and occasional build-ups in the American Iron and Steel Institute (AISI) direct ironmaking pilot plant at Universal, Pennsylvania have been studied by reflected light, transmitted light, and cathodoluminescence microscopy, and phase compositions have been determined by SEM-EDS. The cyclone dust consists of particles of carbon, metallic iron, sulfur-bearing iron, and wustite. Measurements of particles in the sludge indicates that 69% are less than 2.5 um across, 21 % are 2.5-5 um, and 10% are larger than 5 um. Mineralogically the sludge particles are mainly carbon and metallic iron, with minor wustite and sulfur-bearing iron. Build-ups that sporadically develop in the furnace consist of olivine, hercynite spinel, metallic iron, wustite, pyrrhotite, pseudobrookite, akermanite-ferroakermanite and gehlenite. The microtextures shown by the build-ups indicate that much of that material has precipitated at the build-up loci. This study has been supported by AISI and the U.S. Department of Energy.

Jan 1, 1995

By Jean-François Boulanger

The production of rare earth elements from ore usually consists of three steps; the separation of a concentrate of REE bearing minerals; the cracking of the REE minerals to liberate the REE into an aqueous solution and separation of REE into individual elements. This paper describes the results of laboratory tests conducted on a carbonate-rich REE ore containing bastnaesite and monazite. The tests cover the whole processing sequence of beneficiation, preparation of the REE solution using a caustic leach followed by acid leach to break monazite and bastnaesite and liberate REE into an aqueous solution and the partial separation of the REE using solvent extraction. Details on the product quality and process performances (recovery and impurities removal) are given for each studied step. The paper also discusses the economic advantage of separating the REE rather than producing a mixed REO product to be sold to a refinery for REE separation. A mini-pilot plant version of the process is currently planned.

By SM Rao

Nuclear Fuel Complex (NFC ) , Hyderabad (IN DIA ) , is engaged in the manufacture of nuclear fuel assemblies and zircaloy structural components required for the Indian nuclear power reactors. The production of zirconium oxide, sponge and zircaloy materials through chemical and hydro - metallurgical processes generates many effluents containing valuable zirconium and hafnium . This paper deals with the various processes such as multiple crystalization, phosphate precipitation, ion-exchanges amine solvent extraction etc, for the treatment of these effluents and subsequent recovery of valuable zirconium and hafnium .

Jan 1, 1992

By Ljiljana Solujic

The need for the removal of mercury from the precious metals extraction circuits may be influenced by process, environmental, as well as by occupational hazard reasons. In these circuits mercury is mainly present as cyanide complexes. The effectiveness of any stabilization method will be influenced by the high thermodynamic stability mercury-cyano species exhibit in an aqueous solution. In this study, we have investigated the utility of the trisodium salt of trimmercapto-s-triazine (TMT) for precipitation of mercury from the corresponding cyano-complexes. The influence of pH molar ratio of TMT to Hg, coagulant and flocculant additions, excess of free cyanide, as well as the presence of other metal-cyano species on the effectiveness of mercury precipitation were investigated in detail. Also, a "teal world" precious metals mill effluent initially containing ~7 ug/mL (ppm) of Hg was treated and A was found that greater than 99.8% of the mercury was removed from the solution as am insoluble Hg/TMT complex.

Jan 1, 1996

By J. Rastas

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

Jan 1, 1990

By David R. Jessey

An ore microscopic and geochemical study of the nickel-cobalt occurrence in the Southeast Missouri Mining District has revealed several significant relationships. Siegenite [(Ni,Co)3S4] is the dominant nickel-cobalt sulfide in the ores, however, several other members of the thiospi¬nel group (AB2S4) occur: carrollite (CuCo2S4), nickelean carrollite [(Co,Ni,Cu)3S4], fletcherite [Cu(Ni,Co)2S4] and polydymite (Ni 3S4). In addition, bravoite [(Ni,Fe)S2], vaesite (NiS2), millerite (NiS) and gersdorffite (NiAsS) are present. Thiospinel composition varies dramatically within the district. Paragenetic studies have shown that the stratigraphically lowest thiospinels are the most cobalt-copper-rich. A detailed ore microscopic study of the AMAX Lead Company Buick mine has also shown significant changes in mineralogical association, texture and grain size of the siegenite along the north-south strike of the major ore bodies. Siegenite commonly replaces and veins chalcopyrite and is subsequently replaced by sphalerite. Less commonly, siegenite and chalcopyrite are observed to form linear replacements along sphalerite grain boundaries. The grain size of the siegenite varies markedly, but in a predictable north-south pattern that is consistent with a genetic model formulated from geo-chemical data. The compositional as well as textural trends displayed by the thiospinel mineralization could be exploited to optimize recovery of any or all thiospinels of economic interest.

Jan 1, 1981

By F. Kongoli

Viscosity is an important parameter of copper smelting and converting processes. It affects the settling of matte or metal droplets in the slag, distribution of elements etc, Despite this importance, confusion exists on the viscosity of copper smelting slags as a result of disagreements found among the measured viscosity data of several authors especially in the slags of high ferric iron content and close to magnetite precipitation. In this work a critical review of the existing data on the viscosity of copper smelting slags has been first carried out and the effect of oxygen potential on the viscosity of copper smelting slags has been clarified through a coupled quantification of viscosity and liquidus temperature. The confusion in the literature has been clarified and the importance of the relation between the viscosity and the liquidus temperature is discussed,

Jan 1, 2003

By G. L. Liu

"Deformation Banding ( DB ) in cold rolled mild steel has been experimentally established by microstructure investigation. Deformation banding model includes such deformation mode when it is applied to rolling texture simulation. The cause for the occurrence of deformation banding is the reduction of the total work for plastic deformation through a relaxation of the deformation constraints. In the first DB model, all grains are assumed to band from the first deformation step. Such an unrealistic assumption has been eliminated in the new model by the introduction of a banding criterion based on an energy minimizing approach. The prediction is closer to the measured texture by applying banding criterion and setting critical resolved shear stresses (CRSS) ratio for { 110 } and { 112 } slip modes to 0.85.IntroductionBased on the continuum theory of plastic flow and deformation mechanism of crystallographic dislocation slip, Taylor's FC ( Full Constrain ) theory [1] has been widely used in texture modeling. As the process of cold rolling of sheet materials produces a microstructure consisting of elongated or equiaxed flat grain or cell, the ""lath"" and ""pancake"" relaxed constraints ( RC ) models [2, 3] were introduced as the successful improvements over the classical FC model. It has been also recognized that crystals may split into different orientations during deformation and the term deformation banding is used to describe such deformation processes [4, 5]. Lee et al. [6, 7] pointed out that the success of the RC theory in predicting textures depends on the physical processes of deformation banding. They developed so called Deformation Banding ( DB ) model by considering DB in the longitudinal plane to be accounted for by the RC method and allowing DB in the rolling plane. DB model was applied to simulate the texture development in bee case [8], the predicted bee rolling textures are in reasonable agreement with the measured textures. In the first DB model, however, all grains are assumed to band right upon the first deformation step. A banding criterion was formulated [7] which states that DB will occur if the work used in DB model is less than that in RC model. Such criterion has been incorporated into the original DB model for texture simulation and is referred to as DBC ( Deformation Banding Criterion ) model."

Jan 1, 1998