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By Roberto Parra

The selective reduction smelting of Cu2O in Cu2O-FeOx-SiO2 melts has been studied at laboratory level, using as a feed a dead roasted calcine from a copper concentrate. The purpose of the study was to evaluate the kinetic and mechanisms of the indirect reduction with CO and the direct reduction with graphite from 1260°C to 1350°C. The reduction rate by CO was found to be 10-2 to 10-1 mole Cu2O m-2s-1. The graphite reduction macrokinetics for FeO and. Fe2O3 containing melts, was found to be a first order reaction with respect to the Cu2O concentration, with a kinetic constant of 104 to 10-3 s-1. The reduction rate was not sensitive to temperature nor to stirring, in the range studied. The measured reduction rate is almost one order of magnitude larger than the observed rate for the direct reduction of FeO.

Jan 1, 1999

By Isabel Lázaro

A detailed study has been undertaken into the electrochemistry of the leaching of chalcopyrite in acidic solutions containing ferric ions. Mixed potential measurements have shown that the maximum potential achievable on a chalcopyrite disk in a ferric sulfate medium lies within the so-called passive or prewave region in the anodic behavior of chalcopyrite. The very low current densities due to the anodic oxidation of chalcopyrite at potentials in the region of the mixed potential has made studies of the initial stages of dissolution difficult. However a careful rotating ring-disk electrode (RRDE) study has enabled data to be obtained for the stoichiometry of the initial dissolution reaction to be obtained. Thus, in addition to the detection of soluble iron and copper as products in this potential region, a soluble sulfur species has also been detected. A comparison of the experimental with the expected collection efficiencies of the products on the ring has revealed that this soluble sulfur species is likely to be thiosulfate. The characteristic transient anodic behaviour of chalcopyrite in this potential region has been interpreted in terms of a rate limiting solid-state diffusion process. Thus, extrapolated rates based on reported measured solid-state diffusion coefficients for the mineral at elevated temperatures have been shown to be consistent with the potentiostatic current-time transients. Furthermore, comparative studies of the anodic characteristics of the copper sulfide minerals covellite and bornite has confirmed their greater reactivity in this potential region. The results of this investigation have been combined with a parallel study of the non-oxidative behaviour of chalcopyrite in order to derive a model for the dissolution process which is consistent with other published studies of the electrochemistry and dissolution of the mineral.

Jan 1, 2003

By Fu-Shen Zhang, Mengjun Chen, Jianxin Zhu

"A novel approach for foam glass preparation, namely vacuum-aided powder sintering technique, was preliminarily investigated in the present communication. The key point of which was to prepare foam glass at a negative pressure. Compared to normal powder sintering process, the new approach could benefit the foaming process by shorting the holding time, reducing the amount of foaming agent and especially decreasing relative density of the product. Optimum conditions were 750 °C, 1000 Pa, 5 min and 1 wt.% foaming agent, respectively.IntroductionFoam glass represents a highly valuable solution for thermal and acoustic insulation, since it possesses a generally higher mechanical, chemical and thermal stability than other foams'1'. The first industrial processing for foam glass production, the direct introduction of gases (""blowing"") into the special molten glass, can be dated back to the end of 1930s'2'. At present, almost all foam glasses is prepared by powder sintering technique instead of blowing,3 since it reduces the temperature by several hundred degrees. Moreover, as fine glass powders or similar powders can be used to substitute corresponding glasses by this technique, considerable attention has been focused on the production of foam glass by considering fully recycled glasses, coal fly ash, or other solid wastes as raw materials,4 especially CRT glasses'3' 5', on the point of environmental protection.In a previous report'6', when discussing the lead removal and recovery from CRT funnel glass by a pyrovacuum process, we found that foam glass could be prepared at a negative pressure. Therefore, in this communication, the similarities and differences between the powder sintering process for foam glass at normal and negative pressure was preliminarily discussed."

Jan 1, 2011

By G. A. Brooks

The problem of treating concentrates with increasingly higher levels of arsenic and antimony is compounded by the trend to stricter environmental guidelines regarding the disposal of smelter wastes. Much of the arsenic and antimony from non-ferrous processes is recovered as oxide fume. The options for handling these fumes include recycling them to the smelter, stabilising and disposing of them, and recovering values from them. Whilst arsenic oxide has little value, there is a market for antimony oxide and this provides an incentive for devising techniques for separating antimony oxide from arsenic oxide before disposal of the arsenic oxide. Arsenic can be separated from antimony oxide by selectively volatilising the more volatile arsenic trioxide from a mixed oxide sample or by selectively condensing the less volatile antimony tetroxide at high temperatures, leaving arsenic trioxide to condense out at lower temperatures. The results of selective volatilisation experiments at 379 to 587 °C indicate that it is difficult to achieve an arsenic content below 5.0 wt.% using air or nitrogen as carrier gas due to the formation of solid solutions between the two oxides. Injection of oxygen into a mixed vapor stream improved separation by selective condensation and antimony tetroxide containing as low as 0.23 wt.% was obtained in laboratory experiments.

Jan 1, 1994

By Suzzann Nordwick

Over the past decade, significant advances have been made in the development of sulfate-reducing bacteria (SRB) technology to treat acid mine drainage (AMD). Bench-scale testing, field demonstrations, and engineered applications of SRBs for the treatment of AMD will be presented. Designs include an in situ bioreactor installed in the subsurface workings of the Lilly Orphan Boy Mine in 1994, the SRB bioreactors installed at the Calliope Mine from 1998 to 2001, the integrated biological reactors built at the Surething Mine in 2001, and the ongoing development of a replaceable cartridge system. SRB technology benefits include the reduction of dissolved metal ions to insoluble metal sulfides and the neutralization of the AMD resulting from the production of bicarbonate from the oxidation of organic nutrients. This paper will address engineering design criteria including the selection of organic media and system permeability and complete mitigation of AMD. Research was funded under Interagency Agreement No. DW899388-70-01-1 between the US EPA and the US DOE and was conducted by MSE Technology Applications, Inc., through the National Environmental Technology Laboratory (DOE Contract No. DE-AC22-96EW96405) at the Western Environmental Technology Office located in Butte, Montana.

Jan 1, 2003

By René Bustamante

The subject of this paper is a comparative evaluation of different copper smelting gas cooling techniques, using "productivity and quality" criteria. The first section presents a brief description of the operation of the radiant and the evaporative cooling systems, focusing on the differences between each other, in particular regarding. a) mass and energy balances; b) gas flow, temperature and composition; c) dust concentration and recovery. This section includes a brief discussion of the "client-server chain", i.e. the links between the cooling equipment and the down-and up-stream operations. More in particular, the up-stream server relationship impacts on the operating stability of the furnace, and in turn on furnace down-time and Cu production losses; and the down-stream client relationship affects the operation of the electrostatic precipitators, in terms of workload and cost of handling larger quantities of dust of a given dust size The second section deals with the development of indexes to measure and compare value added through the "utilization, productivity and quality" that can be expected of both cooling methods at the physical and economic levels, and the impact on the overall smelter productivity and the final cost composition of copper. The final section presents the results and includes a discussion of the comparative advantages and disadvantages of both cooling systems.

Jan 1, 1999

By David R. Sadedin

The highly negative Gibbs free energies of hydrogen atom reactions suggest that refractory oxides such as titanium dioxide should be easily reduced by hydrogen atoms. These reactions appear to be most favourable at low temperatures; oxides should be reducible even at room temperature. Since hydrogen atoms are produced in plasmas containing hydrogen a number of investigators have used hydrogen plasmas of various sorts to test these possibilities for reducing refractory oxides, in particular TiO2. None of these attempts has succeeded, a small degree of reduction being achieved in only a thin layer near the surface. A deeper consideration shows that several factors complicate the reactions expected on the basis of the negative Gibbs free energy. One factor is that the back reaction by water molecules produces molecular hydrogen, not hydrogen atoms, and the metal atoms that have been reduced may be immediately re-oxidised. In plasmas there are complications due to diffusion, thermal and charge boundary layers and charged particle reactions. Interpreting the results of hydrogen atom reactions is difficult. Hydrogen is not detectable by electron dispersive spectroscopy and amorphous products are not determinable by x-ray diffraction. Another consideration is economics. The cost of producing hydrogen atoms has a large bearing on the metals for which hydrogen atom reduction may be competitive. In this paper these factors are discussed, some necessary basic studies are highlighted and the general principles of a laboratory reactor are given, together with the results of tests using ZnFe2O4, ZnO and TiO2 as test oxides.

Jan 1, 2006

By Alexander V. Suvorin, Vladyslav M. Sokolov

"The traditional technologies for production of the coprecipitated and deposited catalysts are analyzed from the standpoint of diversion of application of the feedstock and increase of efficiency for its usage. The options for return of the metals of spent catalysts to the catalysts production are described. The novel environmentally friendly and cost efficient approach for reutilization of the spent catalysts is realized in practice. It anticipates application along with spent catalysts of the waste generated in the catalytic productions. Reutilization of the Ni-containing catalysts is referred as an illustration. Introduction The recent development of large catalytic manufacturing for organic and inorganic synthesis, and petroleum refinery as well as for applied environmental catalysis has brought about increase and diversification of catalysts production. The generation of spent catalysts has been increased correspondently. The feedstock for production of catalysts is mostly metals in a form of nitrates, carbonates, hydroxides, hydroxydcarbonates. Sometimes salts of organic acids, of ammoniates, of chlorides and of sulphates occur. All these materials are scarce and expensive. So their repeated use by reutilization of spent catalysts is very actual issue. The traditional recycling the Fe-, Cr-, Ni-, Cu- or Zn-containing spent catalysts are carried out by pyrometallurgical reclamation of pure metals or alloys. They can not be used directly in production of catalysts [1, 2]. The hydrometallurgical approach is used for recycling spent catalysts with PGM, W, Mo, Co, Ni or Cu. It provides production of salts of these metals in a form of sulphates, chlorides, carbonates, hydroxydcarbonates and sometimes nitrates or ammoniates. Only a limited number of these salts can be used directly in production of catalysts. Material losses during catalysts production The basic feedstock for manufacturing coprecipitated and deposited catalysts that may be produced from the spent catalysts is aqueous solutions of metals nitrates. Their production is based on application of nitric acid as a dissolvent. About half of it is lost with the flue gases in a form of nitrates vapor and nitrogen oxides (II, IV). The last compound is generated by reaction:"

Jan 1, 2008

By Susumu Imashuku

A pseudoternary phase diagram of the BaO?ZrO2?ScO1.5 system is established and the conductivities of the scandium-doped barium zirconate are measured in wet conditions. According to the phase diagram, the molar fraction of scandia in the barium zirconate phase that equilibrates with the cubic zirconia (ZrO2) and scandia (Sc2O3) phase is 0.03. On the composition line, where the molar fraction of barium oxide (BaO) is 0.50, the solubility of scandia into barium zirconate is 0.27 as a molar fraction of scandia. At around 500 °C, the conductivities of scandium-doped barium zirconate are estimated to be almost same as that of yttrium-doped barium zirconateThe activation energies for bulk proton conduction in scandium-doped barium zirconate (0.57 eV for BaZr0.90Sc0.10O3-d) are higher than that of yttrium-doped barium zirconate (0.44 eV for BaZr0.90Y0.10O3-d). In addition, the bulk conductivity of scandium-doped barium zirconate in this study is 10 times higher than the reported conductivities in the temperature range of 75 °C to 300 °C.

Jan 1, 2006

By John O. Burckle

For years, the measurement of fugitive emissions from the primary copper converter has defied all attempts based on inferential measurements, It has been concluded by virtually all investigators that the only dependable tech¬nique to measure these emissions would be to completely enclose an operating converter to permit the capture and measurement of all emissions. However, complete enclosure with a metal hood is difficult; many of the most serious fugitive emissions result during periods when the converter must be attended with crane-operated equipment. This approach would require either opening of the enclosure to permit the entry of large items of equipment or completely new methods for charging and tapping converters' The installation of the air curtain hooding system at ASARCO's Tacoma smelter has permitted a quantitative approach to the direct measurement of the fugitive for the first time. In this program, the fugitives captured by the air curtain were measured at a downstream sampling point in the exhaust side of the air curtain system during the various portions of the converter cycle. Emission factors were established for sulfur dioxide, filterable particulate (method 5), inhalable particulate, and selected trace elements.

Jan 1, 1983

By C. J. Newman

The new Kennecott Utah Copper smelter, started in 1995, was designed to be the cleanest smelter environmentally in the world. The plant is operating at production rates above the original design capacity. Copper concentrate is smelted in an Outokumpu flash smelting furnace. Matte is granulated and processed using Kennecott-Outokumpu flash converting. Copper anodes are processed in a modernized copper refinery using the Kidd Process while anode slimes are processed for precious metals recovery using a unique hydro-metallurgical process. To allow the production of high quality cathode, using modem smelting and converting technology to minimize emissions, impurity control had to be carefully addressed. All process bleed streams from the smelter and refinery are treated in a hydro-metallurgical plant to fix impurities in a stable form, allow for the rejection of impurities as required and recover valuable metals. Special technology was developed for the copper refinery to ensure production of high quality cathode from anodes containing high levels of impurities. The smelter routinely achieves a sulfur capture in excess of 99.9% which is equal to less than 2 kg of SO2 per tonne of copper produced. This paper describes the design of the smelter and refinery and includes recent production and emission data and modifications carried out to allow operation at above the original design rates. It emphasizes the unique features required to achieve environmental and quality goals and compares environmental performance data to that published on other smelting operations. The processing of intermediate streams, the management of recycled materials and the impurity control strategy will be covered in detail.

Jan 1, 1999

By C. J. Newman

In January 1999, a redesign of the Kennecott Flash Converting furnace settler was initiated to enhance furnace integrity and extend furnace life. This furnace uses Kennecott-Outokumpu Flash Converting technology to produce copper directly from copper matte. A detailed assessment was made of all technology available around the world before making a decision on the design features to be incorporated in the new design. The new design includes the following: redesign of all sidewall cooling elements to include the latest cooling element technology; redesign of the furnace hearth to include a stadium hearth at the reaction shaft end of the furnace; redesign of the furnace hearth to include a stepped hearth design adjacent to the furnace sidewalls; addition of flat settler roof cooling elements .around the reaction shaft; replacement of reaction shaft transition elements with an improved design and improvements to the furnace cooling element monitoring systems. The Flash Converting furnace was shut down on a planned basis in July 2001 to implement these improvements after 29 months of operation, converting more than 1,000,000 tonnes of matte. During the 30 day shut down, the improvements were successfully completed, with furnace start up in August 2001

Jan 1, 2002

By Hector M. Henao

The FeOX-CaO-SiO2 base slag at intermediate oxygen partial pressures is very often used in non-ferrous smelting processes. This slag would also contain Al2O3 and MgO because these compounds are normal components in the ore and the refractory of a furnace. The objective of the present work is to determine the effect of Al2O3 or MgO addition on the liquidus temperatures of the plain FeOX-CaO-SiO2 slags in the atmosphere between intermediate pO2 of 10-6 and that of iron saturation at 1250 and 1300 °C. The experiments were carried out at given mass%CaO/(mass%CaO+mass%SiO2) ratios ranging from 0 to 1 and at spinel-tridimite double saturation. The experimental results show that the effect of Al2O3 or MgO addition on the plain FeOX-SiO2-CaO slag is not uniform and depends on the content of Al2O3 or MgO, the oxygen partial pressure and the mass% CaO/mass% SiO2 ratio. It is apparent that Al2O3 or MgO addition enlarges the spinel or wustite saturation area at almost all the oxygen partial pressures and temperatures of this research. The obtained phase diagrams will be useful in the metallurgical industry to assist in the selection of slag chemistry, operation condition and development of new processes.

Jan 1, 2006

By Jaeheon Lee

Gold-copper alloys are shown to form during the cementation of gold on copper in a solution containing 0.25M [S2O32-] at 25oC. The alloy composition is strongly dependent on the initial Cu:Au ratio in solution and ranges from Au3Cu to AuCu3. XPS results for Au, Cu, S, and O are reported as a function of depth through an entire deposited film with an initial solution containing 20 ppm [Au] and 30 ppm [Cu]. The deposit contained about 20 atomic % gold and was predominantly Cu3Au. Underpotential deposition (UPD) theory is discussed as a mechanism for explaining the formation of these alloys. Several other systems that produce alloys during contact reduction/cementation are also discussed.

Jan 1, 2003

By Adam C. Powell

A new Cahn-Hilliard phase field model of transport-limited electrochemistry describes phase boundary motion due to oxidation and reduction reactions at metal-electrolyte interfaces. Benchmarks demonstrating the accuracy of the method include open circuit voltage and closed circuit current in metallothermic reduction, and linear stability theory in metal electrolysis, including a new stability criterion for reduction of liquid metal from liquid electrolyte. The model is applied here to understanding cathode interface stability in titanium electrolysis e.g. in the SOM process developed with Uday Pal, and to structure evolution in subhalide reduction of titanium dichloride by magnesium developed by Toru Okabe. Potential for application to new fuel cell and battery systems is also discussed.

Jan 1, 2006

By Hee Dong Jang

Crystalline metal oxide nanoparticles such as lithium cobalt oxide (LiCoO2) and indium tin oxide (ITO) were synthesized from sprayed droplets of aqueous precursor solution by flame spray pyrolysis. Complete thermal decomposition of the aerosol precursors was obtained at high flame temperature. Molar concentrations of the precursor solution, and the flow rate of combustion gas such as hydrogen, oxygen and air were varied to control particle size, size distribution and crystal structure. The crystalline nanoparticles synthesized were nearly spherical, and their average primary particle diameters ranged from 11 to 35 nm for LiCoO2 and from 8 to 15 nm for ITO.

Jan 1, 2006

By Motoyasu Sato

Highly pure pig irons were produced in a multimode microwave reactor from powdered iron ores with carbon as a reducing agent in the nitrogen atmosphere. The grains in compacted powder absorb microwave energy selectively. Microwave-matter interaction creates thermal non-equilibrium state microscopically and enhances chemical reactions and the phase mixing at the grain boundaries very rapidly. The visible light spectroscopic techniques was used to monitor the progress of the reactions. Up to 650°C, the heated powders radiate the continuous spectrum of blackbody emission. The small non-equilibrium hot spots rise, move and finally burst in to brighter light emitting from all over the surface at 650°C. CN molecules and Fe (I) atoms were identified in the recorded spectrum. These bursts are similar to the ?ignition propagation? normally observed in chemical reactions. The line spectra originated from CO molecules have not been detected yet. The solid-solid reaction could be expected between the iron oxides and carbon to produce CO2 directly. A loss in the sample weight was accelerated during the excess-emission. These are the clear evidence that microwaves cause thermally non-equilibrium state and accelerate reduction process. The reduction of iron ore is completed at 1380°C and relatively very pure pig iron was produced. It should be noted that the impurity level of Mg, S, Si, P and Ti is only 5-10% of what is found in the pig irons produced by modern conventional blast furnaces in the steel industries. The necessary amount of carbon needed was 1/2 compared to conventional blast furnace to produce the unit weight of steel, if we applied renewable energy or nuclear power for the microwave excitations.

Jan 1, 2006

By Meyer Steinberg

"Some early experiences of a Cooper Union Chemical Engineer on the Manhattan project and his latest studies on CO2 Greenhouse Gas Mitigation Technologies are presented. Mitigating Global Greenhouse effect while maintaining a fossil fuel economy, requires improving the efficiency of conversion and utilization of fossil fuels, use of high hydrogen content fossil fuels, decarbonization of fossil fuels and sequestration of carbon and CO2 applied to all energy consuming sectors of the economy including electric power generation, materials production, transportation and industrial domestic heating. Decarbonization means removal of carbon as C or CO2 either before or after fossil fuel utilization and sequestration means long term disposal of C or CO2. The review will cover the principles of removal and recovery from power plant, stacks, the oceanographic and geological disposal of CO2 and the conversion of CO2 to gaseous and liquid transportation fuels. The global economic aspects of CO2 mitigation technologies are touched upon.IntroductionThis is an odyssey of a chemical engineer. My career started with the production of U235 at the Gaseous Diffusion Plant in Oak Ridge, Tennessee and the production of PU-239 metal at Los Alamos on the Manhattan Project. After 40 years at Brookhaven National Laboratory, I wound up performing studies on CO2 mitigation technologies. The following is a power point presentation on the subject of global warmingThe DOE is proposing to increase its sequestration development program in order to maintain the utilization of our vast resources in coal both for power and for transportation fuel production. Congress is considering steps to promote energy efficiency in attempts to solve not only the CO2 problem, but also the prime problem of energy supply. We will be promoting increases in energy efficiency as time goes on."

Jan 1, 2008

By O. Morfín

The most probable source of Pb contamination in the perennial reach of Aravaipa Creek, Arizona, has been determined using Pb isotope ratios and total metals analyses of samples collected from the ephemeral and perennial reaches and mine wastes located in the Aravaipa Mining District . Previously, elevated levels of Pb, Cd and As in fish in the perennial reach of Aravaipa Creek, a protected wilderness area,, were assumed to be due to off-site transport from abandoned flotation tailings piles located at Klondyke, Arizona upstream of the wilderness area.Our work replaces this inference with isotopic data that allows us to confirm this hypothesis. The Pb/Zn deposits of the district were mined between the late 1890s and the late1960s, with the most significant ore production coming from one deposit in a rhyolite dike swarm on the Western front of the Santa Teresa Mountains, a granitic pluton of Cretaceous-Tertiary age (~65 ma). Mineralogy has been well constrained across the length of the lode system: Pb and Zn sulfides predominate in the NW sector, and a mixed suite of hypogene/supergene Pb sulfide and Pb oxide minerals comprises the majority of its SE corner. Total metals analyses and comparison of metals ratios serve to constrain the source and transport of certain metals within different parts of the system. Pb isotope ratios in samples, obtained by ICP-MS analysis, define two distinct contributors. The first end-member (208Pb/204Pb = 38.513 to 38.721 and 207Pb/204Pb= 15.550 to 15.598) is characteristic of the mixed, oxide/sulfide ores at the SE end of the deposit. A second end-member (208Pb/204Pb = 38.855 to 38.946 and 207Pb/204Pb = 15.610 to 15.625) characterizes samples taken from the NW, purely Pb sulfide end of the lode. Pb isotope ratios from perennial reach sediments are closely correlated with ratios given by samples from the Klondyke tailings site and by Pb sulfide samples from the NW sector, the primary source of ores processed at Klondyke.

Jan 1, 2003

By Alysson Tadeu Pereira Almeida

Steels with low concentrations of nitrogen, hydrogen and carbon have been in large demand lately. The RH process is a secondary refining process that can simultaneously attain significant levels of removal of these interstitial elements from liquid steel. In the RH process, the melt circulation rate plays a very important role in determining the productivity of the equipment, since it affects the decarburization rate. In the present work, a physical model of a RH degasser in a 1:5 scale of an industrial reactor has been built and used in the study of the circulation rate and of the kinetics of decarburization. The effects of the gas flow rate and of the configurations of the nozzles used in the injection of the gas have been analyzed. The decarburization reaction of liquid steel was simulated using a reaction involving CO2 and caustic solutions. The concentration of CO2 in the solution was evaluated using pH measurements. The experimental results indicated that the kinetics of decarburization can be described by a first order equation. Based on the results, it was possible to determine the contributions of the decarburization in the upleg snorkel and in the vacuum vessel.

Jan 1, 2006