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By Andrew Case

The Port Nickel facility in Braithwaite, Louisiana, is known for pioneering hydrometallurgical processes for the 'separation and recovery of nickel, cobalt and copper. Ten years ago, in 1985, a new CRI-MET process for the recovery of molybdenum, vanadium, nickel, cobalt and alumina from spent catalysts was developed and implemented. Spent- catalysts from the petroleum industry consietute the majority of feed. These are not only a valuable-source of metals, but due to EPA regulations are frequently classified as hazardous under RCRA. Molybdenum and vanadium are selectively leached in an oxidative hydrothermal step. Alumina is then extracted in a caustic digestive leach. The unique technology produces four primary commercial products l molybdenum trioxide, vanadium oxide, aluminum trihydrate and nickel-cobalt concentrate. This paper discusses the process, modifications. during ten years of operation, and the relationship of these modifications to the future of the catalyst recycling business.

Jan 1, 1995

By Robert E. Moore

Synthetic spinel is proving to be a highly effective refractory for specific applications, but its cost limits applications. Formation of spinel from a raw material such as diaspore or bauxite could provide a simple and less costly starting material. In the study reported here, finely ground (-325 mesh) diaspore from Missouri and bauxite from Guyana and China are combined with hard burned MgO (-325 mesh) in appropriate proportions to yield spinel and spinel with secondary phases. A classical sintering and dilatometer study was completed, followed by a microstructure study to determine completeness of the reactions and morphologies of the reaction products.

Jan 1, 1993

By Richard B. Diver, Mark D. Allendorf, Daniel E. Dedrick, James E. Miller, Roy E. Hogan, Andrea Ambrosini, Eric N. Coker, Anthony H. McDaniel, Nathan P. Siegel, Gary L. Kellogg

"Converting carbon dioxide and water to hydrocarbons is an attractive option for storing solar energy and, coupled with appropriate CO2 capture technology, for recycling carbon and impacting atmospheric CO2 concentrations. For any process, high solar-to-fuel efficiency is necessary for large scale viability and favorable economics. Thermochemical approaches for solar-to-fuel conversion are potentially highly efficient as they avoid the inherent limitations of photosynthesis and also sidestep the solar-to-electric conversion necessary to drive electrolytic reactions. Solar-driven two-step metal-oxide-based thermochemical cycles for producing the components of syngas, CO and H2, from CO2 and H2O are the basis of the “Sunshine to Petrol” project. Multi-cycle production of both H2 and CO has been demonstrated over several iron- and cerium-based compositions fabricated into monolithic pieces both in the laboratory and at the National Solar Thermal Test Facility. These compositions are being developed for deployment in a unique and continuous solar-driven reactor prototype, the counter-rotating-ring receiver reactor recuperator or CR5.IntroductionThe interconnected challenges posed by increasing global competition for petroleum and the increasing concentration of atmospheric carbon dioxide are now widely recognized. Meeting these challenges requires recognition that although hydrocarbon fuels are ideal energy carriers, they can no longer be thought of as primary energy sources. It is necessary to take the realistic view that our conventional fossil fuels are in fact “stored sunlight” in the form of “sequestered carbon.” This view leads to a search for options to use and store sunlight more directly.Sunshine to PetrolIn combusting hydrocarbons we unlock the energy for utilization, but we also release the carbon to the atmosphere. However, nature teaches us that with an appropriate persistent energy source, e.g. solar irradiation, it is possible to effectively reverse the combustion process and “reenergize” CO2 and H2O back into hydrocarbon form."

Jan 1, 2010

By D. Papazoglou

This work was undertaken to investigate the thermodynamic and kinetic feasibility of using hot sulfur dioxide bearing gases from smelting processes to selectively sulfate the nickel in nickel laterite ores for subsequent extraction in water. The environmental benefits ofthis approach, as opposed to releasing the gas to the atmosphere, and the economic benefit of directly utilizing the S02 rather than converting it to sulfuric acid are strong drivers for such a process. A thermodynamic analysis indicated that selective sulfation of the nickel could be feasible under appropriate conditions and these were explored through a series of laboratory scale experiments. Laterite samples were reacted at temperatures between 500 and 800°C with an equilibrated mixture of sulfur dioxide, oxygen and nitrogen in a fixed bed reactor. Tests were conducted on saprolitic ore from Bulong, Western Australia, limonitic ore from New Caledonia and garnieritic ore from Indonesia. Nickel extractions were highest from the limonite and relatively low from the other ores. The maximum selective extraction of nickel from the limonite in a single stage sulfation was 73%. Sulfation of other elements present in the laterites was also examined. A two-stage process was also identified which involved sulfation using a strong sulfation potential followed by weaker sulfation potential to attempt to convert ferric sulfate formed in the first stage to ferric oxide. This increased the extraction for the limonite ore to around 84% Ni, 95% Co and 2% Fe. Direct sulfation of laterite could be feasible in locations where sulfide smelting or roasting operations are relatively close to laterite deposits.

Jan 1, 2003

By M. J. Adam

The U.S. Bureau of Mines has investigated the partitioning of complex minerals to simpler phases using sulfidation reactions for selective extraction of mineral values. This report describes research in which thermal processing of the complex Ti-bearing mineral ilmenite (FeTi03) resulted in partitioning of the valuable Ti metal to the simpler compound rutile (TiO2). Samples of ilmenite were blended with elemental S for thermal treatment at various temperatures under controlled atmospheres in an effort to dissociate the Fe from the ilmenite complex. Product characterization revealed that the Fe was partitioned 'from the ilmenite, forming a rim of pyrrhotite/pyrite (FeS/FeS2) on a rut il e core. The products were agate milled and then subjected to cursory magnetic and flotation techniques in an attempt to physically separate the partitioned phases. Partitioning results and phase concentration data are reported relative to thermal treatment variables and physical separation techniques.

Jan 1, 1991

By R. Steven Izatt

Green chemistry principles will be discussed, and examples will be given of the use of Molecular Recognition Technology (MRT) to selectively separate specialty metals such as cobalt, nickel, bismuth, rhenium, molybdenum, indium and germanium from various primary and secondary feed streams. Recovery of these metals has numerous advantages including (i) conservation of valuable resources, (ii) prevention of environmental damage, and (iii) elimination of capital and operating expenses due to re-processing or disposal of metal-bearing streams.

By Xuemei Zheng, Aiyuan Ma, Chao Liu, Guojiang Li, Chenyu Sun, Jinhui Peng, Libo Zhang, Yongguang Luo

In this paper, the removal of fluorides and chlorides from blast furnace dusts by water vapor enhanced microwave roasting was investigated, combined with the advantages of microwave selective heating and based on a thermodynamic analysis of zinc and lead halides. According to proposed reactions in the process, detailed experiments were systematically conducted to study the effect of roasting temperature, holding time, air flow, water vapor flow rates, and stirring speed on the efficiency of the removal of F and Cl. The results show that 97.26% of F and 64.23% of Cl could be separated when the condition of the roasting temperature of 650°C, stirring speed of 80 rpm, holding time at 60 min, air flow of 350 L/h and water vapor flow rate of 8 mL/min was optimized.

Jan 1, 2016

By John W. Ahlrichs

Microscope, electron microprobe and x-ray diffraction have been used to provide quantitative evaluation of products from the mill, smelter, refinery and other metallurgical processes. Phase compositions and their quantities are necessary for an adequate understanding of the various products obtained throughout an operation and in laboratory testing. By careful evaluation, important information can be gained in improving recoveries and increasing grades at various stages of processing. Four case histories are discussed in this paper. Quantitative microscopic counting techniques are applied to mill products to determine degrees of locking and liberation of the economic minerals. Rapid, but accurate evaluation aids the metallurgist to develop or improve the grinding and flotation circuits. In the smelter, the identification and quantification of the phases are important for predicting reaction mechanisms and kinetic trends. Mineralogic techniques have been applied to conventional smelter products, and to those obtained in laboratory tests for newly developed innovations to smelting. Small, but important, values of gold occurrences in ore are difficult to determine. Evaluation of gold usually requires special separations into various mineral concentrates, followed by assays and mineralogic determinations of the products. Numerous occurrences of solid solution constituents can be treated as by-products, but often they are deleterious to metallurgical treatment. Most solid solution problems can be unraveled by the mineralogist's tools.

Jan 1, 1981

By S. M. I Kytö, J .. K. Mäkinen, K. Saarhelo

"At the Outokumpu Oy Harjavalta Copper Smelter the control philosophy of the flash smelting process has been changed from the slow feed-back control to feed-forward control. This is important as the fluctuations in the flash smelting furnace matte grade and slag temperature are desired to be minimized.The system is based on a specially designed automatic sampling device and the Outokumpu Courier 20 on-stream X-ray fluorescence analyzer. A microcomputer-based Analyzer Operator Station (AOP) controls the system and calculates the process parameters for the furnace from the analyzed chemical composition and other existing data.A considerable reduction in the deviation of the matte grade and slag temperature has been gained. This has resulted in conservation of energy and refractories, lower copper losses and higher through-put in the flash smelting furnace and converters.1.0 IntroductionThe flash smelting technology for copper concentrates was developed at the Outokumpu Oy Harjavalta Smelter soon after the World War II. The incentive for this development was shortness and high price of any form of energy. The fact that smelting can be carried out autogenously, without external energy by utilizing the latent heat of sulfide combustion was known decades before, but Outokumpu Oy was the first company to take the advantage of this knowledge in practical operation. A further advantage of this technology was that the SO2 containing gases suited well for sulfuric acid production, thus minimizing the detrimental effects on the environment (1).The very heart of the flash smelting process is the reaction shaft of the flash smelting furnace (see Appendix I). Heating up of the dried feed mixture, dissociation of several compounds, ignition and oxidation of the feed take place very intensively in the reaction shaft during 2 - 3 seconds, which the fine grained particles reside in the reaction shaft. A very accurate control of the amounts of the feed materials as well as of oxidizing gases, fuel, etc. is of primary importance."

Jan 1, 1989

By R. Boom, Y. V. Meteleva-Fischer, B. Kraaijveld, H. Kuntzel

"Segregation of impurities during refining of metallurgical grade silicon (MG-Si) is an option to produce solar grade silicon (SG-Si). Directional solidification is a last step in production of SG-Si effective for removal of metallic impurities. The possibility is investigated to use metallic impurities originally present in MG-Si for removing boron and phosphorus. MG-Si has been treated using two methods: 1) alloying with calcium and 2) refining with Na2O-CaO-SiO2 slag, both by controlled cooling. The microstructure of silicon and the impurities distribution have been studied before and after the treatments. Using EPMA phosphorus and boron have been detected in 1-2 wt% concentration range in several intermetallic compounds in grain boundaries after both treatments. This observation points to a different possible mechanism of silicon refining from boron and phosphorus. Controlled cooling improves migration of phosphorus and boron to the silicide phases in grain boundaries, which can be removed by acid leaching treatment.2. IntroductionStandards for silicon solar cells and growing demand on “green” energy require economical and efficient route to the production of solar grade silicon. Refining of cheap metallurgical grade silicon is one of the promising options, where application of existing metallurgical approaches can result in cost-efficient production on industrial scale. Focus in refining is on impurities, which are most difficult to remove: B, P, Al, Ti, due to their large segregation coefficient in silicon and low vapour pressure [1]. Moreover, more environmentally friendly technology in comparison to the traditional Siemens process [2] will be in accordance with societal needs. Based on properties of common impurities in metallurgical grade silicon, alloying refining and slag refining are suggested as competitive techniques having potential effect on removal of impurities harmful for conversion of solar energy [3, 4]. Alloying with Ca followed by acid leaching was found to be effective for removal of Fe and Ti from silicon [5] and to enhance also removal of boron [6] and phosphorus [7, 8]. In the work of Inoue et al. [8] drastically increasing removal of phosphorus from silicon has been observed with an increase of Ca content and a thermodynamics-based explanation was provided. Since phosphorus has been found to condense in the secondary precipitate mainly composed of CaSi2, it can be removed together with iron and titanium by consecutive acid leaching treatment. Slag refining is one of the metallurgical methods proposed to be effective for refining of metallurgical grade silicon from boron [9, 10]. Slags with additions of the following oxides to silica have shown positive effect on removal of boron: CaO [11-13], Na2O [11,14]. Mechanism of slag refining from boron is based on oxidation of boron followed by its incorporation in the slag network [9,11]; the same mechanism is suggested for refining from phosphorus taking into account that oxides of boron and phosphorus are known as network-formers [15]."

Jan 1, 2012

By M. Okido, O. Takai, Z. Zhao, M. Ishikawa, R. Ichino, K. Kuroda

"Electrolytic method was applied to calcium phosphate coating on titanium plates as an excellent technique for high density and intensive contact of coated films on biomaterials. The effect of H2O 2 as oxidation reagent on coating characteristics was examined to obtain biomineral films. Solution was containing 7.0 X 10·3 mol/dm3 ofCaC12 and 3.0 X 10·2 of Ca(H2PO4)z, kept at 55 ""C. All deposits were hydroxyapatite (HAp) in this study, independent of H2O 2 concentration, applied cathodic potential and solution pH. In the case of H2O 2 addition, an increase in cathode current started at the low potential, namely, ca. -0.2 V (vs. SCE). In contrast, the current increased at more than ca. -1.4 V in the solution without H2O 2 addition. H2O 2 appeared to be an effective reagent for increasing nucleation density and improving adhesion of deposits on titanium plates.IntroductionIn recent years, many researches have been undertaken to develop the techniques of calcium phosphate coating on titanium or bioglass for medical implantation. High density and intensive adhesion of coating are necessary for adding bioaffinity to these materials and for inducing bone morphogenesis on them when implanted in human body.1) Electrolytic deposition has been a newly developed method as high-speed deposition process. By this method, the supersaturation of calcium phosphate can be increased just in the vicinity of metal substrates and the heterogeneous nucleation is promoted on them. In this process, H2O is reduced according to eq. (1) on the cathodically polarized electrode"

Jan 1, 2000

By John J. Dunkley

Recent years have seen the increased use of hydrometallurgy in the smelting and refining of metals. However this is often used as a final refining step, following an initial pyrometallurgical smelting process. Huge amounts of material are produced as melts which have to be cast, comminuted, and taken up into solution or leached. A common method is to granulate the melt and then grind it. In the case of metallic melts this can be difficult or unfeasible due to the ductility of the granulated particles. Water atomisation is capable of replacing the granulation and grinding stages with a single process step that can process in excess of 30t/hour of melt into particles as fine as 50 microns. Applications in operation in Co, Cu, Ni, Ag, Au, Pt and Rh refining are discussed together with potential applications in copper smelting.

Jan 1, 2003

By Guan-zhou Qiu, Shui-shi Liu, Yu-feng Guo, Tao Jiang

"The preparation of high-quality synthetic ruitle from electric furnace titanium slag was systematically investigated by activation roasting followed by acid leaching process. The results showed that impurities such as Ca and Mg in titanium slag can be effectively removed and TiO2 grade of the product was markedly improved by the process. High-quality synthetic rutile containing 88.54% TiO2, 0.42% (CaO+MgO) was obtained under the conditions that roasted with 7.5%(wt) H3PO4 at 1000 oC for 2h, followed by two-stage leaching in boiling dilute sulfuric acid for 2h. Mechanism studies showed that anosovite solid solution and silicate minerals were reacted with phosphoric acid in the roasting process. As a result, titanium components in titanium slag turned into rutile (TiO2) and impurities were transformed into acid-soluble phosphate and quartz.IntroductionWith the gradual depletion of natural rutile and the rapid development of titanium industry in China, the natural rutile reserves cannot satisfy the requirement for production of titanium pigment and titanium sponge. Ilmenite is, therefore, becoming main raw material for titanium industry. However, because of its low TiO2 grade, it generally requires preconcentration to titanium-rich material such as titanium slag or synthetic rutile [1-3].Ilmenite resources are extremely rich in Pan-xi area of China, which account for 90.54% of total ilmenite reserves in China [4]. The titanium slag produced by electric smelting of ilmenite concentrate has high contents of Ca and Mg, and is not suitable as a raw material for chloride process and titanium sponge production. Therefore, upgrading titanium slag to prepare raw material suitable for chloride process and titanium sponge production has important significance for the development of China's titanium industry."

Jan 1, 2011

By Chris Twigge-Molecey

As emission constraints for metallurgical plants become more difficult to meet; control of major, multi-vessel, flue systems become more critical. Control instabilities can result in significant loss of system capacity or emissions to the environment. This paper will discuss the use of dynamic simulation techniques to optimize both the design and control strategies for these systems. A significant ,safety hazard is associated with pressure excursions from process upsets or equipment failures. Pressure rise rates of up to 10 kPajsec can occur. These cannot-be followed by conventional controls. Fail-safe high speed venting is required to protect both the furnaces and operating personnel'. Design options, sizing techniques and practical problems are discussed.

Jan 1, 1992

By Harsh Deep Chopra, Jason N. Armstrong, Susan Z. Hua

"Existence of anisotropic Curie temperature materials [E. R. Callen, Phys. Rev. 124, 1373 (1961); J. Appl. Phys. 32 S221 (1961)] is a longstanding prediction - materials that become paramagnetic at a lower temperature along certain crystal directions while remaining magnetically ordered in other directions up to a higher temperature. Validating Callen's theory, we show that all directions within the basal plane of monoclinic F e1Ss (pyrrhotite) single crystal remain ordered up to 603 K while the c-axis becomes paramagnetic at 225 K. Results prompt a re-evaluation of existing magnetic materials with a focus on magnetic characteristics along different crystal orientations above instead of below the ordering temperatures. Theoretical guidelines for identifying new materials with large anisotropy of Curie temperature are also given, and analysis protocol to characterize them in a self-consistent manner is discussed. Materials with such a large directional dependence of Curie temperature open the possibility for uniquely new devices and phenomena, including energy storage and spintronics devices.IntroductionThis paper is an overview of our recently published work on anisotropic Curie temperature materials [l]. As a background, ferromagnetic and ferrimagnetic materials are characterized by a critical temperature below which magnetic interactions prevail over thermal agitation, leading to the appearance of a spontaneous magnetization. Above this critical point, called the Curie temperature, thermal energy eventually overcomes magnetic interactions and the material becomes paramagnetic.It is less well known that the Curie temperature varies with the orientation of the crystal. In ordinary ferromagnets this orientation dependence of Curie temperature is negligible because of the vanishingly small ratio of anisotropy to exchange energy, i.e., the spherical or isotropic exchange term dominates. Thus Curie temperature in ordinary ferromagnets appears to be an isotropic property, and assigning it a single characteristic ordering temperature suffices. However, a 'small' difference is not equivalent to being the 'same', and under appropriate set of conditions the anisotropy of Curie temperature is predicted to become appreciable, as discussed in the following.In formulating the theory of 'anisotropic magnetization' [2, 3] E. R. Callen and H. B. Callen first discussed the ""interesting possibility"" of anisotropic Curie temperature [2] or ACT; Callen and Callen noted that it was W. J. Carr, Jr. who initially raised this question, and they discussed it in detail at the Conference on Magnetism and Magnetic Materials (NY, November 1960), see footnote on page 320 of Ref. [2]. Soon thereafter, E. R. Callen developed the theory underlying the anisotropy of Curie temperature and conditions conducive to its observation [4, 5]."

Jan 1, 2013

By M. W. Kennedy

Prediction of the thermal duties of copper coolers in freeze lined furnaces is challenging. Where copper coolers are immersed in liquid slag the heat transfer is often defined by a natural convection cell immediately adjacent to the wall, in the absence of other factors producing forced convection. Slag coolers are typically not fully immersed, slag temperature, liquidus and superheat can vary, and bath levels may change significantly with batch tapping, leading to substantial variations in radiation heat fluxes. Radiation heat transfer is discussed with reference to the non-obvious impact of slag liquidus on radiation losses in the exposed cooler sections. Reference is made to literature and the results of analytical and FEM models.

By A. S. Usrnani

Due to both turbulence and the highly variable geometry of castings, a realistic numerical simulation of the metal flow is prohibitvely expensive with current technology. However, when the chief purpose is to achieve realistic thermal fields a precise How simulation is not necessarily required. In this paper we assume a laminar flow regime and obtain the flow field by solving the incompressible Navier-Stokes Equations using a velocity-pressure segregated semi-implicit finite element method. The free metal surface is predicted by advecting a pseudo-concentration function via the computed How field. This involves an explicit finite element solution of a pure advection equation. The thermal field is calculated by solving the convective-diffusive energy equation by an explicit finite element method using the computed flow field and the location of the free surface. All the advection terms are discretized using a Taylor-Galerkin method. The interface between the metal and mould is modelled using special interface elements. The model is demonstrated by solving practical example problems. The results show that a sharp thermal front is maintained during the course of filling without excessive diffusion. The heat diffusion in the mould can be controlled by varying the metal mould heat transfer coefficient.

Jan 1, 1994

By Akira Yazawa

Experimental results for the distribution ratios of various elements between the slag, matte and/or copper in the silica-saturated copper smelting system were summarized. The experiments were carried out under an oxidative smelting condition with S02 gas flow, and also a reductive smelting condition equilibrating with metallic copper or iron. To evaluate the results thermodynamically, the availability of one atom cation base expression for the constituent compounds is emphasized from both of theoretical and practical standpoints. Both of oxidic and sulfidic dissolutions in slag are postulated for some elements such as copper, nickel and lead., and the experimental results are reasonably explained thermo-dynamically. The results for the mutual solubility between matte and ferrite slag and the distribution of minor elements between liquid copper and ferrite slag are also discussed.

Jan 1, 1983

By J. C. Agarwal

Slags produced by modern smelting furnaces contain copper values which are unacceptably high for discard. The electric arc furnace is employed commercially to clean copper from flash furnace slags but the addition of highly oxidized converter slags to an electric furnace has created operational problems. Highly oxidized Noranda Reactor slags have not been processed successfully in a pyrometallurgical process. These slags, which contain large concentrations of copper (5 to 10 per cent), are treated in slag concentrators (controlled cooling, crushing and milling, and flotation) which produce a copper concentrate that must be resmelted. Though commercially operable, it will be shown that the slag concentrator has important process and cost disadvantages as compared to a pyrometallurgical process. In this paper an economic comparison is made between a pyrometallurgical process and the slag concentrator. For the analysis, five hypothetical smelting plants are considered. Each plant treats 1200 tons of copper concentrate per day and produces 109,000 tons of copper annually. The plant configurations used in this study are:

Jan 1, 1976

By Hong-ying Xia, Bao-bao Wang, Jin-hui Peng, Bing-guo Liu, Li-bo Zhang, Zhi-qiang Li

Based on optimization using response surface methodology designed by Box- Behnken, to study the interaction of wet industrial salt with moisture drying temperature (50-90 ); duration (10-50s); and the weight of the materials (20-60g). The results show that: the experimental parameter conforms to the quadratic equation model to influence the moisture content and the dehydration speed., in analyzing the significance and the interaction of various factors, the optimum by the Design Expert software conditions for drying with microwave radiation include temperature of 90 , duration of 10s, and sample mass of 26g. Verified by experiment, the moisture content after drying is less than 0.25% and the dehydration rate reached 1.37g/min, between the predicted value and the actual value confirmed good fitting degree.

Jan 1, 2015