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By D. Georgiou

Direct sulphuric acid leaching of nickeliferous limonites is the process of choice to recover nickel and cobalt from equatorially located lateritic ores. These ores are rich-in-iron (-45 wt%) existing in the form of goethite enriched with nickel. The merit of this process is due to its high nickel selectivity because of simultaneous iron separation and acid regeneration. Under acid leaching conditions (-250 to 270°C) iron follows an acid dissolution-hydrolytic precipitation path yielding a very low concentration level depending on temperature and acidity of the final leach liquor. The primary precipitation product of iron is hematite which also forms as a scale on reactor internals along with co-existing aluminum. In this paper, an overview of the behaviour of iron solid products under process conditions is made. The evolution of goethite to hematite transformation, as well as the role of iron in reactor scale production, are studied using SEM/EDX characterization techniques.

Jan 1, 1995

By A. P. Paiva

Although the advantages of Solvent Extraction for separation/purification of relatively concentrated solutions are well known in Extractive Metallurgy, its use for the recovery of elements present in low levels only recently has been discussed, with particular attention devoted to precious metals. In this work, the extraction behaviour of Cyanex 471X towards silver, from an acidic chloride medium is reported, the extraction and stripping isotherms and related kinetic features analysed. Results on the selectivity of silver extraction against high contents of iron, copper and lead are discussed. Phosphine sulphide extractants are generally associated with solvation mechanisms: analysis of the extraction pathways along with the possibility of reaching a suitable loading in the organic phase are also presented.

Jan 1, 1993

By G. R. Adams, N. Y. Tang, N. Qiang

"Aluminum is the most important alloy addition to Zn baths for controlling the reaction kinetics between the steel substrate and molten Zn in continuous galvanizing operations. Due to the complexity of the Zn-Fe-Al ternary system, the measurement and control of effective bath Al remains a challenge for modem galvanizers. The successful development of Al sensors has made the real-time measurements of bath Al contents possible. To facilitate their application, a computer interface and a palm-size data logger have been developed by Cominco. Plant applications indicated that the sensor possessed sufficient accuracy for process monitoring and control. The working mechanism of the Al sensors and Cominco's development work is described, and the results of sensor applications are presented.IntroductionControl of bath Al content is critical in modem continuous galvanizing because it has a strong influence on coating structure and properties and the overall product quality. The control of effective bath Al content (Al in liquid solution) is particularly critical for galvannealing where a high bath Al content may lead to incomplete alloying during post annealing, and a low bath Al content may result in other operation problems, such as excessive bottom dross accumulation and difficulties in coating thickness control. The desirable accuracy of the Al control is within ±50 ppm of target levels. In principle, such an accuracy is achievable for modem chemical analysis facilities, such as atomic absorption photospectrometer (AAS) and induction-coupled plasma (ICP). However, a recent study carried out by the International Lead and Zinc Research Organization (ILZRO) indicated that such an accuracy is rarely achieved in the zinc and steel industries.(1)"

Jan 1, 1997

By T. T. Chen

The manganese oxide scales, consisting mainly of MnO2, characteristically occur in banded colloform structures which adhere to porous layers of PbSO4 and PbO2 that oxidized from the rolled Pb-0.7% Ag anodes. Hydrous Mn oxides, Mn3O4 and amorphous Mn oxides are believed to be also present. Tiny particles of gypsum, PbSO4, SrSO4 and AgCl are entrapped in the colloform masses. The gypsum originated from the Zn electrolyte; strontium carbonate was added to the ZnSO4 solution to control Pb, and silver originated from the anodes. Some of the colloform bands contain minor amounts of Pb, implying a limited degree of dissolution of the Pb during electrolysis. Other colloform bands incorporate trace amounts of Zn. Colloform structures permeated with silica gel are presumably caused by the high silica content of the electrolyte.

Jan 1, 2009

By Jan G. H. du Preez, C. Viviers, B. J. A. M. van Brecht, H. E. Rohwer, Nicole M. Sumter

"At the basis of metal ion separation lies some particularly metal ion specific chemical property which lends itself towards exploitation. This could be in the form of an anionic complex or a neutral chelate complex. In the former a cationic centre with a particularly high affinity for the complex will have to be designed. In the latter case a stereospecific chelate ligand containing the correct symmetry and type of donor atoms will have to be designed. In both above cases the ""active centre"" can be entered in a from that it can function in different media of hydrophobicity, eg a precipitant, a resin or a solvent extractant. Recent results obtained in this laboratory will be used to illustrate how the above variables can be exploited to develop improved processes for the separation of base metal and platinum group metals.IntroductionThe separation of metal ions in hydrometallurgy can be performed broadly speaking with two major aims. Firstly the separation/removal of a certain group of metal ions, either as a means of preconcentration or as a removal from effluent as part of a purification process and, secondly the removal of a specific metal ion from an industrial stream in order to produce a specific metal in a pure form. This latter operation is by far the most difficult of the two and is becoming more so in the light of the fact that the world is moving in the direction of lower grade ores and increasing pollution. Such a process can be divided into three essential parts, firstly the molecular one in which an active centre is required to obtain specificity, secondly a matrix within which this active centre must function, i.e. as part of a resin or solvent extractant and thirdly the design of the total system to optimize the realization of the operation."

Jan 1, 1996

By C. Dresen

This paper discussed the reaction kinetics of the reduction of industrial phosphate pellets for P4 production. In the reduction process of various phosphate ores, the following parameters were investigated: Diffusion of the phosphorus oxide and other gaseous products from the reaction mixture after having been reduced on the reductant (coke) surface. Influence of silica on reaction kinetics. Temperature influence. Influence of mineralogy and morphology (different ores). Particle size influence of silica and coke. Experiments were carried out in a vertical tube furnace with 2 ores, 2 types of silica and one type of coke. Selected experimental conditions simulated furnace conditions. The following conclusions could be made: Reaction rate increases with the addition of SiO2 into the pellet. The reaction rate increases above 1350°C (melting temperature of the slag). Mixing different ore types in the pellets leads to differences in reduction kinetics. Particle size of the coke particles influence reduction kinetics. The amount of slag formation is influenced by silica addition, coke size and temperature.

Jan 1, 2002

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 G. A. Brooks

Reactive ball milling has been proposed as a new route for producing carbides from oxides through carbothcrmic reduction. It is claimed that through milling oxide and graphite powders to the nanoscale, amorphous materials with very high reactivity are formed, that allows for easy transformation of the starting material to another in a subsequent thermal process. Thermodynamic analysis of this proposed process suggests that unless particle sizes are reduced to below 10nm, then reduction in size alone cannot explain a change in the stability of oxides. Even with nanometer scale powders, the products formed need to have a lower total surface energy than the reactants before a chemical change will occur. A model developed by Bhattacharya and Arzt for predicting localized temperature changes based on milling conditions suggest that temperarure rises less than 400 K will be achieved in laboratory conditions. The present calculations suggest that nanometer scale powders formed through high speed ball milling (>10 mls) may have undergone a process analogous to melting and quenching. Further work is required to fully distinguish these features.

Jan 1, 2003

By M. Misra

The finely dispersed kerogen particulates present in the dilute suspension can be coagulated with the aid of a hydrophobic organism, Mycobacterium Dhlei. The initial coagulation and aggregation are strongly dependent on pH and organism concentration, the isoelectric points of oil shale kerogen and Mycobacterium phlei are at pH 3 and 1.8 respectively. As a result the aggregation is rapid around pH 3. Preliminary results show that it is quite possible to use microorganisms for enhanced dewatering of kerogen concentrate produced by froth. flotation.

Jan 1, 1991

By C. Lupi

Zinc impure solutions as spent electrolytes, leach liquors coming from aqueous treatment of both minerals and solid waste, need to be purified before undergoing the treatment to obtain the final product. Solvent extraction is one of the most selective operations particularly when many metallic ions are present in solution. Zinc pure solutions are frequently obtained using DZEHPA as extractant. In this work an investigation on zinc extraction effectiveness of naftenic acid was carried out. After determining the best diluent and the optimal extractant concentration, the partition coefficient was determined as a function of temperature, equilibrium pH and zinc concentration. Finally same batch tests to determine the equilibrium curves at room temperature on exhausted electrolyte coming from zinc cell were carried out by using naftenic acid, D2EHPA and TBP. The pH giving, for each extractant, the best extraction yield was selected in order to compare the equilibrium curves. Experimental results show that all the examined extractants are very effective in zinc extraction if the process conditions are appropriately selected. In order to avoid an impure solution pre- treatment and to obtain the maximum ertraction yield the appropriate solvent can be chosen.

Jan 1, 1998

By D. S. Barr

The Freeport McMoRan chlorination circuit is comprised of four related processes: ore chlorination, gas scrubbing, chlorine supply and excess hypochlorite removal ("hypo kill"). Each of these processes are described, and related to the pertinent mineralogic components in the carbonaceous ore feed to the plant. The chlorination system in use at Jerritt Canyon to passivate forms of preg-robbing organic carbon has proven to be a cost effective and efficient means to recover gold from low sulfide carbonaceous refractory ores, where gold may not be specifically associated with either the sulfides or the carbon.

Jan 1, 1987

By Lan Li, Izaak Williamson

"The efficient separation and storage of CO2 from power plant flue gases can reduce the amount of CO2 released into the atmosphere and mitigate global warming. Potential candidates for industrial applications are solid sorbent materials. Crucial factors to control the efficiency of porous sorbent materials include the framework and pore structure, and the chemical and physical reactivity of CO2 within the pores. Computational modeling approaches, based on density functional theory (DFT) and van der Waals-DFT, have been applied to nanoporous solid – manganese dioxide a-MnO2. We found that the types and charges of cations as dopants in the a-MnO2 and the concentration of CO2 influence the structural features of a-MnO2, which control its CO2 selectivity performance within the flue gases.IntroductionCarbon capture and storage is a technique to separate large quantities of CO2 from power plant flue gases before being released into the atmosphere. Porous solids are a potential candidate as sorbents to “trap” CO2 through chemical or physical adsorption on their porous surfaces[1]. Such separation efficiency is determined by the size and shape of its pores and by the interaction between the porous surface and the gas adsorbates. The incorporation of cations into the pore can act as a means of structural support and alter the pore diameter to be comparable to the kinetic diameter of the gas adsorbate, such as CO2.A porous solid of particular interest for CCS is manganese dioxide a-MnO2, an octahedral molecular sieve (OMS) composed of edge-sharing MnO6 octahedra that are linked into a nanoporous framework[2]. The framework consists of (1×1) and (2×2) tunnels, referred to as OMS-2. Due to the larger tunnel size, cations and gas adsorbates prefer to reside along the (2×2) tunnel axis of the OMS-2. As seen in Figure 1, a potassium cation K+ is located in the (2×2) tunnel, known as cryptomelane-type MnO2. Its pore diameter of ~ 4.6 Å gives it a good CO2 selectivity performance, because the diameter is comparable to the kinetic diameter of 3.3 Å for CO2[3]. Alternatively, replacing potassium K+ with other cations, e.g. barium Ba2+, sodium Na+ or lithium Li+, in the OMS-2 tunnel is of great research interest, due to the effects of their concentrations, types and charges on the CO2 selectivity efficiency and sorption hysteresis phenomenon[2,4]."

Jan 1, 2014

By Gustavo Díaz, Miguel A. García, Carlos Frías

"Under the auspices of the Commission of the European Union, a consortium composed of six European organi~ations has conducted a project to scale up the PLACID electrowinning cell to industrial size within the Placid process development. This paper is concerning the results and achievement of the industrial cell prototype after more than 1,000 hours operating time and about 10,000 Kg electrolytic lead production. In general, results have been very satisfactory, demonstrating the ability ofthe PLACID electrowinning cell to produce top quality electrolytic lead (> 99.99 %) with high current efficiency and low energy consumption.IntroductionThis paper is concerning the development of an industrial size PLACID electrowinning cell within the PLACID process development. This project began on January 1993 and was finished on April 1996.Lead metal production and manufacturing industries produce large amounts of dusts and also lead bearing slags. Spent lead-acid battery recycling also produces lead oxides from the battery pastes rather similar to those mentioned above. Those lead secondary materials are hazardous and difficult to handle by usual procedures.Existing processes to treat-lead oxides may inflict considerable damage on the environment, incur high operating costs and have limitations to produce top quality lead.The main aim of this project has been to develop a novel hydrometallurgical process able to deal with different lead bearing materials, mainly lead oxide secondaries: lead-acid battery pastes, lead fumes, furnace slags, oxide residues, etc., producing ""four nines"" pure lead in an efficient manner with a benign influence on the environment; it is called the PLACID process."

Jan 1, 1997

By Gabriel A. Torma

This paper provides infonnation on selected technologies available for remediation of metal contaminated soils and industrial effluent solutions. Because some of the industrial sites are contaminated with organics (solvents, gasolines and oils), an effort has been made to introduce the most frequently used cost-effective cleanup methods, such as "bioventing" and "composting." The microorganisms involved in these processes are capable of degrading organic soil contaminants to environmentally harmless compounds: water and carbon dioxide. Heavy metals and radionuclides contaminated mining and industrial sites can be remediated by using adapted heap and dump leaching technologies, which can be chemical in nature or bio-assisted. The importance of volume reduction by physical separation is discussed. A special attention is devoted to the remediation of soils by leaching (soil washing) to remove heavy metal contaminants, such as chromium, lead, nickel and cadmium. Furthermore, the applicability of biosorption technology in the remediation of heavy metals and radionuclides contaminated industrial waste waters and acidic mining effluent solutions was indicated.

Jan 1, 1996

By Jerome P. Downey

Technologies developed within the field of extractive metallurgy to recover, concentrate, and purify metals and industrial minerals from ores, have served as the foundation for all of the subsequent environmental remediation, materials recycling, and waste management technologies. This paper discusses the application of classical extractive engineering principles to the development of a thermal process for the recovery of mercury from solid wastes. Process development is presented as a series of logical stages, which begin with a thorough characterization of the site-specific waste, move on to bench and pilot scale testing of the process options, and end with a functional process flowsheet. This paper also presents thermodynamic data on many mercury species of interest to the minerals, power, and chemical industries. These data can be used to model the speciation and recovery of the mercury as a function of various process parameters.

Jan 1, 2003

By D. W. Collins

The uptake of gold from halide solutions by activated carbon has been investigated using various techniques. Halide systems typically exhibit combined adsorption-reduction type behavior. In an attempt to gain more information about the nature of these processes, samples of synthetic highly-oriented pyrolytic graphite (HOPG) were contacted with aqueous solutions of gold-iodide. HOPG represents a model structure for activated carbon comprising of basal- plane sites, edge sites, and various defect sites. Two basic instrumental methods were used to examine the uptake of gold by HOPG. The first was standard X-ray photoelectron spectroscopy (XPS). The other involved several scanning probe techniques. XPS clearly indicated a preferred uptake of gold at edge sites. However, iodine appeared to be distributed on both basal-plane and edge sites. At low iodine additions, tapping mode AFM showed that clusters were concentrated along steps and surface defects. At high iodine concentrations, the HOPG surface was uniformly covered by iodine.

Jan 1, 1998

By Ibrahim Yusufoglu, Cem Kahruman, Mert Zoraga

In this study, a strontium sulfate mineral (celestite) was converted to strontium oxalate in solutions containing ammonium oxalate as a reactant. The experiments were carried out under isothermal conditions. The effects of stirring speed, ammonium oxalate concentration, particle size and temperature on the conversion rate were investigated. During the conversion process, definite volumes of solutions were taken from the reactor after different reaction times for the determination of sulfate ions using ICPOES. Fractional conversions of strontium sulfate were determined at different times and fractional conversion vs time diagrams were generated. It was found that the conversion of strontium sulfate was increased by increasing the ammonium oxalate concentration and temperature in addition to decreasing the particle size. The effect of stirring speed was negligible on the reaction rate. It was observed that above 328 K, a protective layer of strontium oxalate was formed on the strontium sulfate particles. X-ray Powder Diffraction technique was used for characterization of solid substances.

Jan 1, 2014

By Hongmin Zhu, Qiuyu Wang, Shuqiang Jiao, Guojing Hu

"The equilibrium between titanium ions and metal titanium was investigated in fluoride-chloride molten salt. The electrochemical properties of titanium ions in fluoride-chloride were studied on a molybdenum electrode by cyclic voltammetry (CV) and square wave voltammetry (SWV). The equilibrium constant of the equilibrium between titanium ions and metal Ti was calculated in KCI-NaCl- 2.5wt %K2 Tif 6 at the temperature of 1073K.IntroductionTitanium, the ninth most abundant element in the earth's crust, is endowed with high strength, low density, excellent flexibility, strong spring back characteristics, high-temperature performance, corrosion resistance and biocompatibility. These characteristics make titanium eminently suitable to be used in aerospace, marine industries, and harsh chemical environments. Although it has many excellent properties, the application of titanium in industry was limited by its high-cost. Therefore, many methods have been investigated for producing high-purity titanium at low cost. Electrolysis, involving the extraction and preparation of pure metal from ore using an electrolytic process, is considered a promising method for titanium metallurgy. Many studies have focused on the electrochemical behaviour and electrodeposition of titanium in molten chloride, fluoride, and chloride-fluoride electrolytes (1-IOJ. The electroreduction mechanism of Ti3+ ions in molten alkali chlorides has previously been studied by several workers. Two reduction steps, Ti3+ -Ti2+ -Ti, have been observed in various molten alkali chlorides [IJ. One reduction step, Ti3+ -Ti, has been observed in alkali fluoride molten salts l21. The behaviour of Ti4+ in fluoride or chloride-fluoride molten salts has also been investigated in the literature; it was proposed that the reduction of Ti4+ ions in the molten salts proceeded in a two step process: Ti4+-Ti3+-Ti l3l or a three step process: Ti4+ -Ti3+ -Ti2+-Ti ri. 4l Indeed, the stability of the titanium oxidation states depends on the bath composition l5l. The valence state was Ti2+ in alkali chloride melts, which was a lower oxidation state and correspondingly, in alkali fluoride melts, the higher oxidation states ofTi4+ and Til+ were more stable.The aim of the present work is to explore the effect of F/Cl atomic ratio on the equilibrium between titanium ions and metal titanium in fluoride-chloride at the temperature of 1073K. The electrochemical properties of titanium ions in fluoride-chloride were studied on a molybdenum electrode by cyclic voltammetry (CV) and square wave voltammetry (SWV). The solubility product of the equilibrium between titanium ions and metal Ti was calculated."

Jan 1, 2012

By Hong N. Vu, Jitka Jandova

"Gypsum and limestone methods were examined in this study to process zinnwaldite wastes originating from dressing Sn-W ores mined in the Czech Republic. These wastes containing 0.20-0.30% Li and 0.10-0.20% Rb were subjected to magnetic separation to obtain a zinnwaldite concentrate with 1.36% Li and 0.94% Rb. It was observed that processing of the zinnwaldite concentrate with gypsum resulted in almost 96% recovery of Li into aqueous liquors, whilst rubidium extraction was only 25%. At the same time, it is possible to extract almost 92% Li and Rb from the identical zinnwaldite concentrate if the concentrate is processed by limestone method. Lithium carbonate, a final product of both methods was recovered from the refined sulphate solution using K2CO3 as a precipitation agent and/or from unrefined hydroxide solution using gaseous CO2. In the continuation of this study, rubidium will be separated from carbonate solutions after Li2CO3 precipitation as RbAl(SO4)2, an intermediate for Rb2CO3 production. IntroductionLithium is used as an alloying constituent in lightweight alloys, as a heat transfer medium in nuclear reactors and as a component in primary and secondary batteries. With the development of a new generation of electric vehicles, the lithium demand will dramatically grow. Lithium chemicals find extensive application in many industrial branches such as metallurgical, glass, ceramic and pharmaceutical industries. Rubidium compounds are predominantly used in psychiatry and medicine, in magneto-optic modulators, solid-state lasers, phosphors and components of electrolytes for fuel cells. The four most important lithium minerals are amblygonite, spodumene, petalite, and lepidolite. Spodumene LiAlSi2O6 (6.0-7.5% Li2O) and petalite LiAlSi4O10 (3.5-4.5% Li2O) belong to aluminosilcate minerals. Lepidolite (Li.Al)3(Al.Si)4O10(F.OH)2 (3.30-7.74% Li2O), lithium mica, is the most important representative of the mica minerals, a subgroup of the aluminosilicates. It frequently contains 3–5% Rb2O and eventually caesium. Zinnwaldite, which has the general formula K(Li.Al.Fe)3(Al.Si)4O10(F.OH)2 (2-5% Li2O), is regarded as a variety of lepidolite with a high iron content. Commercial amblygonite is a complex phosphate (Li.Na)Al(F.OH)PO4 (up to 9.88% Li2O), however, its deposits have not been commercially exploited because of their small size. Natural brines with a high lithium chloride content are important in the industrial production of lithium [l]"

Jan 1, 2008

By Chu Yong Cheng

The solvent extraction (SX) processes of the three pressure acid leach (PAL) nickel plants in Western Australia have been reviewed. The use of intermediate precipitation, solids/liquid separation and re-leach in the three W A nickel plants make these processes complicated and costly in capital and ?operation. The research work carried out by the SX group at the AJ Parker Cooperative Research Centre for Hydrometallurgy I CSIRO Minerals has led to the development of direct solvent extraction (DSX) processes to recover and purify nickel and cobalt from leach solutions. The simplicity of the process flowsheets and the expected savings in capital and operating costs are the major advantages of the new DSX processes over the reviewed processes. By using a new synergistic organic system in semi-continuous tests with a pilot plant leach solution (after iron precipitation) from BHP-BiIliton Stainless Steel Materials, the metal values (Ni and Co) together with zinc and copper were separated from the major impurities (Mn, Mg and Ca, together with Cl) in the first SX circuit. The co-extracted manganese, magnesium and' calcium were easily scrubbed out. After stripping, the metal values (Ni and Co) together with zinc and copper were concentrated, resulting in a much smaller second SX circuit and equipment in the down stream processes. The extraction and stripping kinetics of the metals with the new synergistic organic solution were very fast. The extraction and stripping almost reached steady state within 0.5 minutes. Semi-continuous test work with a synthetic leach solution, 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 Stainless Steel Materials showed that manganese, calcium, copper and zinc can be effectively and efficiently separated from nickel, cobalt and magnesium by extraction, scrubbing and stripping. This led to the development of another DSX process using D2EHPA to recover nickel and cobalt from leach solutions.

Jan 1, 2003