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By Guy Deschênes

Thiourea solutions can be used as leach liquors to treat gold ores or slimes. It is also efficient to elute resins or strip solvents that were loaded in cyanides solutions. The hydrogen pressure reduction is a practical step to recover gold and silver from leach solutions, and strips and eluates without any destruction of thiourea. It is a critical point because these processes have to consider the recycling of the liquors to be irore economical. The effect of temperature, pressure, acidity, compotation of the solution and the nature of catalysts on pressure reduction by hydrogen were investigated. An electranetallurgical study was? carried out to investigate the mechanism. The composition of the products was studied by different analytical methods. The process shows a good selectivity to precipitate gold and silver in a thiourea solution containing iron and copper. Gold and silver concentrations can be decreased to 0.2 ppm and 0.1 ppm at respectively 70 KPa H2 and 28°C. No decomposition of thiourea was evident during the tests. Metals such as nickel powder or platinum activate the reaction and improve the reduction.

Jan 1, 1989

By Chunlin Chen

Nickel-sulfide minerals are normally associated with copper and iron sulfides and often contain a minor amount of valuable metals such as cobalt and detrimental impurities such as arsenic. Metal losses in slag vary from process to process during the pyrometallurgical production of nickel and, depend on the feed composition, slag chemistry and operating conditions. Maximiz the metal recovery is one of major considerations to optimize operating condition for nickel smelting/ converting processes. At the same time, the deportment of minor elements between various phases during nickel smelting is of great importance by smelter operators. The Multi-Phase Equilibrium (MPE) is a thermodynamic package developed by CSIRO for simulating reactions between phases in multi-component and multi-phase systems [1]. Over the years the capability of the MPE model has been extended to cover the behavior of a large number of elements in high temperature systems. The sulfide smelting module of the MPE, which covers the minor elements such as As, Bi, Sb, Pb, Se, Te, Sn, Co and Zn, is capable of modeling the deportment of major and minor elements between various phases during nickel smelting. In this article the application of the MPE model in modelling the nickel smelting process is presented. The modelling results on the majors and minors are compared with the plant data. The deportment behaviour of arsenic in nickel smelting was analysed and the impact of slag chemistry on slag properties was modelled. These results can assist process metallurgists in exploring the optimum fluxing strategy for smooth operation and the potential practices for improving arsenic removal.

By Corby G. Anderson

Hydrometallurgical technology for the pretreatment of refractory gold concentrates has been developed at Sunshine Mining and Refining Company. It employs a patented nitrous-sulfuric acid pressure leaching process which' was proven industrially at the Sunshine refinery. Additionally, pretreatment for removal of antimony and some other impurities is done with alkaline sulfide leaching. This paper will discuss the successful application of these two technologies for pretreatment of a refractory gold concentrate prior to CIL gold recovery. A complex gold concentrate composed of pyrite, arsenopyrite and stibnite was tested. Results of antimony leaching in alkaline sulfide media will be discussed including some details of a novel and selective recovery method for gold leached by polysulfide or thiosulfate" Also, the factors important in and the results of the application of nitrogen species catalyzed pressure leaching to refractory gold concentrates will be detailed.

Jan 1, 1996

The cleaning of copper containing fayalite slag using a CuFe alloy was studied under an oxygen pressure ranging from 10-7 to 5 X 10-11 atm at 1200º c. The reduction of copper from fayalite slags by Cu-Fe alloys was found to be very effective. For example, at a P 02 of 10-7 atm, the copper content in the slag was reduced from 4.1 to 0.402 wt. percent after 90 min. of reaction time using a Cu- 5.27 wt. percent Fe alloy. The copper reduction rates were found to be independent of P02 in the gas phase when using Cu-Fe alloys which exhibit an iron activity of greater than 0.4. A mechanism for slag c1eaning is proposed based on the concept that the Cu-Fe alloy lowers the oxygen potential of the slag according to Eq.1 1, fol1owed by the reduction of cuprous oxide by wustite as shown in Eq.2. Here X represents element X in the alloy phase while (X) represents the element in the slag phase. The copper and iron transfer behaviour obtained in this study are explained by a ?Stepwise equilibrium model.

Jan 1, 1985

By C. Kathryn Sole

The close proximity of cobalt and nickel on the Periodic Table and their frequent occurrence together in nature means that their separation in primary hydrometallurgical flowsheets is not only often necessary, but requires the use of innovative chemistry to achieve high selectivity. Today, increasingly stringent demands for the high-purity cobalt and nickel salts required for battery applications in consumer electronics, electric vehicles, and solar applications are again challenging the state of the art. The evolution of cobalt–nickel separations is traced from the basic precipitation technologies employed in 1960s, through commissioning of the first cobalt solvent-extraction plant in South Africa in 1974, to the commercialisation of organophosphinic-acid extractants (which provided a step-change improvement in selectivity) and their eventual widespread use in the 1980s and ’90s. This was followed later by their sulphur analogue, which enabled different possibilities for laterite processing in the new millennium. Separations in chloride media, which take advantage of the different speciation chemistries, and nickel extraction by oximes in ammoniacal systems are also discussed. More recently, chelating and solvent-impregnated resins have added further dimensions to the possibilities for flowsheet design and enabled higher purity products to be attained from both primary and secondary sources. Selected case studies and flowsheets are described.

By Kimiaki Utsunomiya, Yasumasa Hattori, Yoshiaki Mori, Toyokazu Okubo

"The effect of various operating conditions on splashing behavior in a Peirce-Smith converter has been investigated with a 1/5.7 scale cold model. Dynamic similarity between the model and a commercial converter was attained by setting the modified Froude number in the model experiments in· the range for normal converter operation. It is known that for a given modified Froude number the dimensionless penetration length of gas into the liquid phase increases as the liquid density decreases. Moreover, penetration· length has a large effect on splashing behavior. Therefore, a heavy liquid, a mixture of water and lead concentrate was used as the liquid phase. It was concluded that the amount of splash dramatically decreases with a reduction in the buoyancy energy per, unit liquid mass and an increase in the horizontal distance between the tuyere tip and the edge of the mouth.IntroductionSubmerged gas injection is widely used in practice in ferrous and nonferrous pyrometallurgical operations to achieve large gas-liquid contact areas and good agitation of liquid for rapid chemical reaction. The common application in ·nonferrous industry is the Peirce-Smith converter with multi-tuyere for copper and nickel matte converting. This process has been used for over 100 years because of its effectiveness in mixing of the molten bath, as well as its merits of the engineering simplicity. However, the mechanisms which · determine the blowing performance is poorly understood, and the design and operating conditions of the Peirce-Smith converter varies widely from plant to plant, such as by diameter, length, mouth angle, tuyere position and level of molten matte. Smelters have continuously made an effort to increase converter productivity, implying maximum tuyere blowing rate. Above a certain critical blowing rate, splash of molten matte from the converter mouth becomes unacceptable because of dangerous ejection and accretion buildup around the converter mouth, which results in interference with effective hood sealing. In fact, a 1993 converter survey[!] reported that splash was a major limiting factor for blowing rate and 54% of responding plants from around the world regard it as a limiting condition[2]. In order to increase tuyere blowing rate a study of the effect of various operating conditions on splashing behavior is expected."

Jan 1, 2000

By K. Osseo-Asare

"The molecular structural and solution chemical characteristics that underlie the surface activity of solvent extraction reagents are highlighted, with particular emphasis on the tendency towards reverse micelle and microemulsion formation. The physicochemical factors that lead to microemulsion-enhanced solvent extraction with chelating extractants are elucidated. Membrane-based contactor systems are described which are uniquely suited for enhanced solvent extraction with microemulsions. The possibility of combining solvent extraction with microemulsion-mediated materials synthesis is discussed. IntroductionThe discovery of new selective extractants has resulted in major breakthroughs which have helped to establish solvent extraction as a versatile separation technology (1-3). A complementary strategy towards new process development is to seek new ways of using the available reagents. This paper explores this second approach. From a molecular structural standpoint, an extractant may be viewed in terms of two components: a polar functional group and a hydrocarbon radical. In the conventional view of solvent extraction, this molecular structure serves two main purposes: The polar functional group provides the binding sites for complexation of metal ions, while the organic group is needed to render the resulting metal-extractant complex organic-soluble. But are these the only properties of the organic and the polar groups that are relevant to the solvent extraction process?In this paper, attention is directed to the fact that solvent extraction reagents possess the molecular structures of amphiphiIes; that is, they are characterized by the presence of spatially separated hydrophilic and hydrophobic groups on the same molecule. A case is made for the view that this amphiphilicity offers interesting opportunities to develop new separation processes which collectively may be described as enhanced solvent extraction (4-6)."

Jan 1, 1996

By V. I. Lakshmanan

Crown ethers are gaining importance in separation technology specifically for rare earth elements (REE, La to Lu plus Y) and precious metals (Au, Ag, Pt, Pd, Rh and Ir) due to their specific binding ability, metal complex stability and high extraction efficiency. The selectivity of crown ethers in extraction of these metals depends on different factors, including the cavity diameter and nature of a donor atom of the crown ether, size and charge of the metal ion, diluents and counter ion. Demand for strategic REE and precious metals are consistently increasing in the world while the separation of these metals is most challenging tasks. In this paper, the use of crown ethers in separation of REE and precious metals, reaction mechanisms and simplified process flowsheets will be elucidated. New reagents with high selectivity for the separation of these metals are further expected to produce high purity metals.

By Hylton McWhinney, Doanh Tran, Jewel Andrew Gomes, George Irwin, Sameer Pallavkar, Md Islam, David Cocke, Mohammad Rafiqul Islam

"High-performance nickel-based nanocrystalline zinc oxide adsorbents have been prepared adjusting Ni/Zn mol ratio of 1 :5 by thermal decomposition, coprecipitation and sol-gel method for selective adsorption of thiophene in liquid hydrocarbon fuels at ambient temperature and pressure. To understand the nature of reactive adsorption of thiophene (C4H4S) on Ni/ZnO, the effect of preparation techniques, morphological and textural structure on the desulfurization activity was investigated. A model fuel (20 mL) consisting of pentane (C5H12) and thiophene was prepared and adsorption experiments were performed by a batch method under ambient conditions. The physicochemical behaviors of the fresh adsorbents were obtained using X-ray diffraction (XRD) with EDAX, scanning electron microscopy (SEM). The sulfur concentration in the mixture was monitored by UV-vis spectrophotometry. The adsorption reaction confirmed that ZnO played a crucial role in taking up S element to convert it into ZnS. The deposition of nickel on ZnO is an innovative approach which takes advantage of the selectivity of Ni towards S-species and the high adsorptive capacity of ZnO support.IntroductionLow temperature deep desulfurization of fuels via selective adsorption of sulfur compounds keeping coexisting aromatic hydrocarbons and olefins intact is receiving increasing attention in the research community worldwide in order to satisfy the upcoming environmental regulations and fuel specifications. The sulfur compounds in the transportation fuels is a matter of concern when global crude oil slate is becoming heavier and sourer and environmental restrictions on both the refining process and the refined products are becoming more stringent. According to the current refinery technologies, the sulfur content in refinery fuel is typically around 300-500 ppm by weight (ppmw) [1-3]. Starting in 2006, sulfur limits in highway diesel and gasoline were set to 15 ppm and 30 ppm, respectively. During combustion sulfur in the fuel are converted to toxic sulfur oxide (SOx) and contributes to air pollution and acid rains [ 4]."

Jan 1, 2011

By Richard D. Hangi

Process mineralogy techniques are uniquely applicable to industrial problems related to the extractive metallurgy of nickel, cobalt, and associated metals. Reflected 1ight microscopy, together with selected determinations by scanning electron microscopy-energy dispersive spectrographic analysis and electron probe microanalysis, provides the means to identify the ore minerals cobalt and nickel ores, determine the abundance of each ore mineral, assess the extent of intergrowth between the cobalt and nickel minerals and other ore and gangue minerals in the ores and concentrates, and predict the potential success of cobalt and nickel extraction by grinding, flotation, pyrometallurgical, and hydrometallurgical treatments. In addition, the extent of locking of the cobalt and nickel minerals with each other and with the gangue minerals can be directly observed by reflected light microscopy. Where ores have been treated by hydrometallurgical procedures, reflected light microscopy can serve to determine the causes of excessive leach consumption. Finally, the partitioning of cobalt and nickel between high-temperature synthetic phases produced by pyrometallurgical treatment can be precisely determined by process mineralogy techniques. Case histories from cobalt and nickel deposits illustrate the value of applied mineralogical techniques in the study of cobalt and nickel ores, beneficiation, hydrometallurgial, and pyrometallurgical products.

Jan 1, 1993

By H. Yin, T. Emi

"Advantages of gas/flux injection technology as materialized in the main stay unit processes for steelmaking are depicted covering hot metal pretreatment through secondary refining. Current status of micro-kinetic issues involved in the injection technology are reviewed including gas-in- metal, gas-in-slag, flux-in-metal, metal-in-flux and three-phase dispersion systems with reference to macro-kinetics. Key problems are briefly addressed to further develop injection technology for steelmaking processes.1. FROM PAST TO PRESENTApplication of gas injection to steel industry started in early 1950's when inert gas bubbling via stopper rod, lance, or porous refractory plug was practiced to make the temperature of steel melt in ladle uniform The gas bubbling in ladle was then extended to slightly removing hydrogen ti'om the steel melt tapped from Electric Arc Furnace (EAF) and Basic Open Hearth Furnace (BOH) when vacuum processing facilities were not popular. Later, oxygen gas injection via calorized steel pipe into molten steel bath in BOH Furnace was also put into operation to promote the decarburization to increase the productivity of the process. This line of development has been made in parallel with more profound processes, i.e, top blowing Basic Oxygen Furnace (BOF) for primary steelmaking and side blowing Argon Oxygen Oecarburization (AOD) vessel for decarburizing stainless steels.On the other hand, injection of fluxes into steel bath was first industrialized in Germany in 1960's, Primary objective was to desulfurize steel melt in ladle by injecting CaC2 or CaCrCaO mixture via lance under neutral slag cover with good success. Difficulties in injecting fluxes without clogging and rippling at a desired flux/gas ratio, and durability of injection lance were resolved in due time to bring forth many injection facilities to flourish for versatile refining operation. Top injection of fluxes from main oxygen lance to BOF was also industrialized as LDAC to promote early slag formation. A new process then emerged which injects oxygen gas and fluxes together through concentric annular tuyere, installed at the bottom of the BOE into steel melt. This process, developed in Germany [Oxygen Bottom Maxhutte (OBM)] and brought into maturity in USA (Q-BOP) and Japan in a large scale operation, became the predecessor of the combined blowing (top and bottom blown) BOF which dominates modern steelmaking."

Jan 1, 1996

By K. P. V. Lei

The U.S. Bureau of Mines investigated a hydrothermal sulfidation procedure to recover lead and silver from plumbojarosite. The plumbojarosite, generated during pressure-oxidative leaching of zinc concentrate in a commercial operation, contained, in percent, 25.4 pb, 18.8 Fe, 1.4 Zn, 29.5 SO,2-, 3.2 s?, 13.4 total sulfur, and 7.4 oz/ton Ag. The sulfidation was conducted in an autoclave and converted the plumbojarosite to amorphous iron oxide and liberated the lead and silver as sulfides. The best operating conditions were using 50 9 of plumbojarosite and 7 pct s? (2.04 9 S? added) in 500 mL of 2.0 mol/L NH3, 150? C, and 1 h. The sulfidation product contained, in percent, 37 Pb, 28 Fe, 6 S2-, 2 SO,2-, and 11.2 oz/st Ag. Ferric chloride leaching extracted 98 pct Pb and 97 pct Ag from the sulfidation product.

Jan 1, 1990

By I. Iwasaki

Platinum group elements (PGE) are often found in arsenide and sulfarsenide minerals as inclusions in copper-nickel bearing gabbroic rocks. Major losses of platinum in flotation have been attributed to the poor recoveries of the arsenic minerals. Flotation characteristics of a synthetic nickel arsenide and arsenopyrite were studied through rest potential and oxidation rate determinations, surface analyses, and micro-and batch-flotation tests. The use of nitrogen during grinding and flotation together with copper activation improved the PGE recoveries from Duluth Complex ores. The flotation behaviors of the sulfarsenide minerals are still unresolved. The role that electrochemical interactions play among arsenides, sulfarsenides, sulfides and grinding media on their f10atabilities is discussed.

Jan 1, 1988

By Christopher B. Vierrether

Reflected light microscopy, scanning electron microscopy, and electron microprobe analysis have been used to determine the mineralogy, phase percentages, grain sizes, textures, and partitioning of cobalt and nickel in two cobalt-nickel rich mattes. These mattes were prepared by submerged bath smelting from a flotation cobalt-nickel concentrate containing 4.8% cobalt and 5.1% nickel. The concentrate was derived from lead-zinc-copper ores of the Viburnum Trend, southeast Missouri. Eleven discrete phases have been distinguished in the matte samples, three of which contain significant cobalt and nickel. The phases are cobaltpentlandite ((Co,Ni,Fe)9S8), cobalt-bearing marmatite ((Co,Fe,Zn)S), shandite (Ni3Pb2S2), bornite (Cu5FeS4), galena (PbS), magnetite (Fe3O4), pyrrhotite ((Co,Ni,Cu,Fe)1_xS), chalcocite (Cu2S), CuPbS phase, metallic copper, and metallic silver. Cobaltpentlandite and cobalt-bearing marmatite- occur in coarse grains (50 µm) that would separate readily during grinding, but shandite contains small (5 - 10um), abundant inclusions of pyrrhotite and bornite.. Some mineralogical variations between the two matte samples were due to differing degrees of oxidation during smelting,

Jan 1, 1988

By C. Ek

In bismuth metallurgy, low-copper high-sodium mattes are by-produced. Different charges containing mixtures- of crude mattes, oxidized matte, and/or copper sulfide concentrate and/or copper silicate ore have been smelted to give a rich matte and a disposable slag, then converted to obtain blister copper with high recovery and a rich slag to be recycled.

Jan 1, 1983

By H. K. Fouad, L. A. Guirguis

The starting mill strip solution· for this study· is an ammonium uranyl tricarbonate solution of pH 8.2 containing 20g uranium/liter, after a DEPA/TOPO extraction process from sulfuric acid leaching liquor. To the first portion of the concentrated acidified strip solution, hydrofuoric acid is added at 95°C in reduced condition to obtain uranium tetrafluoride. The second portion of the uranyl carbonate strip is subjected to a precipitation step by admixing 0.3 volume of non-solvent precipitating agent such as acetone per volume of uranium. ·Uranium oxide (U30 8) is obtained from this precipitate by calcination for half an hour at 800°C in air. The third portion of the strip solution is neutralized to a pH 6.5 with sulfuric acid to precipitate iron and other contaminants. The solution is further acidified to a pH 1.85 with continuous air bubbling to remove CO2, followed by H2Ch precipitation at pH 3.5 to obtain uranyl peroxide. The latter is reduced by stannous chloride to obtain uranium trioxide dihydrate UO3. 2H20. Identifications, characterization· and purity of these products are carried out by complete chemical analyses, Scanning electron microscope study, tap density determination, X-ray diffraction and infrared spectroscopic investigations. The achieved results agreed well with that of the published data for these nuclear grade purity products.

Jan 1, 2000

By Paul Van Negan

During the last decade, MHO has continued to diversify the feed. of its Hoboken smelter. The range of feed materials including larger proportions of precious metals has been extended and the production of minor metals has been developed. These diversifications have required further improvements at the smelter. Attention has been particularly focussed on an increase of productivity, compliance with emission standards and achievement of the highest recoveries of valuable elements. The assaying and sampling facilities have been considerably expanded and the different processing steps of the smelter are now also systematically controlled and managed by simulation models. The charge preparation at the sinter plant, returns handling, sinter conditioning and corresponding ventilation systems have been completely renewed. The annual smelting requirement is now achieved with two blast furnaces instead of three. This is the result of rebuilding and enlarging one of the furnaces and, of a completely new concept of the charge proportioning and charging systems, together with oxygen enrichment and blast air preheat. Ventilation capacity has also been drastically increased. A 7 MVA electric furnace for cleaning the slag from both blast furnaces. contributes to improving the overall metal recovery.

Jan 1, 1990

By A. A. Bustos

A model was developed to simulate the blow-by-blow operation of the converting process. From the weights, compositions and temperatures of all converter feeds the model calculates the composition and tonnage of both converter matte and slag as well as bath temperature at the end of each blow. The development of the model and its application to the converter aisle operation are described. There is good agreement between model predictions and observed results. At the present time the model is being used to investigate different converting schemes and their effect on pay metal recoveries, slag chemistry and temperature of the bath. Future work involves the use of the simulation model as a process control tool for the converting operation.

Jan 1, 1988

By Guy L. Fredrickson

A modified transpiration reactor was used to measure the composition of the equilibrium gas phase formed above compounds in the Hg-O-S system at high temperatures (600 to 900K). A thermodynamic database {(AGo°f AH°t. AS°t)} for-HgO, HgS, HgSO4, Hg2SO4, HgSO4?HgO, and HgSO4?2HgO was developed based on the experimental results. Prior to this study, only estimated data were available in the literature for the sulfates and oxysulfates at temperatures above 298K. A series of vapor pressure' stability diagrams were constructed from 473 to 973K with isobars of Hg(g), HgO(g), S2(g), and SO3(g). These diagrams were found to be significantly different than those available previously and do provide insight to the phase relations of importance during the thermal processing of Hg-containing wastes. The thermodynamic results were used to conduct a series of Gibbs energy minimization calculations for a thermal processor' afterburner system for the treatment of HgS-containing wastes. The retention of Hg in the discharge calcine was examined as a function of temperature and excess air. Hg was found to report to the calcine as HgSO4, Hg2SO4, or HgSO4 HgO depending on the process conditions, and Hg retention occurs at temperatures as high as 930K. The precipitation of Hg-containing phases from cooled afterburner discharge gas starts at approximately 900K and the cooling of the gas an additional 30K (to 870K) results in over 50% of the Hg being preCipitated as HgS04?HgO. It was also determined that for small amounts of Hg present in sulfide concentrates during roasting, the Hg will be retained as HgSO4 or HgSO4?HgO at temperatures as high as 870K.

Jan 1, 1996

By Taufiq Hidayat

Accurate description of complex phase equilibria provide the foundations for the improvement of non-ferrous pyrometallurgical smelting and recycling processes. Recent advances in microanalysis and experimental techniques enable accurate phase equilibria characterisation. Quantitative microanalytical techniques including Electron Probe X-ray Microanalysis and Laser Ablation ICP-MS enable the concentrations of major and minor elements present in different phases in samples to be accurately measured providing data that cannot be obtained using bulk chemical analysis techniques. High-temperature equilibration experiments coupled with the subsequent analysis of elementary reactions at micro- and macro-scales ensure the attainment of equilibrium conditions, and therefore, ensure true phase equilibria information is obtained. Examples of the application of the improved methodology on the investigation of phase equilibria of low-order and complex, multi-component gas/slag/matte/metal/solids Cu2O–PbO–ZnO–Al2O3–CaO–MgO– FeO–Fe2O3–SiO2–S systems and the distribution of minor element are provided. The experimental study is closely integrated with thermodynamic database development for the above system. Example of implementation of the research outcomes into industrial operations is demonstrated.