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By Zdzislaw Miczkowski

At KGHM Polska Miedz S.A, a direct flash smelting process is used for smelting of chalcocite concentrate for the production of blister copper. The paper presents a model of complex oxidation process of single concentrate grains smelted at KGHM. The description covers main chemical reactions, phenomena of heat and mass exchange inside the grains and between a grain and the surrounding space. In the model, two zones describing the course of process inside the grain were distinguished: ? The first one, which moves faster towards the centre of a grain, both organic and carbonate carbon are freed, The process takes place without the presence of oxygen and results in an increase of the temperature in the core of the particle. ?The second zone moves slower into the grain and the rate of the movement is determined by the presence of oxygen, In that zone the sulphur is eliminated and the oxidation of the organic compounds vapours moving from deeper layers of a grain takes place. Based on the results of laboratory tests, the coefficients that describe the oxygen transportation into the grain and decide the progress in the chemical reaction were determined, The paper contains the results of model calculations for single grains reacting in environment of various content of oxygen as well as the results of model calculations for the laboratory reactor system.

Jan 1, 2003

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 Zhang Chuanfu, Tan Pengfu

"A thermodynamic model is developed to simulate nickel flash smelting process. In the nickel flash furnace, oxidation of concentrate occurs at one end, and reduction of slag occurs at the other. The model makes use two zones, namely the reaction shaft/settler zone and the appendage zone and accounts for 6 phases (matte, slag, silica, magnetite, Cu-Ni alloy and gaseous phase), 13 elements (Ni, Co, Cu, Fe, S, 0, N, C, H, Si, Al, Mg and Ca) and 33 chemical components in nickel flash smelting system. The compositions of matte, slag and gaseous phases in equilibrium are calculated by using the data of free energies of formation and activity coefficients of components. Two nickel sulfide species are used to allow for the modeling of sulfur-deficient mattes. The model predictions are compared with the known industrail data from Kalgoorlie Nickel Smelter, and excellent agreement is obtained. The model can be a very useful tool for monitoring and optimizing the actual industrial operations of nickel smelting process. The distribution behaviors of Ni, Co, Cu, Fe, S and 0 in the nickel smelting furnace depend on the process parameters such as smelting temperature, volumes of air, the content of the elements~ charge and oil.1. IntroductionThe nickel flash smelting furnace essentially consists of a reaction shaft where nickel sulfide concentrate is partially oxidized with air, a settle zone where matte and slag are allowed to separate, and a slag cleaning end where coke is added to provide for the reduction of the oxidized nickel from slag, and electrodes are used to provide heat.The theoretical model to consider a mass balance for copper flash furnace is developed by S. Goto and R. Shimpo[1][2J. However, this can not be true for nickel flash furnace as a whole since oxidation of concentrate occurs at one end (in the reaction shaft/settler), and reduction of slag occurs at the other (in the appendage). Despite these limitations, an acceptable pseudo-thermodynamic description of the furnace can be achieved using essentially two zones, namely the reaction shaft/settler zone and the appendage zone. Compositions of gas, slag and matte in two zones are calculated."

Jan 1, 1998

By R. Leiby

Prior to March 1992, the only component of the lead acid battery that was not recycled by East Penn Manufacturing Company was the sulfuric acid electrolyte. This acid was unusable in new batteries because the iron level was found to exceed new product specifications. The development of a liquid ion exchange process to remove the iron from the acid allows East Penn to currently recover over three million gallons of sulfuric acid annually. The process is based upon the use of an iron selective liquid ion exchange material or solvent to extract iron from the sulfuric acid electrolyte followed by regeneration of the solvent. Equilibrium and kinetic data for the extraction and regeneration steps were collected in order to scale up the process to commercial scale. An electrochemical process for the treatment of the acid used in the regeneration step was, also developed which significantly reduces the volume of strip acid required in the process.

Jan 1, 1995

By E. Allain

Extraction of basic metals from sulfides by conventional pyrometallurgical processing leads to the emission of SO2. To avoid this inconvenient, low temperature selective chlorination of sulfide concentrates could be an alternative. However, such process generates hazardous chlorides SxCly. A part of sulfur chlorides such as SCI2 can be recycled as a chlorinating agent of metal sulfides. Hydrolysis of sulfur chlorides, using a solution containing Na2S.9H2O, led to the recovery of more than 90 pct of elemental sulfur. Reduction of SxCly by hydrogen was investigated between 300 °C and 800 °C. About 70 and 90 pct of elemental sulfur were recovered from SC12 and S2C12, respectively. A flow sheet for the chlorination of metal sulfides and the treatment of sulfur chlorides was suggested.

Jan 1, 1998

By Zhengjie Chen, Wenhui Ma, Jijun Wu, Kuixian Wei

The gasification reactivity of PC (petroleum coke), strengthened by addition of different potassium carbonate proportions using different grinding medium, was investigated by using thermogravimetric analysis (TGA). Results showed that the gasification reactivity of PC not only increased with the increase of catalyst-loaded, but also showed the effective improvement by anhydrous alcohol. The PC was mixed with potassium carbonate [K2CO3] catalyst at 0.5%, 0.8%, 1.0% and 1.5%, and then ground wet with distilled water. The CO2-gasification rate of PC was only 77.35%, 80.55%, 84.07% and 85.88% under the gasification temperature 1100 °C and holding time 120 min, at different K2CO3 respectively. However, when the PC was ground in anhydrous alcohol at the same condition of catalyst-loading, the gasification rate of PC reached 95.43%, 96.63%, 95.50% and 95.61% at the holding time of 108 min, 101 min, 74 min and 35 min, respectively. It was shown by FTIR, SEM and EDX determinations that the anhydrous alcohol used as the grinding medium can further improve the gasification reactivity of PC when compared with the distilled water.

Jan 1, 2016

By Alan M. Russell

In recent years, several rare earth intermetallic compounds with the B2-type structure have been reported to exhibit high tensile ductility and high KIC fracture toughness at room temperature. These materials retain considerable ductility even at 77K. These are noteworthy findings because most intermetallics possess poor room temperature ductility and low fracture toughness unless one or more special contrivances are applied (e.g., doping with small additions of interstitial elements, offstoichiometric compositions, testing in ultra-dry atmospheres, etc.). This paper summarizes recent findings on rare earth B2 intermetallics. These include the determination of the active slip systems; the strain rate sensitivities; yield strength maxima at elevated temperatures; the search for possible twinning and stress-induced phase transformations; ab initio calculations of their defect energies and the anisotropy of dislocation line tension. Potential applications of these materials and the possibilities that this study may suggest strategies for increasing ductility in other intermetallic compounds are discussed.

Jan 1, 2008

By James C. Withers

There is no production of rare earth metals in the U.S. in spite that the U.S. is the largest consumer of rare earths in some form that includes consumer and Department of Defense (DoD) devices. The one U.S. mine has been purchased by the Chinese that even enhances their monopoly on rare earths. A research effort has demonstrated rare earth oxides can be extracted from bastnaesite ore as well as coal ash at efficiencies in the upper 90s percent. The rare earth oxide can be carbothermically treated to produce an oxycarbide which is highly electrically conductive. The rare earth oxycarbide can be used as an anode in anhydrous fused salts electrolysis to produce a highly purified rare earth powdered metal. It is also possible to electrofractionate the individual metals which can be combined with co-deposition of iron and boron to produce the highly magnetic alloy Nd2Fe14B.

Mar 1, 2018

By Liuyin Shi, Kang Liu, Fengqi Zhao, Yan Song, Zhiping Yang, Xing Fan

Due to the high energy consumption, long technical process, low usage rate of vanadium during the traditional smelting vanadium steel process, a new method for decarburization by CO2 to directly smelt vanadium-containing steel in blast furnace was proposed. In this paper, the thermodynamics of CO2 decarburization in molten iron process was calculated out by FactSage. The thermodynamic calculations indicated that in standard state, the transformation temperature of C and V was 1357 °C; the oxidation order of element was Si, C, V, Mn and S when using CO2 as oxidant. The experiment of blowing CO2 temperature showed that decarburization reaction temperature was 1550 °C, carbon content could be decreased to 0.676%, the decarburization rate was 88%. There was no effect on vanadium content in molten iron during the decarburization process, vanadium content was 0.323%, which meets the request of vanadium mould steel.

Mar 1, 2018

By Joseph Bloch

The hydriding of bulk metals and alloys is a gas-solid reaction in which a hydride product layer is initially nucleated adjacent to the gas-solid interface and continues to grow until a complete transformation of the parent (a) phase into the hydride phase. The combination of measurements of the overall hydriding kinetics of samples having defined shapes and dimensions, together with examinations of partially hydrided samples, enables the presentation of the reaction rate in terms of an appropriate reaction model. A common and important type of topochemical development of the hydride in bulk metals and alloys involves a hydride layer formed on the metallic surface. The continuity of the layer can affect the reaction rate. The rate of hydrogen absorption in a sample, in the presence of a hydride layer, is usually analyzed using a model combining several sequential steps in which the hydrogen is transferred from the gas phase into the reaction site. Coupling the flux equations across the layer under proper steady state conditions, results in a complex rate equation in which the steady state rate of hydrogen absorption (proportional to the hydride layer velocity) is expressed in terms of the pressure, temperature, the rate constants of the sequential steps and the critical concentrations of hydrogen in the hydride. Generally, the rate constants of the individual microscopic processes are comparable in magnitude, so that the overall rate is not controlled by any of the specific sequential steps. However, there are two limit cases related to the first stage, the adsorption, for which the general rate equation is much simpler, namely, the fast and the slow adsorption approximations. Using this limit cases, equations are derived for the steady state hydriding rate of a given system. These equations provide means to anticipate the pressure dependence of the steady state absorption rate under low pressures, close to Peq and under very high pressures. At the low pressure regime both the fast and slow absorption cases yield linear pressure dependence. For the very high pressure range, it is found that the rate become independent of the applied pressure. The rate is given then by a combination of the individual rate constants of the system and the critical hydrogen concentrations. The model is shown to apply in several real cases, such as ZrCo, LaNi5 and titanium.

Jan 1, 2002

By J. A. S. Tenorio, K. S. Barros, D. C. R. Espinosa

Considering the risks involving the use of cyanide, other complexing agents have been evaluated for the treatment by electrodialysis of the effluent of brass electrodeposition and among them, EDTA is interesting since it has been already tested for many years to separate ions. The main objective of the present paper was to evaluate the occurrence of fouling and scaling on the surface of the anion-exchange membrane HDX 200 by the construction of chronopotentiometric curves and speciation diagrams in different conditions (pH between 10–12 and proportion of cupric ions of 30%, 50%, 70%). According to the results, the chronopotentiometric curves did not show additional inflexion points typical for the cases which occurs fouling and scaling for the pH values evaluated, which is in accordance with the speciation diagrams of the solutions constructed with the aid of Hydra-Medusa software. Hence, the pH and the proportion of cupric ions did not show influence on the curves behavior.

Mar 1, 2018

By R. S. Celmer

The distributions of cobalt, molybdenum, copper, and selenium between nickel matte and silica-saturated iron silicate slag have been determined in the region of the metallic saturation boundary, at 1523 K. Results are given as a function of the composition of the coexisting Fe-Ni alloy and the activity of iron in the system. Under strongly reducing conditions, these minor elements display a marked preferential accumulation in the sulphide phase. It is shown that the dissolution of cobalt and molybdenum in slag follows an oxidative mechanism, and distribution equilibria are correlated with the oxygen potential. From these data, the thermodynamic properties of cobalt in nickel matte are computed. Further, comparisons of minor element partitions are made between the nickel and copper matte smelting cases under metal saturation conditions.

Jan 1, 1988

By Wei Luo, Yuanbo Zhang, Zhixiong You, Zijian Su, Guanghui Li, Tao Jiang

"In this study, the appropriate sintering process parameters for low-grade ferromanganese ores were investigated. The results showed that, under the condition of natural basicity (R=0.03), the optimal parameters were obtained as follows: moisture of mixture 9 .1 %, coke powder 9 .9% and sintering negative pressure 7 KPa. And the corresponding yield, ISO tumbling index and utilization coefficient reached at 80.18%, 61.27% and 1.515t·m-2·h-1, respectively. Under the optimal parameters, the emission of harmful gases, such as S02 and NOx, were reduced evidently with 30% of coke powder replaced by biomass charcoal. Moreover, it was found that the basicity had obvious effects on the quality of the sinters when it changed between 0.03 and 2.4. The ISO tumbling index gradually decreased from 61.27% to 55.47% with the basicity increasing from 0.03 to 1.2, then, it began to increase after the basicity further increased to 2.4.IntroductionManganese is mainly consumed by steel and battery industries, particularly in the steel plants and ferroalloy units. The consumption of metal manganese in the ferroalloy industry accounts for 85%-90% of the total Mn [1-2]. Therefore, ensuring sufficient manganese alloys is essential to meet the rapid development of steel industry. Recently, rich-manganese slag containing high grade Mn (>40%), low Fe (1%) and P (<0.03%) is considered as superior raw materials for manganese alloys. While the sinters made from manganese ores are major raw materials for producing rich-manganese slag with the increasing exhaustion of natural rich manganese lump ores [3-5]."

Jan 1, 2013

By E. W. Lithgow

Commercial volumes of nickeliferous laterite ores overlie part of a 90 km long belt of peridotites in central Dominican Republic. Protores are serpentinized harzburgites and dunites, with lesser serpentinite. The ore mineralogy consists mostly of goethite, serpentine-group minerals, quartz and poorly crystallized, x- ray amorphous materials. Minor constituents are hematite, gibbsite, olivine and enstatite. In the Ore Dressing plant the mine feed is subjected initially to proper sizing and blending to produce a homogenized mix. Subsequent drying and upgrading, by selective crushing and screening of rock fragments through a Barmac circuit, complete preparation of the ore for pyrometallurgical processing.

Jan 1, 1993

By G. Kyle Green

Zirconium chlorinator residues contain an array of rare earths, scandium, unreacted coke, and radioactive thorium and radium. Because of the radioactivity, the residues must be disposed in special waste containment facilities. As these sites become more congested, and with stricter environmental regulations, disposal of large volumes of wastes may become more difficult. To reduce the mass of disposed material, the U.S. Bureau of Mines (USBM) developed technology to recover rare earths, thorium and radium, and unreacted coke from these residues. This technology employs an HCl leach to solubilize over 99% of the scandium and thorium, and over 90% of the rare earths. The leach liquor is processed through several solvent extraction stages to selectively recover scandium, thorium, and rare earths. The leach residue is further leached with an organic acid to solubilize radium, thus allowing unreacted coke to be recycled to the chlorinator. The thorium and radium waste products, which comprise only 2.1% of the original residue mass, can then be sent to the radioactive waste facility.

Jan 1, 1995

By Zhenfeng Zhou, Qingguo Xue, Jingsong Wang, Guang Wang, Yuanyuan Zhang

The oxygen blast furnace is a new technology for ironmaking, where the oxygen and CO2-stripped blast furnace top gas are blown into the blast furnace replacing the conventional hot air. The oxygen blast furnace could reduce the consumption of coke and emission of carbon dioxide. In this chapter, a three-dimensional numerical model was developed to simulate the lance-blowpipetuyere-raceway region of a blast furnace, and the flow and combustion behaviors of coal particles were investigated based on an oxygen blast furnace. Compared with the traditional blast furnace, the combustion characteristics in the raceway of the oxygen blast furnace were different. In addition to the combustion of coal and coke, the combustion of large amounts of reducing gas was included. The coal combustion of different oxygen content (70, 80, 90, 100%) were investigated. The simulation results indicated that the coal burnout was only 21.64% at an oxygen content of 70%, a decrease of 51.52%, compared with a traditional blast furnace. The coal burnout was increased with the increase of oxygen content. When the oxygen content is 100%, the coal burnout was 90.38%, an increase of 17.22%.

Mar 1, 2017

By Ayşe Ece Yıldızçelik, Mehmet Buğdaycı, Onuralp Yücel

ZrB2 and TiB2 are significant metal borides. They are being used in various industrial areas from space technology to nuclear industry owing to their physical properties such as high melting point, high thermal/electrical conductivity and low density. Present study was conducted in two main stages: self-propagating high-temperature synthesis (SHS) reactions and leaching. ZrO2, TiO2, B2O3 were used as starting material and Mg was used as a reductant to produce ZrB2-TiB2 powders via SHS. Therefore, it was aimed to determine production parameters, leaching conditions and comprehensive examination of final product features. The samples were characterized by using chemical analysis (AAS), XRD, XRF and SEM/EDS techniques.

Jan 1, 2015

By Gus Van Weert

Solvent extraction of iron from zinc refinery liquors has been investigated before, mainly on the MEHPA / HC1 stripping combination. Leakage of chloride into the zinc electrolyte and the costs of handling the ferric chloride eluate have prevented this option from being adopted. This work explores the stripping of the ferric loaded organic phase with nitric acid to take advantage of the possibility of regenerating up to 6N nitric acid, and clean spheroidal hematite production by autoclave treatment of ferric nitrate solution. The work was carried out with DEHPA (di 2-ethyl-hexyl phosphoric acid) in kerosine. Degradation testing proved the DEHPA to be very stable, when exposed to nitric acid solutions up to 6N and temperatures up to 70" C over a period of five days. Ferric iron was removed completely froma synthetic hot acid leach liquor, irrespective of the DEHPA concentration. Stripping the ferric turned out to be the problematic step. Although the stripping efficiency was considerable better at 50 than at 20° C, it decreased with increasing DEHPA/Fe ration in the organic phase. Eluates of no more than 5-10 g/l ferric nitrate were produced. surprisingly, nitric acid was found to be a less efficient stripping agent than sulphuric at equivalent normality and its efficacy levelled off above 4N. It was concluded that DEHPA does not appear to be the S.X. reagent to take advantage of the low cost autoclave decomposition of ferric nitrate opportunity in zinc hydrometallurgy and that another S.X. reagent, also resistant to nitric acid, but based on weaker compound formation is needed.

Jan 1, 1998

By Laura Angeles, Martin Reyes, Ivan Reyes, Miguel Perez, Francisco Patiño, Mizraim Flores, Elia Palacios

Chemical and mineralogical characterization of a sulphide ore from the mining district of Zimapan, Hidalgo, Mexico, was performed in order to obtain accurate information on the composition of the ore to optimize the subsequent flotation process. A combination of techniques was used: Scanning Electron Microscopy (SEM) with Energy Dispersive Spectrometer (EDS), X-ray diffractometry (XRD), Inductively Coupled Plasma (ICP) and Fourier transform infrared spectroscopy (FTIR). The SEM mapping confirmed the presence of the elements: Ca, Si, Fe, K, S, Al, Zn, Mg and Mn. The XRD analysis suggests that the ore matrix is calcite; additional species found were wollastonite, johannsenite, and pyrite, among other impurities. The FTIR analysis performed for the aqua regia insoluble showed the presence of calcium oxide, copper oxide and silicon oxide. The results for the ICP analysis were:13.31% S, 2.55% Fe, 0.46% Zn, 0.03% Cu, 0.06% Pb, 0.07% Mn, 0.09% As, 0.01% Sb and 0.08 grton-1 Ag.

Mar 1, 2017

By Hu Long

In this, the first systematic study of the oxidation of orpiment (As2S3) in sulfuric acid solution under oxygen pressure at temperatures above 170°C, the effects of retention time, temperature, particle size, oxygen partial pressure, the concentration of sulfuric acid and pulp density were evaluated. The effects of cupric and ferric ions on the oxidation rate of As(III) to As(V) were also examined. The products of oxidation are As(III), As(V), SO42- and elemental sulfur. At temperatures ranging from 170 to 230°C, most of the arsenic was found to be in the trivalent state, and oxidation to As(V) with oxygen was very slow. This was confirmed by attempting to oxidize a synthetic arsenious solution. However, the rate of oxidation of As(III) to As(V) is rapid in the presence of ferric ion. Elemental sulfur was found at all temperatures investigated, which can be further oxidized to sulfate at high temperature.

Jan 1, 1999