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By Kenneth P. Michalek, James E. Kelly, Jonathan A. Dantzig

"Many investigations have been reported regarding the simulation of continuous casting with emphasis on in-mold heat transfer. These analyses have been limited, however, because they require either estimation or measurement of the characteristic heat transfer between the ingot and the mold. In this paper, a self-consistent model 'is presented for calculating the heat transfer between a solidifying continuous casting and the mold, in the context of the continuous casting of steel. Using both thermal and stress analyses, the air gap formed during continuous casting is calculated and used to compute the heat transfer coefficients. Iteration between the thermal and stress analyses is used to determine a self-consistent solution. IntroductionThe continuous casting process for steel is illustrated schematically in Fig. 1. Molten steel is tapped into a tundish from which it flows at a controlled rate into the continuous casting mold. The initial shell of the casting forms in the mold by transfer of heat from the metal through the mold wall to the cooling water. The remainder of the casting is solidified by application of water sprays, and/or radiation cooling below the mold.Heat transfer in the mold portion of the process is important because it controls the formation of various defects which are deleterious to subsequent processing. Examples of defects formed in this region are surface irregularities, such as cold folding and oscillation marks, and more serious defects, such as longitudinal or transverse cracks. A more catastrophic problem which may occur is a breakout, in which the shell ruptures and molten steel is discharged in an uncontrolled way."

Jan 1, 1986

By Leiting Shen

The thermodynamics of tungsten ore decomposition in mineral acid and alkaline solutions were studied. The published thermodynamic data of tungsten minerals were collected and assessed. The Gibbs energies of CaWO4 (−1538.43 kJ/mol), FeWO4 (−1053.91 kJ/mol), MnWO4 (−1206.08 kJ/mol), H2WO4 (−1003.92 kJ/ mol), and Na2WO4 (−1455.58 kJ/mol, aq) at 25 °C were adopted in the calculation using HSC software. The results show that CaWO4 is decomposed more readily in Na2CO3 solution than in NaOH,while FeWO4 andMnWO4 aremore reactive inNaOH solutions. Froma thermodynamic point of view, tungsten ore decomposes easily in acid solutions despite most ΔGo T increasing slightly with temperature. Oxidizing Fe2+ to Fe3+ in acidic solutions facilitates decomposition of FeWO4, and the reaction of CaWO4 in H2SO4 solution occurs more easily than in other mineral acids, due to the formation of sparsely soluble CaSO4. The results fit well with the experimental data and industrial experience previously reported in the literature.

By R. T. Seaman

Pressure oxidative treatment of whole ores and/or mineral concentrates is used to leach or liberate metals of value for downstream recovery. Silver, when present, is often lost in processing, precipitating as a cyanide-insoluble jarosite in the residue. Depending on pressure oxidation conditions, the degree of silver loss to jarosite can vary dramatically. Batch bench-scale testwork is often performed to define that loss, and then assess the implications in continuous operations. This paper focusses specifically on the impact of CESL pressure oxidation conditions on silver recovery, and discusses limitations of batch bench-scale testing as well as means of overcoming these limitations to better predict silver recovery in the scale up from bench-scale to continuous operations. Since silver is only partially soluble in both sulphate and chloride media, it will gradually leach and deport to a jarosite as oxidation progresses. When a silver-insoluble anion, for example iodide, is dosed prior to oxidation, there is a marked improvement in silver recovery from batchgenerated residue; however, that benefit is not consistently seen in continuous operations. The difference has been attributed to the dynamic solution conditions in the batch test, specifically the first few moments of oxidation. Using these principles, a predictive correlation has been established between initial leach concentrations of iron and acid and ultimate silver recovery with iodide addition.

By Thomas Weyand, Thomas Claridge, Dale Nickels

"This paper addresses the initial results of a project to evaluate the suitability of copper mining tailings as raw material for the production of structural products using PMET’s patented technology. Preliminary testing indicated that high performance structural products were possible using these materials. A demonstration scale project produced approximately 1,500 bricks in various colors. These products fall under under ASTM C- 73 and were found to present properties suitable for severe weather applications. Although the products in this project were of typical brick dimensions, other products are possible, for example concrete block substitutes or pavers. These products from the PMET process are commercially known as Brixx. This paper will provide operational details of the production process, mineralogy and mechanical properties of the products.INTRODUCTIONPMET has developed process technology that can convert various siliceous waste materials into competent structural products. This technology is the subject of US patent # 6,068,803. In general, the process consists of mixing lime, water and the major feed stock, pressing to form a “green” shape, and curing the product in an autoclave for 6 hours with saturated steam at ~200oC. The curing process forms Tobermorite, which acts as a crystalline binder. Freeport-McMoRan approached PMET to see whether mine tailings from the Sierrita mine, containing significant amounts of clay, might be a suitable feed material for the production of structural products. “Brixx” is the commercial term used to describe the resultant structural product formed in the test work. This paper is a preliminary evaluation of a technology that is being considered by Freeport-McMoRan. This report is not an endorsement by Freeport-McMoRan of the process or products, nor is it a commitment to use this technology."

Jan 1, 2008

Based on experimental and computer simulation results from our group, we report a systematic, atomic level analysis of carbon dissolution from carbonaceous materials in molten iron. Experimental results on graphite / Fe-C-S system were obtained using carbon dissolution studies, XRD and FESEM investigations and were supplemented with Monte Carlo simulations. Three basic mechanisms, namely carbon atom dissociation rate, interfacial phenomena and mass transfer in the melt were found to be responsible for the overall dissolution process. While mass transfer in the melt is governed by the concentration gradients, melt composition and temperature; impurities present in ash play a significant role in the interfacial phenomena. For less ordered forms of carbonaceous materials, carbon atom dissociation rate depends strongly on the degree of long-range order and is an important rate controlling mechanism in the overall dissolution process. A systematic comparison of dissolution rates for a variety of coal-chars, natural and synthetic graphites has been carried out in an attempt to identify rate-controlling mechanisms. The structure of the carbonaceous material appears to be an important underlying factor in the carbon dissolution process.

Jan 1, 2003

By R. L. Nyirenda

One of the problems with ammoniacal-ammonium carbonate leaching of EAF carbon steelmaking flue dust is that zinc present in spinel phases is not leached. This paper presents results of test work in which prior to leaching, EAF dust was reduced with CO containing gas to decompose the spinels into zinc oxide and iron bearing phases, mainly metallic iron and wustite. From such reduction products, the amount of zinc leached increases but the iron co-leached becomes extensive. The effect of various leaching parameters such as liquor concentration and redox potential on zinc and iron dissolution has been investigated. Supplementary experiments utilizing pure zinc oxide and pure iron phases were also carried out. Results show that the co-dissolution of iron from severely reduced EAF dust cannot be prevented. This is because the wustite phase contains zinc which can only be leached when iron also dissolves. Further, the zinc bearing wustite phase is not totally soluble so that the residue cannot be made zinc free. In the absence of air, dissolution of metallic iron hardly occurred, though in leaching experiments of a long duration its transformation to a spinel structure was observed.

Jan 1, 1992

By R. H. Crist

Reactive components of algal cell walls include uronic and alginic acids: In addition, many marine species have half ester sulfate groups which function as fixed anions. Associated metals vary with the media, eg., Ca and Mg in fresh water (FV) and Na, Ca, Mg in seawater. . These metals readily exchange with aqueous phase protons or metal cations. A plot of the total amount of metal cations displaced by protons vs .. pH shows one inflection at pH 4 for FV algae and' in addition a second inflection at pH 2, 3 for marine algae. The first inflection is interpreted as. Indicating the cations associated with carboxyl groups ,and the ,second with half ester ?Sulfate groups. The exchange capacities of various aigal ,species vary widely. When FV algae is placed in a Pb2+ solution,- the amount of Pb2"' deposited on the algae is. Equivalent to the. Total Ca2?, Mg2, and H+ displaced? thereby confirming the ion exchange mechanism. Ion exchange equilibrium constants are reported for the displacement of ca2+ from Vaucheria. With Mg2+, sr2+, Cd2+, Pb2+_ and Na+ as well as the reverse reactions. Cd2+ can .be removed partially from algae by precipitating it as CdS or Cd(OH) 2 Pb2+ and Cu2+ are also partially removed as the hydroxides. Rates of reaction for various alkali hydroxides decrease with increasing .unhydrated cation radius. It is concluded that theory is useful in predicting viable applications for algae in pollution abatement.

Jan 1, 1991

By Kenneth McGowan

"The aluminum industry is the 5th largest consumer of energy and the largest consumer of energy on a per-weight basis. Process heating accounts for 25% of the energy consumed to manufacture aluminum. Consequently, the generation of this energy results in the production of a significant amount of CO2 (over 3.75 million metric tons in 2003)1. As a result, the Aluminum Industry Technology Roadmap of 2003 listed the development of improved refractory materials as a goal to reduce energy use and decrease greenhouse gas creation. The result of a R&D effort addressing this desire is the development of patented microporous refractory materials for metal contact applications in all furnace areas including the belly band. It has been demonstrated that this material can reduce energy consumption up to 38% in furnaces and significantly reduce heat loss in launder and trough systems. Furthermore the material developed is non-wetting and remains un-penetrated by metal throughout its lifetime. The material does not contribute to the formation of corundum. As a result, the energy efficiency of an older lining remains intact compared to standard refractory materials which may have an initial high insulating value (such as lightweights and board) or standard dense refractory (even with penetration inhibitors) both of which show a rapid increase in thermal conductivity as the refractory is penetrated with aluminum and formed corundumIntroductionThe aluminum industry is the second largest producer of metal in the United States, behind the iron and steel industry. It is the 5th largest consumer of energy and the largest consumer of energy on a per-weight basis. Process heating is required to melt, hold, purify, alloy, and heat treat the metal and accounts for 25% of the energy consumed to manufacture aluminum. As such, process heating is the second largest energy consuming operation. Smelting, which utilizes an electrolytic reduction process is the largest energy consuming operation1.Most process heating is accomplished through the use of fossil fuels, either directly or indirectly. The choice of fuel is dependent on a plant’s location and fossil fuel availability. Table I shows the processes impacted by refractories and the calculated BTU’s generated by usage of the respective fuels as well as the Metric Tons (MT) of metal passed through each process in 20001."

Jan 1, 2009

By Kotaro Ogura

"The electrolysis process in which CO2 is selectively reduced to C2H4 at a three-phase(gas/solution/metal) interface on a copper-mesh electrode has been developed in a concentrated solution of potassium halide. At open-circuit potential, CO2 is captured on the electrode by being inserted into the double-layer consisting of halide anions specifically adsorbed and potassium cations which are located in the Helmholtz inner and outer layers, respectively. CO2 thus activated is subjected to the electrochemical reduction. In the early stage of reduction, CO2 is converted to formate radicals that are adsorbed on the electrode by taking the place of halide anions. The reductive coupling of these radicals results in the formation of intermediates such as -CH2C(O)- and CH2=CH-, and C2H4 is finally produced. The catalytic activity of the electrode process involving the insertion of CO2 into the double layer is not deteriorated at all during the electrolysis, and the continuous reduction of CO2 to C2H4 is possible with the addition of inorganic acid under the assistance of natural energy.Carbon dioxide is a serious pollutant released from fossil fuel power station, internal combustion and many industrial operations. The easy release of CO2 to the air has caused the global warming, and the technique which intends to curtail CO2 by pushing it back into the ground has been suggested. However, this problem should be greatly mitigated if CO2 can be converted to innocuous substances. Especially, the reuse of CO2 as fuels and chemicals is extremely effective not only for the mitigation of the global warming but also against the depletion of the fossil fuel reserves. Several processes for converting CO2 to valuable compounds have been proposed including hydrogenation over heterogeneous catalyst at high temperature and electrochemical and photochemical reduction. In the conversion and cutback processes of CO2, however, it is of importance that the process is feasible under mild conditions, because the secondary generation of CO2 is feared if high energy is required and supplied with a fossil fuel. In this meaning, the electrochemical reduction of CO2 taking place at room temperature, which is similar to photosynthesis, is promising. From the practical point of view, it is further necessary that the conversion rate is high enough and the product is satisfactorily valuable."

Jan 1, 2008

By A. E. M. Warner

Inco Limited has long and extensive experience in converting nickel-copper primary smelting mattes over a broad range of nickel/copper weight ratios and combined nickel-copper-cobalt contents. At the Copper Cliff Smelter, the composition of the converter product matte has to meet the requirements of the matte separation process; at the Thompson Smelter, converter matte of a different composition is cast into anodes for nickel electrorefining; and in Soroako, Indonesia, a very low copper product matte is granulated for the Japanese market. Recently, Inco has conducted pilot plant testing of three possible nickel-copper matte continuous converting routes, namely flash converting, oxygen top blowing-nitrogen bottom stirring, and tuyere blowing. This test work has generated substantial new information on nickel-copper matte converting chemistry. This overview paper reviews the metallurgy of nickel-copper matte converting, in particular the behaviour of cobalt and the operating conditions required to meet the iron and sulfur specifications of the product matte. The relevant thermodynamic information is used to discuss the industrial data.

Jan 1, 2003

By E. Maziar Sauber

In order to prepare a more desirable feedstock for a rare earth elements separation refinery, cerium, a penalty element in the refinery feedstock, should be removed from the mixed rare earth elements oxide or carbonate feedstock. In this study, cerium (III) to cerium (IV) oxidation by calcium hypochlorite and subsequent precipitation was used to remove cerium from a mixed rare earth elements chloride solution. A factorial design of experiments was used to determine the effect of process variables such as temperature, pH, and oxidizer addition on the oxidation of cerium (III) using synthetic solutions. Under certain test conditions, all of the cerium was successfully removed from the chloride solution, and some REE accompanied cerium and reported to the precipitate. This proposed technology can allow for low cost removal of cerium from mixed rare earth elements chlorides.

By Ximeng Zhu

The electrochemical behavior of mineral and coal pyrites in stirred and quiescent alkaline boratelsulfate solutions @H 7.9-10.5) have been investigated using cyclic voltammetry. Significant differences in the electrochemical response of these pyrites were observed. At the mineral pyrite surface, three anodic peaks at about -0.8 V, -0.1 V and +0.5 V (SCE) have been detected along with their corresponding reduction peaks. The first two peaks correspond to FeIFeOI) and FeOI)lFe(III) oxidation. The third peak is present for quiescent conditions but disappears as a distinct peak when the electrolyte is stirred. In the upper voltage region +0.30V (SCE), the current increases markedly during stirring and the reactions correspond to the oxidation of pyrite with the formation FeOII) oxides plus elemental sulfur. Also there is evidence that Fe oxy-ions form. Coal pyrites, under rapid sweep conditions display only the first two anodic peaks, the associated reduction peaks and an additional reduction peak corresponding to one or more of the high voltage oxidation products. After prolonged exposure to high potentials, coal pyrite displays reactions similar to those of mineral pyrite but at much higher current densities demonstrating the much higher reactivity of the coal pyrite. The reactivity sequence was Upper Freeport coal pyrite > Pittsburgh coal pyrite > mineral pyrite.

Jan 1, 1991

By Akio Ohta

The Hyuga smelter has been producing ferronickel by a rotary kiln-electric furnace process in Miyazaki, Japan. Several approaches to improve our operation have decreased the electrical energy consumption. A new process was developed to decrease the cost of energy even further. Oil and technical oxygen are injected through lances to heat up the calcined ores (calcine) instead of the electric power. Main problems during the development of the process were the short life of the water-cooled lances, the check on security of the safety system and the eruption of combustion gases through the calcine bed. These problems have now been overcome successfully, and stable operation can be maintained. The addition of 1 Litre of heavy oil per tonne of ore can save the electrical energy requirement by 8.6 kwh per tonne of ore. The new process has resulted in a reduction of the electrical energy consumption by more than 10 percent

Jan 1, 1992

By D. Bruce Wilson

The reaction of oxygen and solid aluminum produces the well-known surface coating of aluminum oxide, Al2O3. Thermodynamic properties and kinetic mechanisms of this reaction are extensively documented. Less well-defined are the corresponding liquid phase reaction and reactions which would be characterized. as 'burning' of aluminum. This paper reviews the solid aluminum-oxygen reaction as a foundation for discussing the flammability of aluminum in oxygen-enriched atmospheres. Appropriate thermodYDan3ic analysis and kinetic reaction mechanisms are developed. Available models of aluminum burning are reviewed and evaluated, The appropriate information for design of engineering applications of aluminum in oxygen atmospheres? is summarized.

Jan 1, 1996

By P. J. Mackey, J. B. See, D. G. C. Robertson

The production of iron and steel and non-ferrous metals by pyrometallurgical processes will remain a critical element in meeting the demand for materials in both developed and developing nations. Given the important need to reduce and minimise greenhouse gas emissions the technological focus of future pyrometallurgical R&D by universities and industry alike must concentrate on sustainability issues such as improved energy efficiency, recycling and waste minimization. Continued efforts are also needed on process optimization and new process development with a view to reducing capital and operating costs of the new large “mega” plants. Using the academic and industrial backgrounds of the authors, the present paper reviews the current status of R&D in pyrometallurgy in university departments with a particular emphasis on sustainability issues. The role of industry and government laboratories is also reviewed although primarily for developed countries. The paper also includes comments and suggestions on the future requirements for education and R&D in pyrometallurgy in developed countries to maximise sustainability. It is also suggested that future R&D in pyrometallurgy will be even more concentrated in developing countries – most notably China.

Jan 1, 2014

By M. Jortikka

The smelting process of the old reverberatory furnace including its capacity has been improved over the years in different ways eg. with oxy-fuel burners, parallel reactors with the reverb or with various modifications of the reverb furnace itself. The future reverb modifications with old concepts are difficult or impossible as the increased copper losses in slag call for separate slag treatment and particularly the process modifications do not solve the environmental issues but instead mean unavoidable high capital and operating costs in gas cleaning and sulphur recovery. During the last decades improvement in process performance and increase in capacity of copper flash smelters has been achieved easily by substituting the pre-heated process air by highly oxygen enriched air. The flash furnaces of today, however, are inherently designed to operate with high oxygen enrichment. Further process improvement with a view to production costs and capacity increase as well as to the more stringent environmental requirements is possible with even higher oxygen enrichment. This, apart from the advantages it generates, requires improvements in and careful design of the feed system, concentrate burner, furnace cooling and the off-gas line as well as adaption of the flash converting instead of the conventional Peirce-Smith converters. A logical answer even for the revamping of the reverb smelters in the future is the total replacement of the reverb furnaces with flash smelting together with flash converting. This paper discusses the possibilities for future process improvements of the existing flash smelters taking into account the process concepts, equipment modifications and capital aspects not forgetting the environmental issues. The revamping of the PASAR smelter in Philippines is introduced as an example of a recent success story.

Jan 1, 1994

By B. R. Davis, Neale R. Neelameggham, R. E. Brown

The element Calcium element has a unique place in the production of etals, intermetallics and other compounds. The unusualness arises from the fact that we have several possible reductants – metallic calcium, calcium carbide, calcium cyanamide and calcium hydride. A review of how metallic calcium is manufactured and utilized is presented. The difficulties involved in producing the metal in large quantities and price implications are noted. . Fundamental thermodynamics of how these act as reductants are shown, along with the historic application of these in metal production during the past century and a half. Alternate applications as to how to control the cost of the reductant is indicated, such as the numerous attempts in making low cost titanium utilizing direct or indirect calcium reductant.

Jan 1, 2014

By Richard W. Lawrence

Leaching of copper from sulfide minerals using biooxidation offers a potential route for copper recovery. Oxidation of . sulfide sulfur can proceed either; to sulfate or to elemental sulfur depending on mineralogy and process conditions. The advances in commercial application of biooxidation for sulfidic gold ores has made available operating and cost data which allow the derivation of conceptual costs for copper ore processing for comparison with conventional processing routes. Although costs for copper biooxidation generally remain high relative to conventional smelting, application might be competitive in specific cases. Biooxidation becomes more competitive in the general case if the cost ofS02 emissions in pyrometallurgical processing were to be internalized to a greater degree than currently required. This paper describes the technical aspects of biological processing of copper sulfide ores and concentrates, specifically with respect to the fate of sulfur. The environmental and economic implications of the biooxidation route are discussed in relation to conventional processing.

Jan 1, 1996

By Jürgen Antrekowitsch, Thomas Griessacher

"Heavy metal containing residues are typically hazardous wastes because on the one hand, a deposition gets more and more complicated and on the other hand, the large amounts of metals like Zn, Cu, Fe and Pb represent a significant value. Thus, a post-treatment of these materials with the recovery/recycling of the metals and stabilization of the waste is not only ecological but often also economical. The therefore typically applied recycling processes utilize pyrometallurgical steps, where carbon or carbon monoxide from fossil coal and coke is used as a reducing agent, which results in large amounts of CO2 emissions. An alternative option is the application of a hydrogen-rich gas emitted in biomass utilization processes as a carbon-neutral reducing agent. Investigations in a retort process which were done at different temperatures and times showed excellent results concerning the achievable reduction rates and final contents of the heavy metals for various residues.IntroductionNowadays heavy metal containing residues like electric arc furnace dust (EAFD), dust from cupola furnaces, waelz slag, etc. are declared as hazardous wastes in a growing number of countries due to the leachability of the heavy metals in these residues. For that reason it is no longer possible to landfill these materials or use them for road construction or disposal works. Some land filling activities, carried out until now, have only been realizable because of some process modifications or cost intensive post-treatment steps of these residues. But the disposal capacities for such materials are decreasing, therefore increasing the prices. The second point for the growing disposal limitations is the stringent environmental legislations and regulations, which restrict the number and amounts of materials which can be dumped [1 – 5].From the other point of view these heavy metal containing residues usually have high contents of zinc, lead, iron, etc., which represent a significant value and therefore a big potential to recover these metals. This is why in recent years the number of recycling processes and the amount of recycled heavy metal containing residues have continuously increased. These recycling processes have the target to recover the valuable metals from the residual materials in the form of a saleable product as well as the stabilization of the slag produced in these processes [5, 6]."

Jan 1, 2011

By A. E. M. Warner

In co Limited has long and extensive experience in converting nickel-copper primary smelting mattes over a broad range of nickel/copper weight ratios and combined nickel-copper-cobalt contents. At the Copper Cliff Smelter, the composition of the converter product matte has to meet the requirements of the matte separation process; at the Thompson Smelter, converter matte of a different composition is cast into anodes for nickel electrorefining; and in Soroako, Indonesia, a very low copper product matte is granulated for the Japanese market. Recently, Inco has conducted pilot plant testing of three possible nickel-copper matte continuous converting routes, namely flash converting, oxygen top blowing-nitrogen bottom stirring, and tuyere blowing. This test work has generated substantial new information on nickel-copper matte converting chemistry. This overview paper reviews the metallurgy of nickel-copper matte converting, in particular the behaviour of cobalt and the operating conditions required to meet the iron and sulfur specifications of the product matte. The relevant thermodynamic information is used to discuss the industrial data.

Jan 1, 2003