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By Takeshi Nagano

Copper pyrometallurgy in Japan has experienced quite fundamental changes in last fifteen years. The severe environmental restriction coupled with increase of energy costs accelerated the development work of the new continuous process in Mitsubishi Metal Corporation. After several years of pilot plant test work the commercial plant was put into operation at Naoshima Smelter in 1974, the design capacity of which was 4,000 tonnes of copper per month. Many modifications and improvements have been incorporated into the process and 7,200 tonnes per month of copper production was achieved in 1983, proving that continuous process was much more economical than conventional process. It is now possible to design and operate the continuous process in wide range of capacity. This paper will review the process and describe the progress of the process in these 10 years. 311

Jan 1, 1985

By Karl A. Gschneidner

The magnetocaloric effect has been known for 120 years and has been utilized for cooling about 70 years. But in the last four years significant advances have been made to show that magnetic refrigeration is a viable and competitive cooling technology. Most of the work has focused on reciprocating devices, but rotary apparati are being developed. To date the magnetocaloric properties have been characterized for more than 200 materials. The magnetocaloric effect behaviors have been classified into three types of behaviors. The most common one is found in magnetic materials which exhibit a second order magnetic phase transition. Magnetic materials which exhibit a first order magnetic phase transition account for the second group of materials. Materials which exhibit multi-magnetic phase transitions make up the third group. The best candidate materials for magnetic cooling over the range from -4 to -1 350 K are also presented.

Jan 1, 2002

By S. E. Khalafalla

A method for preparing ferrochromium alloys containing less than 2 pct carbon has been devised in a single vacuum furnace reactor. This method can conserve chromium and should reduce the capital and energy requirements relative to chromite electrothermal reduction. Reduced products containing less than 2 and as low as 0.01 wt pct carbon were obtained by reacting pellets of chromite and carbonaceous reductant mixtures at pressures of 0.1 to 1 ton and temperatures of 1,230° to 1,320° C. The extent of reduction increased with increased temperature and decreased pressure; however, operating conditions were limited due to the onset of significant chromium vaporization at higher temperatures and lower pressures. Foundry coke, anthracite, and carbon black were found to be superior to graphite as reductants. The reduction of chromite to metallics was found to proceed via the carbide intermediates Fe3C or Cr3C2. Lime accelerates the. rate of solid state reduction of chromite and can shorten the furnacin1r time at 1,3000 C under vacuum from 13 hours to less than three hours. Additional lime and silica are added to the hot reduced chromite after releasing the vacuum and raising the furnace. temperature to 1, 700° C. Soaking the charge for about 20 minutes gave a button of low carbon ferrochromium alloy beneath a well-defined slag layer.

Jan 1, 1985

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 G. W. Barton

Process Systems Engineering (PSE) can be defined as the integrated usage of computer-based design and analysis tools. As such, PSE is becoming increasingly important in the chemical and petrochemical industries. This paper shows how a range of PSE techniques have been applied to the zinc electrowinning process. Topics discussed include model development, parameter estimation, steady-state and dynamic model applications, steady-state optimisation and neural network modelling.

Jan 1, 1994

By B. Madelin

Over the last ten years, Minemet Recherche and Metaleurop have used an approach in order to investigate and improve the operation of its Smelting furnace and its lead blast furnaces. This approach gives importance- to three complementary means of investigation : - Probing campains in the industrial furnace (temperature and gas analysis profiles), - Chemical and physical modeling (coke combustion, sinter reduction modes, flows patterns, ?.) , - Staged mass and heat balances or kinetic model. This allows to define the limits of operation of each blast furnace and to predict the influence of operating parameters on the furnace performances. For the zinc Imperial smelting furnace, the probing results show the existence- of both an Isothermal reserve zone at 1015ºc and a chemical equilibrium between ZnO and gas which makes possible the use of a practical model for heat and material balances. In particular, very good prediction on the influences of operating parameters can be made. On the contrary, for lead blast furnaces, the probing results show that the thermal and chemical equilibria are not reached. Consequently, classical models for staged heat and mass balances are not sufficient. The use of the other means allows then to characterize the specific influences of operating parameters on the thermal instabilities of these furnaces and their allowed limits.

Jan 1, 1990

By Yongfeng Jia

Lime neutralization and co-precipitation of As(V) with iron(III) is the most widely used and most economical method for the removal of arsenic from mineral processing solutions and effluents. However, the arsenate fixation mechanism in the coprecipitated solids is not fully understood. It was suggested by various researchers to be a ferrihydrite precipitation process during which arsenate is removed by adsorption on ferrihydrite. In this study, XRD, EXAFS and microprobe were employed for the speciation of arsenic and the effect of various factors on arsenic solubility was also investigated. The results indicate that coprecipitation is a more complicated process than simple adsorption resulting in lower arsenic solubilities. Poorly crystalline ferric arsenate was observed for the first time to be present in the coprecipitated solids. In case of lime as base, there exists some type of Ca-Fe-arsenate association. A general term ?coprecipitate? is suggested to describe the precipitated arsenic-bearing solids instead of those widely used specific terms ?arsenical ferrihydrite? or ?arsenic-bearing ferrihydrite?.

Jan 1, 2005

By Kenneth S. Coley, Michael Pomeroy, Elaine Chen

Recent work on modeling of BOF steelmaking is reviewed, highlighting the critical aspects of each approach. It is concluded that the most successful models should be based on a deep understanding of the mechanisms and kinetics of the critical reactions. The importance of the decarburization mechanism is discussed with particular reference to its role in droplet swelling or bloating which has a profound influence on the droplet residence time in the slag. Conditions which cause bloating are discussed and the rate determining step is proposed to be primarily nucleation of CO bubbles inside the metal droplet with some influence from growth by reaction at the bubble/metal interface. The discrepancy in the super-saturation ratio required for classical nucleation is discussed and an approach using a surface tension modifying parameter is illustrated. Finally, the role of CO nucleation in controlling the driving force for dephosphorization is discussed.

Jan 1, 2014

By Andrea R. Kim, Ramana G. Reddy

Electrodeposition of cobalt from cobalt chloride using the urea and the choline chloride ionic liquid (2:1 molar ratio) was studied to search the optimized parameters for the higher current efficiency. The cyclic voltammetry was tested with 0.2 MCoCl2 using various scan rates to determine the reduction potential in Urea/ChCl at 323 K. Based on the data from cyclic voltammetry test, the transfer coefficient and the diffusion coefficient were calculated as 0.22 and 3.38 × 10−6 cm2/s, respectively. The parameters for electrodeposition of cobalt were various temperatures (323 –383 K), applied potentials (2.4 –3.3 V), and concentration of CoCl2 (0.2–0.5 mol/L). Current efficiency and energy consumption were calculated to investigate the optimal condition for the electrodeposition of cobalt. The highest current efficiency (95%) was obtained under the temperature 323 K, the applied voltage 2.7 V, and concentration 0.5 mol/L of CoCl2. Scanning electron microscope (SEM) and X-ray diffraction (XRD) were used for the characterization of cobalt deposits.

Mar 1, 2017

By Batric Pesic

Reactions of metallic iron were studied in several different aqueous solution systems: water, medium salt solution used for the growth of T ferrooxidans, ferric iron solution and solution containing T ferrooxidans. Each system was studied under abiotic and biotic conditions in the presence of T ferrooxidans and as a function of pH, particle size of iron powder, temperature, ferrous and ferric iron concentrations. It was found that metallic iron reacts with water differently than does with ferric iron in water. Surprisingly, T ferrooxidans were non-functional in the dissolution of metallic iron. Also, the reactions of metallic iron with pure water were indistinguishable from the reactions with water containing medium salts for bacterial growth. The reactions with ferric iron were also independent of medium culture compounds. The mechanisms of metallic iron reactions with ferric ions are different from the mechanisms of metallic iron reactions with water.

Jan 1, 2001

By David Melgaard

A significant emerging recycling, waste minimization problem stems from legacy waste from the nuclear weapons program and from production of power using nuclear fuel. Premium quality metals used in nuclear plants become contaminated, making them unsuitable for reuse. Consequently, decontamination studies were conducted to evaluate the decontamination capacity and partitioning effeetiveness of Electroslag Remelting (ESR). Eight laboratory melts were conducted to evaluate the efficacy of using ESR to transport radionuclides from the liquid metal phase to the liquid flux or slag phase. To determine the decontamination effectiveness, several surrogate compounds for uranium, plutonium and other fission products were added to the melts. During the melts, the melting rate was varied, typical slag additives were used, and two different slag compositions were evaluated. The resultant post-test ingots and slag were then analyzed to determine the partitioning of the surrogates. ESR generally proved very effective in removing contaminates from the metal with a few noted exceptions. -

Jan 1, 2003

By J. E. Klein

Bench scale tests using a stack of ten whole SAES St909 pellets, 6 grams, to crack methane have been completed with pure methane feed. Test conditions ranged from 600 to 800°C at 101 kPa (760 ton) with a methane feed rate of ten sccm. Methane reformation tests, test where hydrogen was passed through a St909 bed after cracking methane, were performed to determine if and how much methane can be generated under "reformation" conditions. Phase structure determinations of St909, composed of a ZrMnFe alloy with aluminum used as a pellet binder, after methane cracking were complicated by the number of materials that can be formed by the elements in the St909 and the carbon from methane cracking. It was determined that the aluminum not only alloys with the Zr, Mn, and Fe in the St909 alloy, but also forms aluminum transition metal carbides in addition to ZrC as the carbon content and the temperature of the St909 increases. Some A14C3 was also found in some pellets. Passing hydrogen over St909 pellets after methane cracking formed methane at various rates in the temperature range of 600 to 800°C. Temperatures of 800°C gave the best methane cracking performance and efficiencies decreased rapidly with temperature.

Jan 1, 2002

By J. M. Demarthe

MINEMET RECHERCHE (IMETAL Group, formerly Le Nickel-Penarroya-Mokta) has studied on a laboratory scale and patented a new process to recover metal values -copper- from sulphide ores and concentrates. It combines a cupric leaching, solvent extraction and copper sulphate electrowinning according to the main following steps - A direct and selective leaching of copper sulphide ores or concentrates at atmospheric pressure with cupric chloride to form cuprous and ferrous chlorides and elemental sulphur. Pyrite remains in the sulphur residue. - The leach solution is separated into two parts -In the first one, air is injected to precipitate iron as goethite. The oxidation step can be easily realized at atmospheric pressure by maintaining an excess of cuprous and-ferrous chlorides in the liquor. Copper is extracted from the second part as cupric ion by an LIX reagent. Direct injection or air in the mixing chamber maintains good extraction conditions, so that only one mixer settler is required. - Iron, in the form of ferrous ion, is not coextracted. - Copper is stripped from the organic phase, transferred into a sulfuric phase and sent to sulphate electrowinning cells, which are now conventional in copper metallurgy. - Only electricity and air are required. After a feasibility study, the next step will be to develop it on a pilot and commercial scale.

Jan 1, 1976

By G. Belardi

The purpose of the study was to check on the level of environmental contamination and to design a project for cleaning up the Abetina Mine area at Piancastagnaio (Grosseto, Italy). Contamination of this area had occurred during the mining and treatment of cinnabar (HgS) over a prolonged period. The aim of the project is to remove the sources of contamination or render them harmless. Mining of the Piancastagnaio deposit started in 1840, mercury metal being extracted from the ore by thermal treatment. Together with Spain, Italy was the first country to produce this metal and was the world leader in this field between 1936 and 1943. Though mercury production in the Monte Amiata region of Tuscany ceased in 1974 the ensuing environmental impact is very evident, taking the form of rusty old mining and processing works, plus waste tips which still contain considerable amount of mercury even after the ore had been subject to thermal extraction treatment. The research which has been conducted included mapping the area to identify the main sources of mercury and arsenic pollution, as well as the level of environmental contamination. Mercury and arsenic values in excess of 16,000 and 150 ppm respectively are encountered in the most highly-contaminated places. The cleanup project has been drawn up on the basis of the field and laboratory investigations. This provides for a combination of remediation measures on the land concerned, as well as in situ inertization of contaminating elements by means of mixtures of chemical compounds such as cyclosiloxanes. Due account has been taken of Italian and EU environmental regulations when establishing the measures for rendering the various polluting element innocuous. 'The efficacy of the inertization techniques has been checked by yield tests in acetic acid and carbon dioxide, reducing the Hg and As contents of the material in the untreated and treated states from maximum values of 7 mgll to minima close to zero.

Jan 1, 1996

By Dolf Gielen

This paper discusses the results of a Western European energy and materials systems engineering study that analyses the impact of greenhouse gas (GHG) emission reduction on the future of the steel and aluminum industry. he technology selection will be significantly affected by future CO2 policies. The avail- ability of C02 removal and storage technology and the social acceptance of this strategy for GHG emission reduction is of key importance for the strategy selection. The use of coal based smelting reduction technologies is optimal in case of weak C02 policies or in case of strong C02 policies and low CO2 removal and storage costs. The selection of CCF or Corex technology depends on the penalty regime. However, if C02 removal proves to be problematic, CCF development fails and strong C02 policies are introduced, the gas based DRI production processes will become more attractive. In both cases, the energy efficiency of the iron and steel industry will further increase in the next decades. The impact of GHG emission reduction on aluminum prices and aluminum use can be significant. However contrary to common notions the aluminum production will be positively affected by GHG emission reduction, notwithstanding the currently high emissions in aluminum production. A combination of emission mitigation in production and significant GHG emission reduction effects further down the product chain cause this effect. A significant potential exists for improved materials efficiency. This potential is generally neglected in energy efficiency and CO2 reduction studies. However improved steel qualities are of similar importance for C02 emission reduction as increased energy efficiency. It remains to see if this potential will be used to its full extent in the next decades. Model calculations indicate that the impact of C02 policies on the competition with other materials will be limited. Greenhouse gas emission mitigation will have much more impact on materials production and waste handling than on materials consumption.

Jan 1, 1999

By P. N. Anyalebechi

The effects of a cross-hatched grooved mold surface topography, casting speed, and superheat on the morphology of solidifying shells of aluminum alloy 3003 have been characterized by a series of immersion tests. The cross-hatched grooves were 0.232 mm deep with wavelength or spacing between 1 mm and 15 mm. The shells solidified at casting speed of less than 10 mm/s on the 1 mm spaced cross-hatched grooved mold surface were fairly uniform with little or no localized variations in thickness. However, the propensity for non-uniform shell growth morphology was exacerbated by an increase in casting speed, melt superheat, and the wavelength of the cross-hatched grooves. This is provisionally attributed to their effects on interfacial heat transfer and wetting of the mold surface by the molten metal.

Jan 1, 2008

By Marcello M. Veiga

Informal gold mining operations in the Amazon emit about 100 tonnes of mercury annually because of poor amalgamation practice. Lack of information and the complexity of mercury transformations hinder effective action to prevent such pollution and/or monitor its extent. In the past, mathematical equations have been formulated to deal with the correlation of natural variables and mercury in biota but often, the error range is too great to provide useful models. Projection of physico-chemical variations in an environment subjected to mercury emissions onto the extent of bioaccumulation is fraught with many uncertainties and unknowns such as internal correlations between variables and the site-specific nature of biota contamination. Often assumptions about closed systems are invalid when applied to natural environments. This work presents a heuristic approach to this problem in which amalgamation methods and natural variables are dealt with using an IF-THEN rule-based system that concludes about levels of emission and risk of bioaccumulation. The system is able to handle uncertain or vague data and yet still provide useful output. Belief in mercury oxidation or dangerous conditions are examined using Fuzzy Logic techniques and Inference Equations. These belief levels are derived from thermodynamic equilibrium data together with field observations of natural variables. This procedure can reduce the need for sophisticated analytical equipment and can provide information and diagnosis to non-technical people.

Jan 1, 1994

By R. H. Eric, A. Chaendera

Gas jet was blown through bottom nozzles of a 1/5th scale CLU model in the presence and absence of slag. Kerosene and water were used to simulate the slag and metal phases respectively. Mixing time increased with increasing bath height and with a decrease in the gas flow rate. It was related to bath weight, bath height and gas flow rate. Slag increased mixing time by about 16% and the mass transfer values by about 32%. Mass transfer rates were higher near the bath surface and in the gas-liquid plume region. They increased with increasing gas flow rate and with a decrease in bath height. A relationship showing the dependence of derived mass transfer coef ficient on the gas injection rate was established. Turbulence characteristics inside the bath liquid were established to vary with location, vessel geometry and gas injection rate.

Mar 1, 2017

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 Victor Stancovski, Uday Pal, Stephen C. Britten

"An in situ electrochemical technique for measuring the concentrations of easily dissociable oxides in slags at temperatures between 1200-1600°C is being developed. The technique utilizes a partially-stabilized-zirconia solid electrolyte (PSZ), which conducts oxygen ions, to separate a reference-gas compartment from the slag of interest. Three types of measurements are currently under investigation which yield different information concerning the slag phase and hence will be combined into a single amperometric device for monitoring the properties of easily dissociable slags.Type I utilizes an open-circuit-voltage measurement between the reference gas and the slag phase. Type II utilizes a potentiostat to apply a direct current potential step or sweep between the inner and outer compartments of the electrolyte, driving oxygen ions from the slag into a reference gas. With the use of open-circuit-reference electrodes, the resulting current-potential profile reveals the dissociation potential and concentration profile of dissociable oxides such as those of iron, manganese, and chromium. Information on the transport properties of the cations can also be generated from these measurements. Type III utilizes a potentiostat with reference electrodes to carefully electrolyze a known volume of slag by removing large quantities of oxygen ions from the slag to the reference gas. The coulombs of charge removed at different applied potentials can be used as a direct indication of the concentration of each dissociable oxide species present within the slag."

Jan 1, 1997