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By Zdzistaw MiGzkowski

At KGHM Polska Miedi 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 ex-change 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 deter-mined 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 E. vanHuyssteen

A method of establishing the relationship between the mineralogy of a sinter and its subsequent processing behaviour in a lead blast furnace is demonstrated. It involves: 1) analyzing the Zn-spinels, hardystonite, larsenite, Pb-silicates, Pb-arsenates, Pb-(Ca)-sulphates and other femtes with an electron microprobe; 2) determining the extent of elemental substitutions in various mineral structures; 3) establishing a sequence in which the various phases formed during sintering. In this manner the relationship between the bulk chemistry of a sinter formulation and the speciation of elements into various phases in the sinter can be established. Specifically, the-substitution of Mg for Zn in hardystonite significantly influences sinter production. Mg substitution releases Zn into the surrounding matrix. This Zn reacts with the Pb-silicate to form larsenite thereby reducing the amount of Pb-silicate available for anhydrite digestion. Excessive amounts of residual anhydrite thus result if the sinter formulation is based solely on the CaO/Si& ratio.

Jan 1, 1993

By Kuo En Chang

Many rare earth - transition metal (RE-TM) compounds absorb/desorb hydrogen reversibly at room temperature and atmospheric pressure. For LaNi5 which is used as a battery material, the electrochemical nature of this process is well known. In the case of Nd-Fe-B which has found wide application as a powerful permanent magnet, the absorption of hydrogen has both significant advantages and disadvantages. However, a fundamental understanding of the hydrogenation process at ambient temperatures and its effect on subsequent corrosion behavior is currently lacking. This paper reports the results of the hydrogenation of NdFeB two alloys, (NdDy)15Fe78.3A10.7B6 and (NdDy)15Fe67Co5V4A12B7, which are compared with that of LaNi5. Results show that hydrogenation can be accomplished by either electrochemical methods or immersion in dilute sulfuric acid. For the latter method, the change in lattice parameter indicates that the level of hydrogen absorbed by the NdFeB particles corresponds fairly closely to an overall composition of Nd2Fe14BH2.7. Cyclic electrochemical charge/discharge experiments show that the maximum hydrogen discharge capacities of the NdFeB, NdFeB-Co-V, and LaNi5 are 40, 60, and 210 mA?h?g-1, respectively. Anodic potentiodynamic polarization measurements and calculated values of icon reveal that absorbed hydrogen in NdFeB-Co-V and the NdFeB may lead to significant increases in corrosion rates.

Jan 1, 1995

By Leonard J. Friedman

The contact process for the production of sulfuric acid has been used commercially since before the turn of the century (1880?s), and rapidly replaced the chamber process after the development of vanadium catalysts in the early 1900's (1910's - 1920's). Plant size has increased from a few tons per week to single train units in excess of 4,000 tons per day. Much of the history of the contact process is in the minds of the few remaining early process pioneers that started in the industry in the 1920's and 1930?s, and in sulfuric acid industry books published in 1921, 1925, 1936, and the last Deucker and West in 1959. Since those not familiar with history are doomed to repeat the failures and mistakes of the past, this paper includes a brief history of the contact process along with the history and development of equipment and materials in each equipment area of the process. The main focus of the paper is to present the development and analysis of equipment and materials in the contact section of the sulfuric acid plant - from the dry tower to stack.

Jan 1, 1999

By Yuanbo Zhang, Zhaokun Tang, Mingjun Rao, Guanghui Li

The ballability of hematite ore with addition of a certain amount of pulverized anthracite and the induration features of anthracite–containing hematite pellets were studied. The results indicate that adding a certain proportion of anthracite can improve the quality of green pellets as well as the roasting performance of roasted pellets. The suitable mass dosage of anthracite is 1.0%–1.5%. Under the conditions of roasting temperature 1280 oC–1350 oC and roasting time 15 min–20 min, the compressive strength of roasted pellets is found to be more than 2500 N/P. Compared with hematite pellets in the absence of anthracite, the proper induration temperature is diminished by 20 oC, whereas optimal induration temperature range expands by 50 oC, and induration time is shortened by 5 min–10 min. Adding anthracite is an effective measure to improve the pelletization of hematite.

Jan 1, 2015

By Chris P. Pistorius

Over the past few decades the carbon intensity of ironmaking and steelmaking has been reduced considerably through improved efficiency in blast furnace ironmaking, partial replacement of coke with less carbon-intensive fuels, and increased use of scrap and direct-reduced iron in steelmaking. To evaluate possible further reductions in carbon intensity accurate process information is needed. A preliminary test of the fidelity of publicly reported data as a source of process information is reported here. The sources are industry roundups of electric furnace furnace steelmaking and blast furnace ironmaking (published by the Association for Iron and Steelmaking Technology), and data recorded by the Environmental Protection Agency under the US Greenhouse Gas Reporting Program. From a comparison for an integrated steelmaking plant and an electric furnace furnace plant, it appears that the values from the two data sources are consistent. The comparison does rely on process details such as the quantitative relationship between injected oxygen and carbon emissions in electric furnace steelmaking.

By K. J. Richards

The converting of copper mattes to blister copper has seen few technical advances since the introduction of batch furnaces using submerged tuyeres over a hundred years ago. The first side-blown converting vessel, operated by P. Manhes in 1882, was an offshoot of the 'Bessemer steelmaking process, and subsequent improvements in the conversion of molten mattes resulted In the Peirce-Smith converter, still the Industry standard today. While Peirce-Smith' converting has served the industry well since the early 1900!s, increasingly stringent environmental regulations, burgeoning energy costs, and a trend toward continuous processing have set the stage for a major improvement in this area of copper production. In contrast to a growing number of approaches for continuous converting using molten copper mattes, Kennecott is developing a process for treatment of solidified matte which allows improved' control, higher oxygen enrichment and a separation or decoupling of smelting and converting operations not possible with the other converting technologies. The new process known as Solid Matte Oxygen Converting, or SMOC, eliminates the need for molten matte transfers, minimizes fugitive emissions, and produces high strength SO2 off gases which substantially reduce offgas handling requirements. The SMOC process, despite additional matte solidification and size reduction steps, offers both capital and operating cost advantages for new smelters and the upgrading of existing plants, when compared with conventional converting technologies. Capital cost reductions of up to 35% in converting, gas handling, and sulfur fixation are indicated. Kennecott has successfully tested the new process concept and continued' development work is now under way to commercialize the technology. This paper reviews the limitations of batch copper converting with emphasis on the need for a continuous process, previous industry approaches to continuous converting of molten mattes, and the new Kennecott development.

Jan 1, 1983

By Omid Marzoughi

In this research, both the kinetics and the mechanisms of the roasting of a sphalerite concentrate from the Bafgh mining complex in Iran were investigated. The oxidation process was performed in a muffle furnace in air and the effects of time and temperature on the degree of oxidation of the zinc sulfide sample were quantitatively studied. The experimental data were fitted to the shrinking core model. In the temperature range of 650–800 °C, the rate-controlling step was the chemical reaction between the zinc sulfide and oxygen with an activation energy of 103 kJ mol−1. On the other hand, in the temperature range of 850–950 °C, the rate-controlling step was oxygen diffusion with an activation energy of 50 kJ mol−1. Also, the roasting process was studied using thermogravimetric (TGA) and derivative thermogravimetric (DTGA) techniques.

By Jesus Gonzalez

Peirce-Smith converters (PSC) are long cylindrical chemical reactors where copper matte reacts with air. Traditionally, air is injected laterally through submerged tuyeres at different subsonic velocities. However, the accumulated experience in steelmaking, particularly in the basic oxygen furnace (BOF) process, shows that the gas bottom injection may improve the mixing efficiency of a liquid pool. The aim of bottom injection is to maximize the copper kinetic energy meanwhile avoiding excessive reactor splashing. When gas is injected from a single orifice at the bottom of a liquid pool, two main gas flow regimes can be identified, bubbling and jetting. In this work, a PSC with bottom air injection is studied by means of multiphase 3D CFD numerical simulations considering multiple air velocities. Special attention is paid to the bubbles and jet formation mechanism. The mixing efficiency is measured by calculating the turbulent kinetic energy of the copper matte.

Jan 1, 2008

By L. Filip

The roast-leach-electrowinning (RLE) process for zinc was modified to treat two typical complex concentrates containing zinc, lead, copper, gold and silver. Laboratory testwork results indicated that the optimum roasting temperature ranged from 700 to 800°C, in order to produce acceptable residual sulfur levels. The calcined concentrate was subjected to a three-stage leach sequence. The resulting leach solution was purified by hematitic precipitation and directed to the recovery of copper and zinc by solvent extraction and electrolysis. Alkaline smelting and subsequent electrolytic purification recovered the lead and precious metals from the leach residue. A flowsheet was developed based on the laboratory testwork results, and demonstrated in a large-scale pilot plant. The recoveries produced during the pilot plant operation ranged from 90 to 92% for zinc and copper, 85% for lead and 90% for gold and silver, respectively.

Jan 1, 1999

By Vadym Drozd, Yongzhou Sun, Shah Najiba, Jiuhua Chen, Andriy Durygin

"Phase transitions of the potential hydrogen storage compound, ammonia borane (NH3.BH3), was investigated using Raman spectroscopy and a diamond anvil cell at high pressures up to 9.5 GPa and low temperatures down to 90K. At room temperature, ammonia borane has three phase transitions in this pressure range. Upon cooling, four new phases were discovered through changes in characteristic Raman spectra. This result provides information about the stability of new bonding characteristics of this potential hydrogen storage material at low temperature and high pressure region.IntroductionDevelopment of hydrogen technology requires the safe, efficient and environmental friendly materials for hydrogen storage and hydrides have attracted much attention as hydrogen storage media. Among chemical hydrides, ammonia borane (BH3NH3) stands out due to its high gravimetric and volumetric hydrogen density ' "". Despite high hydrogen content, this compound is very stable. It releases hydrogen in several steps by thermal decomposition in the temperature range of 100°C to 500°C. Direct thermal decomposition also causes toxic borazine emission. Recent research interests on ammonia borane include destabilizing this compound to lower the dehydrogenation temperature with an enhanced hydrogen release rate using different techniques, e.g. the nanoscaffolds'', ionic liquids"" and acid'"" or transition metal catalysts' ""'. As a molecule of ammonia borane consists of protonic (NH) and hydritic (BH) hydrogens bonded by the polarized dative bond, thermal or catalyzed decomposition requires breaking of N-H and B-H bonding. Still now, the detailed information about the bonding characteristics of ammonia borane is not sufficient to understand details about its phases and structures. The development of methods to enhance hydrogen discharge rate from ammonia borane requires a detailed study about the structural and dynamical properties that control the stability and the intermolecular interactions of this material. This study is motivated to investigate the stability of the existing phases and also to explore the existence of any new phases at different temperatures and pressures which may have enhanced hydrogen release and uptake properties."

Jan 1, 2012

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 Egil Krystad, Merete Tangstad, Kai Tang, Gabriella Trenell

"A new UMG-Si refining concept has been proposed in this paper. Liquid Si and another liquid metal phase (Me) were separated by the molten slag spontaneously based on their different physicochemical properties. Two metal/slag distribution reactions are able to occur in the system simultaneously. Experimental investigation on the B and P distribution equilibria among Si/slag/Me was carried out in the graphite resistance furnace under the inert atmosphere. The B and P doped silicon was in equilibrium with either the SiO2-CaO or SiO2-CaO-l0%CaF2 slags at 1600 and 1650°C, respectively. The pure Fe and Cu metals were used in order to ""capture"" B and P in the slag phases. B and P in samples were determined by the ICP-MS. B and P distribution coefficients for the Si/slag/Me equilibria were compared with the theoretical calculations. The possible kinetic barriers for the Si/slag/Me three-layer equilibria have been analyzed. The metal contaminations in the three-layer equilibria were also examined. The present study provides a new approach for the refining of MG-Si.IntroductionMost of the impurities in the metallurgical silicon (MG-Si) are rather ""dilute'', ranging from few to several thousand ppms. However, the target impurity levels for upgrade metallurgical silicon (UMG-Si) feedstock are often far below the level of ppm. In such extreme case, the conventional refining technologies face the great technical challenges. B removal by slagging has already been implemented industrially. Removal of Pis frequently carried out by the vacuum distillation. The separating treatments for B and P removals lead to increase refining cost, total CO2 emission and longer pay-back time of solar cell module.It is well known that the phosphate capacities of slags in equilibrium with liquid silicon are extremely lower. However, if we introduce another phase that possesses high ""phosphor capacity"" into the Si/slag system, one would expect to continuously remove P from Si through molten slag to the new ""phosphor capturer"". The so-called three-layer refming concept is thus proposed in the present study. Liquid Si and another liquid phase (Me) are separated by the molten slag spontaneously based on their different physicochemical properties. Two metal/slag distribution reactions are able to occur in the system simultaneously."

Jan 1, 2013

By Nourreddine Menad

Plastic materials have been associated with electric and electronic applications since the early days of the electrical industry. Plastics can amount to 30 percents of the scrap mass. Generally, they are treated with flame retardants such as halogenated ones and they can result in different toxic chemical compounds. These plastics can be used as combustibles in the recovery of copper and precious metals. However, during their combustion, halogenated flame retardants can produce dibenzo-p-dioxins and dibenzo-furans. The estimated thermodynamic data of several organic compounds resulting from combustion of electric and electronic scrap, have been used in conjunction with the program HSC to calculate the conditions for dioxin and furan formation. The results show that the formation of the dioxins is dependent on the quantities of carbon, hydrogen, chlorine and oxygen reacting in a given system, as well as on parameters such as temperature and pressure.

Jan 1, 1998

By Björn Saxen

Outotec atmospheric Direct Leaching has so far been implemented for zinc production capacities of around 100,000 t/a. Lately, there has been growing interest for small scale direct leaching plants, producing circa 30,000 t/a of Zn. Such small leaching plants can provide extra front-end capacity in existing roaster-based plants and enable treatment of feed materials not suitable for roasting. In small scale plants the proven OKTOP® 9000 Direct Leaching reactors are not readily applicable, due the large size. For smaller installations a modular approach is proposed providing multiple advantages, such as reducing the construction time and amount of the site work required causing less disturbance to regular plant operation with reduced cost. In this paper, we present advantages that can be achieved by using modular OKTOP®C reactors and discuss also process design when connecting a small scale direct leaching process to an existing zinc plant. Also benefits of direct leaching expansion are presented.

By Baozhong Zhao

Laboratory experiments have been conducted on the removal of As, Sb and Bi from molten copper by SF 6 injection. The results showed that the impurities can be removed by SF6 injection in the? sequence of Sb >As >,Bi and the rate of Bi removal is affected significantly by the concentration levels of As and Sb in the copper melt. Analysis of the experimental data indicates that the impurity removal process is under chemical reaction control rather than by mass transfer of impurity through the molten copper phase. On the basis of experimental results, a kinetic model was developed and the order of chemical reaction and the volumetric chemical reaction rate coefficients of impurity removal were determined.

Jan 1, 1996

By M. I. Zinigrad

A model of an ideal associated solution is presented. This model takes into account the existence of complexes of various compositions, sizes and geometries and allows calculating thermodynamic properties and phase diagrams of binary alloys. The model has been used formerly to calculate thermodynamic parameters and the position of the liquidus line for binary eutectic systems and also those having a stable compound in the solid phase. In all the cases the model parameters were not adjusted rather estimated from melting temperatures of the components. The recent studies dealt with the influence of arbitrary-stoichiometry associates on the equilibrium thermodynamic properties of liquid alloys. The application of the model to eutectic systems and systems having an unlimited solubility in solid and liquid states close to liquidus has been considered. It was shown that if the difference in melting temperatures of the components was small, different types of fusibility diagrams were possible: eutectic diagrams, cigar-shaped diagrams or diagrams with upper or lower azeotropic points. Peritectic transformations could take place when the difference in melting temperatures of the components was large. The present work is devoted to calculation of phase diagrams and thermodynamic properties of binary systems on the basis of chrome.

Jan 1, 2006

By Tianzu Yang, Weifeng Liu, Lin Chen, Wei Chen, DUCHAO ZHANG, HUI XIAO

Carbonaceous refractory materials are widely accepted in many reducing smelting processes such as iron and ferroalloys. Oxidizing processes such as copper concentrate smelting traditionally use magnesia and/or alumina/silica refractory materials. The main objection to the use of carbon-based refractories as the exposed working lining in oxidizing applications is the potential for free oxygen to react with the carbon at high temperature, which could rapidly degrade the refractory lining. In 2013, Outotec and GrafTech conducted joint trials of a thermally conductive, carbonaceous lining for smelting copper concentrates in the Outotec® pilot-scale top-submerged-lance (TSL) furnace in Dandenong, Australia. This testwork had two equally important goals; to demonstrate the ability of carbon refractories to withstand oxidizing process conditions, while ensuring that neither furnace operating conditions nor process stability were negatively affected by the refractory material. The paper discusses the input parameters of the trials, key observations during the testwork program, and the results and conclusions from both process and refractory design standpoints.

Jan 1, 2016

By N. M. Komkov

The main operation of obtaining zinc from sulfide raw materials by hydrometallurgical technologies is the oxidation roasting of zinc concentrates in fluidized bed furnaces. The technical-economic parameters are determined by the parameters of the roasting process, which depend on the composition of the initial raw materials, the temperature of the bed and on other factors. The predetermined roasting temperature is maintained due to the change of specific efficiency as well as to the quantity of the heat removed from the bed. The efficiency of caissons depends at a high degree on the composition and the thickness of the accretion formed on the surface of the caissons. Forecasting the roasting results is impossible unless we know the mechanism of the accretion formation. The aim of the present paper is the thermodynamic analyses of the behavior of the charge compositions under roasting and the determination of the potential mechanism of the accretion formation. The thermodynamic analyses show that under conditions of the oxidation roasting the thermodynamic probability of the formation of zinc sulfate is higher than the probability of the oxide formation until a temperature of873 OK is reached. The thermodynamic probability of the formation of the lead sulfate is higher than the probability of oxide formation in the entire temperature range of roasting. The probability of formation of ferrites and silicates of zinc decreases only insignificantly the sulfate stability. The results of the investigation of the accretions composItion formed under roasting of concentrates with particle sizes less than 0.02 J..lm (60%), containing 65% of sphalerite (ZnS), 12% of pyrite and chalcopyrite (FeS2 and CufeSz) each, 3% of galenite (PbS), 7% of silica and other non-ore minerals, have shown that the composition of accretion varies depending on the depth of the accretion layer. The accretions on the caissons and the thermo-siphons consist mostly of zinc sulfate (more than 50%). The accretions of forehamber consist mostly of zinc oxide. They also contain ferrites and silicates. The formation of the sulfate zinc accretion in the cold parts of the fluidized bed furnace (the caissons and thermo-siphons) may be explained by a lower temperature on the surface and probably by a catalytic influence of the present oxides in the formation of S02 and sulfates. The nature of the structure of the accretion in the hotter parts of the furnace may supposedly be explained by the formation of elemental vaporous zinc during roasting.

Jan 1, 2003

By J. E. Dutrizac

A mineralogical study of a weak acid leach residue from the Clarksville zinc plant of Savage Zinc Inc. was carried out. The study focused on Pb and Cd as these elements most significantly impact on the environmentally acceptable disposal of the residue. The residue consists of major amounts of bassanite, zinc ferrite and various Zn-Pb-Fe-Cd silicate species. Also present are lesser quantities of PbSO4, sphalerite, Fe2O3 quartz, Mn-Pb-Fe oxides, SrS04, (Pb,Sr)SO4 iron gel-silica gel, jarosite and Ti oxide. The principal Cd carriers are the zinc ferrite, which contains up to 9.00% Cd and likely accounts for -45% of the total Cd content of the residue, and the various silicate species which contain up to 6.97% Cd and account for about 45 % of the total Cd. The sphalerite is a minor Cd carrier containing an average of 0.35 % Cd and accounting for -5 % of the total Cd; the other carriers contribute only trace amounts to the total Cd content. The major Pb carriers are PbS04, Pb-bearing silicates and Mn-Pb-Fe oxides. Minor proportions of the total 1.09% Pb content of the residue are carried by SrS04 and (pb,Sr)S04' Trace Ph carriers include the iron gel-silica gel, Fe-Zn-AI oxide and bassanite. The residue after the toxicity characteristic leaching procedure (TCLP) is mineralogically very similar to the initial weak acid leach residue; the amounts of calcium sulphate are approximately the same in the two products. The principal Cd and Pb carriers are also the same as those noted in the initial residue, except that some dissolution and reprecipitation of Pb-Sr sulphate takes place. That the residue fails the TCLP test is likely a consequence of the superficial dissolution of Pb and Cd from species such as PbS04 or Zn-Pb-Fe-Cd silicate.

Jan 1, 1995