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By L. A. Harris

The formation of coke during coal liquefaction can eventually result in catastrophic failure of the conversion system. Coking typically proceeds by the formation of liquid crystals (mesophase) and the subsequent separation of these crystals from the plastic phase formed during heating of coal. The anisotropy of the mesophase makes it readily detectable in the optical microscope under polarized light. This study examines the solids formed during coal liquefaction processing by optical and electron microscopy. Observations on the relationships between the coke morphology, minerals and inert macerals are presented.

Jan 1, 1982

By B. Mishra, W. A. Averill

"The application of various hydrometallurgical, pyrometallurgical and electrochemical processes in the extraction, purification and production of radioactive metals as well as the use of various materials, ego metals and alloys, ceramics, polymers, etc. in the process, construction and handling equipment in the nuclear industry has generated a large stockpile of radioactively contaminated waste material and scrap metal which can not be directly discarded, recycled or considered for long-term storage due to its volume and potential hazards, without the separation of radionuclides. This paper reviews the emerging methods that have been investigated and suggested for dealing with some of these wastes and scrap material.The separation technologies studied for the recovery of radioactive components from the pyrometallurgical and electrochemical processing wastes have been discussed in details with results from some of the recent theoretical and physical modeling work as well as the data obtained from the actual waste treatment. Specific processes shall be described in terms of its advantages and limitations. These emerging separation technologies are being considered by the US Department of Energy as alternatives for dealing with the issues of environmental management [EM] and decontamination and decommissioning [D&D].IntroductionThe high temperature carbothermic or metallothermic smelting reduction methods for metal production are associated with the generation of significant quantity of waste as slags, flue dusts, sludges, residues, effluent salts etc. Certain hydrometallurgical processes also generate lots of aqueous waste due to the inherent nature of the technique. Also, the gas-based reduction processes are not applicable to many stable metal compounds, such as alumina, titania, beryllia, lanthanide and actinide oxides, etc. due to thermodynamic considerations. All these methods cause substantial environmental hazard. There is a need to develop alternative processes which have low waste or ideally a ""zero-waste"" generation.Pyrochemical processes using molten salts provide a unique opportunity for the extraction and refining of many reactive and valuable metals either directly from the beneficiated ore (aluminum, beryllium, neodymium, plutonium, uranium, etc.) or from other process effluent that contain reactive metal compounds. The processes reduce metal compounds electrolytically (A12O 3 and BeCI2) on a carbon anode or by calciothermic reduction (Po, Nd). The by-product, in the latter case, is a calcium oxide saturated halide salt. The waste-treatment to recycle the halide has to be done as a separate step or stored as a contaminated waste. A successful separation technology can provide a new insight to the waste minimization strategy for the nuclear industry."

Jan 1, 1996

By James P. Bennett

EAF slag chemistry and its control have been recognized as important in producing quality steel at a low price for a number of decades. EAF steel producers make lime and dolomite additions to furnaces, controlling the CIS ratios and sulfur pickup from the steel. Existing phase diagram data at 1600°C for CaO, MgO, FeO, SiO2, and Al2O3 was used to write a computer model optimizing slag chemistry for slag foaming and reduced refractory wear. The model, its development, and its use in an industrial steelmaking environment will be discussed along with how the model can improve energy efficiency. The importance of EAF mass balance to account for critical materials like Si in scrap and refractory wear using the model will also be emphasized.

Jan 1, 2003

By James P. Bennett

EAF slag chemistry and its control have been recognized as important in producing quality steel at a low price for a number of decades_ EAF steel producers make lime and dolomite additions to furnaces, controlling the CIS ratios and sulfur pickup from the steel. Existing phase diagram data at 1600°C for CaO, MgO, FeO, SiO2, and Al2O3 was used to write a computer model optimizing slag chemistry for slag foaming and reduced refractory wear. The model, its development, and its use in an industrial steelmaking environment will be discussed along with how the model can improve energy efficiency. The importance of EAF mass balance to account for critical materials like Si in scrap and refractory wear using the model will also be emphasized_

Jan 1, 2003

By H. L. Fraser

A review of the possibilities of performing microchemical analysis in thin sections using a combination of scanning transmission electron microscopy and energy dispersive spectroscopy of x-rays is given. Particular attention is paid to the factors that limit accurate analysis at the highest spatial resolution. As an example of the use of these techniques applied to a potential problem in minerals processing, the identification of iron pyrite and pyrrhotite particles in Illinois, Herrin #6 coal is presented.

Jan 1, 1981

By Mahesh C. Meyer Jha

AMAX has developed a chloride refining process to produce pure nickel and cobalt metals from mixed sulfide .precipitates, Metal chloride solutions, generated in a hydrochloric acid leaching step and purified in a solvent extraction circuit, are converted to metal oxides .and HCI gas by pyrohydrolysis. A pilot plant consisting of a 30-inch diameter fluidized bed reactor and other ancillary units was designed, constructed, and operated for over one year. Process design was aimed at minimizing energy consumption, maximizing conversion efficiency, and achieving simplicity of operation and control. The operation provided valuable information on process scale up parameters, process control strategies, and materials of construction., Several process variables such as bed temperature, solution composition, solution feeding system, bed particle size distribution, and fines recycle system were investigated to determine their effects on process efficiency and the physical and chemical characteristics of the product.

Jan 1, 1985

By G. R. Palmer

The success of future electric vehicles will depend greatly upon the power supply choices made today. Research is presently being conducted by automotive engineers and electrochemists to determine what battery type may be the most promising. Not only are product production and application efficiencies being evaluated but also environmental concerns of reclamation and recycling. Rechargeable batteries using nickel-metal hydride electrodes are strong candidates for these electric vehicle applications. The U.S. Bureau of Mines is investigating hydrometallurgical technology that separates and recovers purified metallic components present in nickel-metal hydride battery scrap. Sulfuric, hydrochloric, and nitric acids are all capable of dissolving the battery electrode alloys given the proper operating conditions. Solvent extraction of the leach solutions using D2EHPA removes iron, and selective precipitation shows promise of recovering the other metals in the H2SO4 and HNO, systems.

Jan 1, 1994

By Gus Van Weert

Solvent extraction of iron from zinc refinery liquors has been investigated before, mainly on the MEHPA / HC1 stripping combination. Leakage of chloride into the zinc electrolyte and the costs of handling the ferric chloride eluate have prevented this option from being adopted. This work explores the stripping of the ferric loaded organic phase with nitric acid to take advantage of the possibility of regenerating up to 6N nitric acid, and clean spheroidal hematite production by autoclave treatment of ferric nitrate solution. The work was carried out with DEHPA (di 2-ethyl-hexyl phosphoric acid) in kerosine. Degradation testing proved the DEHPA to be very stable, when exposed to nitric acid solutions up to 6N and temperatures up to 70" C over a period of five days. Ferric iron was removed completely froma synthetic hot acid leach liquor, irrespective of the DEHPA concentration. Stripping the ferric turned out to be the problematic step. Although the stripping efficiency was considerable better at 50 than at 20° C, it decreased with increasing DEHPA/Fe ration in the organic phase. Eluates of no more than 5-10 g/l ferric nitrate were produced. surprisingly, nitric acid was found to be a less efficient stripping agent than sulphuric at equivalent normality and its efficacy levelled off above 4N. It was concluded that DEHPA does not appear to be the S.X. reagent to take advantage of the low cost autoclave decomposition of ferric nitrate opportunity in zinc hydrometallurgy and that another S.X. reagent, also resistant to nitric acid, but based on weaker compound formation is needed.

Jan 1, 1998

By V. Jiricny

There is a growing need to process galvanized steel scrap from automobiles, etc., in order to remove the zinc coating that otherwise causes problems in remelting of the scrap in electric arc furnaces. One approach that has moved to the pilot plant stage is that of Metal Recovery Technologies, Inc., of East Chicago (MRI). That company leaches the zinc fiom the scrap with a sodium hydroxide solution. The leached and washed scrap can then be returned to the steel industry. What is left is a sodium hydroxidelzincate solution which must be processed to recover the zinc and the NaOH. Presently, this is done by MRI using electrodeposition on planar electrodes at moderate current density and the resulting zinc is in the form of fine powder which is hard to process into, say, zinc for galvanizing. MRI has supported an investigation of a novel electrode, the spouted bed electrode (SBE), for zinc electrodeposition. In laboratory cells, zinc particles with low porosity have been grown up to 3mm in size. Microanalysis of the deposited zinc showed low level of impurities. DC energy consumption values were usually in the range of 2-2.5 kWg which is well below the energy consumption of the existing cells (and of present-day cells for electrowinning from acid sulfate electrolytes). These results were achieved at current densities (few thousand A/m2) that are much higher than possible with conventional electrodes. Discussion is provided of the scale-up of the cell to a commercial scale.

Jan 1, 1998

By U .. C. Rojas, J .. C. Gomez

"Fire Refined Copper (EI Teniente Three Stars) has been produced at Caletones Smelter of Codelco Chile since almost the beginning of its operations.Due to changing features of the copper market, together with the targets on technical efficiency and productivity, it has become more and more relevant for copper industry to reach both, good final product quality and a proper environmental control.At present, copper refining process at Caletones Smelter takes place in two cylindrical tilting furnaces, where solid fluxes are injected through horizontal tuyeres into the molten bath. (Fig. N2 1)Solid reagents are pneumatically conveyed and injected into the liquid copper bath attaining excellent solid - liquid contact, so the impurities removal efficiencies are found to be high. Same injection tuyeres are used to introduce both oxidising agent (normal air) and reducing agent (reformed gas) into the molten bath. Air or nitrogen is used as conveying gas for solid reagents, depending on the process stage.This pap~r gives a fundamental description of the process and industrial results related to the injection of blend of sodium and calcium carbonates to remove arsenic and antimony, silica and granulated reverberatory slag to remove lead and a mixture of calcium carbonate and mineral coal to reduce the selenium content of the fire refined copper."

Jan 1, 1996

By Suresh Sundarraj

A diffusion mass transport model for predicting the microsegregation in a solidifying and coarsening dendritic mushy region of a binary alloy is presented. Two versions of this model are tested; one based on expressing the solute concentration in terms of mole fraction and the other on expressing the solute concentration in terms of mass fraction. On comparing previous model data sets and conditions, used in the analysis of Aluminum-Copper systems, a number of inconsistencies emerge. These inconsistencies are resolved on identifying a single set of data and conditions which take account of compositional density changes, "non-linear" thermodynamics and dynamic coarsening. An additional investigation is carried out to study the effect of assumed cooling mechanisms.

Jan 1, 1992

At its Copper Cliff Smelter, Inco Limited processes a bulk copper-nickel concentrate in two Inco oxygen flash furnaces, The furnace matte is converted to low iron matte for further processing, and the molten converter slag is recycled to the flash furnaces. The flash furnace slag is discarded. Natural gas or coke supplies a minor proportion of the process heat requirements, thus limiting the flash furnace matte grade to the target 45% CuNiCo. Coke addition to the furnace offers a potential means of establishing a reducing barrier on the surface of the molten bath. Such a practice would be conducive to producing sulfur deficient (partially metallized) matte. At the same iron content, the iron activity of sulfur deficient matte is higher than that of regular matte. A supernatant coke barrier could, therefore, be expected to lead to higher nickel and cobalt recoveries, reduction or even elimination of magnetite furnace bottom build-up and increased sulfur elimination as S02 in the flash furnace. Preliminary experiments were conducted in a miniplant flash furnace to investigate the effect on process metallurgy of the suggested modified scheme. This paper presents the experimental results and discusses key aspects of the possible operation of the Inco flash furnace with a coke barrier separating the freeboard from the molten bath.

Jan 1, 2003

By Yanhui Liu, Xuewei Lv, Pingsheng Lai, Chenguang Bai

The purpose of this paper is to study the effect of slag basicity on the Si content in stainless steel master alloys prepared by smelting reduction of Fe-Ni-Cr sinters. Theoretical analysis focusing on the gas, slag and alloy phases of the smelting reduction process at 1600°C was carried out by thermodynamic calculation software----FactSage, showing that the increase of CaO within the slag can result in the decrease of Si within the master alloy. Experiments were also carried out in vacuum melting furnace at 1600°C , and chemical analysis method was used to detect Si content in the alloys. When the MgO content is 9.00%, the experimental results were consistent with the calculated values. However, when the MgO content rises up to 14%, the content of Si in the alloy reaches the maximum when SiO2 equals to 22.81%.

Jan 1, 2016

By E. J. Peterson

Oil shale retorting induces mineral and chemical reactions to occur on the macroscopic and microscopic levels in the kerogen-bearing marlstone. The nature and extent of the reactions is dependent upon process variables such as maximum temperature, time at temperature, atmosphere, and raw shale composition. This report describes the investigation of the mineral, chemical, and trace element release properties of spent shales retrieved from an experimental in situ retort at Occidental Oil Shale, Inc. 's Logan Wash site in Garfield County, Colorado. Correlation between mineralogy of the spent materials and the mobility of major, minor, and trace elements are indicated, and relationships with important process parameters are discussed. The progress .of carbonate decomposition reactions and silicat ion reactions is indicative of the processing conditions experienced by the shale materials and influences the mobility of major, minor, and trace elements when the solids are contacted by water. Shale minerals that are exposed to the extreme conditions reached in underground retorting form high temperature product phases including akermanite-gehlenite and diopside-augite solid solutions, kalsilite, monticellite, and forsterite. The persistence of relatively thermally stable phases, such as quartz, orthoclase, and albite provide insight into the extremes of processing conditions experienced by the spent shales. Leachate compositions suggest that several trace elements, including vanadium, boron, fluoride, and arsenic are not rendered immobile by the formation of the high-temperature silicate produce phase akermanite-gehlenite.

Jan 1, 1981

By Bing Li, Miao Shen, Qiang Wang, Yuqi Chen

Electrochemical methods including cyclic voltammograms, square wave voltammograms, chronopotentiometry are applied to characterize the reduction potentials of Na+ and Li+ ions in LiCl-KCl melts. According to theoretical calculation, the reduction potential for Na+ is slightly more negative than Li+ in NaCl-LiCl-KCl melts at 450℃. However, by electrochemical measurements, the reduction potential of Na+ is slightly more positive than Li+ in the above melt and the potential difference between Na+ and Li+ reaches 0.16-0.2V on an inert W electrode in 1.0-2.0 wt% NaCl-LiCl-KCl melts. An active Pb electrode is used to improve the removal rate of Na+ from LiCl-KCl melts. The reduction potentials for both Na+ ions and Li+ ions on a Pb electrode shift to more positive values and the reduction currents become larger. After 6h electrolysis on a Pb electrode at -3.0V, the practical removal efficiency of Na+ ions reaches 90.12% and the reduced products contain metallic Na and Li with a Na/Li mass ratio of 4.25/1.

Jan 1, 2015

By D. E. Woolley

The rate of reduction of iron oxide from calcia-silica-alumina slag by carbon in liquid iron has been measured over the temperature range 1400-1600°C by monitoring the rate of carbon monoxide (CO) evolution. Slags containing ferric iron have been used in order to study the reduction of both ferric and ferrous cations. Results show that ferric iron is reduced before ferrous iron, so that the ferrous iron concentration increases initially. It is also shown that the rate constant, k, decreases at low reaction rates, or, equivalently, at low concentrations. The authors conclude that the reaction occurs in two periods. During the first period, ferric iron is reduced to ferrous iron. During the second period, ferrous iron is reduced to metallic iron, and the rate-limiting step during the second period is the mass transfer of ferrous cations in the slag phase to the slag-metal interface.

Jan 1, 1998

By Veena Sahajwalla

The cupola furnace is a coke-fueled shaft furnace used as a primary melting unit in iron foundries. Control of chemical composition of the iron tapped from the cupola is a key factor in productivity and quality control. In an effort to develop a control model for the cupola, a fundamental approach based on physical and chemical principles has been taken to describe the melting process. The behavior of oxidation of the solid charge in the stack of the cupola has been studied. Sulfidation of the charge materials by sulfur-bearing components released to the furnace gases from the coke has been described. Carburization of metal droplets of iron and of steel in separate molten streams has been characterized. Finally, reactions with alloying elements in the hearth (well) of the furnace have been defined. These reactions have been described in a computer-implemented model developed to predict the composition of the iron tapped from the cupola. The model has utilized the thermodynamics and kinetics of the oxidation, sulfidation, and carburization reactions, including temperature and physical aspects, in the various zones of the melting unit. The model predictions have been compared favorably with operating results.

Jan 1, 1992

By Yuan-bo Zhang, Gui-hong Han, Yan-fang Huang, Tao Jiang, Guang-hui Li

"Under isothermal conditions, the reduction behavior of oxidized pellets balled with bentonite was investigated with CO-CO2gas mixers in the temperature range from 900°C to 1100°C. The whole reduction of oxidized pellets was followed up by means of weight-loss technique. And the swelling index of pellets was examined by visualizing physical changes of pellet in a horizontal tube furnace. The results present that the reduction rate of oxidized pellets is increased with the increase of reduction temperature. While the swelling index is firstly increased and then decreased with the increase of reduction time and reduction extent, which can be ascribed to the disruptive stresses induced during the transformation of hematite to magnetite. The maximum swelling index is gradually increased with the increase of reduction temperature and CO content.IntroductionWith the rapidly development of iron and steel industry, direct reduction iron has been considered as one kind of high quality burdens in electric furnace steelmaking [1]. At present, ""Two-step"" coal-based direct reduction process, which employs oxidized pellets as raw materials, has been used in industrial production [2]. The reduction behavior of iron ore oxidized pellets has been becoming one of the most frequently studied topics in extractive metallurgy[3]. The heat and mass transfer in direct reduction processes results in a series of stepwise reduction reaction (hematite--magnetite--wustite--iron), accompany with the volumetric swelling of pellets[4]. A lot of literatures have been reported on the reduction model of ferrous oxides and swelling behavior of pellets. A. A. El-Geassy K, et.al [5-7] revealed that the reduction process was controlled by chemical reaction at early stage by employing pure Fe203 as raw materials and CO as reduction gas. Chen Y [8] made research on the reduction kinetics of porous oxidized pellets and obtained the rate constant and activation energy of at different reduction stage. In addition, the swelling and disintegration of iron ore pellets was affected by chemical composition of pellet and reducing parameters, which have been studied by numerous investigators [3,9, 1O]."

Jan 1, 2013

By Qingchun Yu, Baoqiang Xu, Yongnian Dai, Bin Yang, Fulong Zhu

"In this paper, the mechanism of the carbothermic reduction-chlorination process to extract aluminum from alumina in vacuum was investigated. The carbon monoxide (CO) content of the gas, phases of the reduction slag, surface morphology of the reduction slag and the product aluminum were measured by means of gas chromatography (GC), XRD, and SEM. The experimental results indicated that the content of CO in the gas decreased, but Al4C3 increased with time at 1773K during the carbothermic reduction process of alumina. AlCl(g) and graphite (C) were produced by the reaction between Al4C3 and AlCh(g) at 1773K, and then aluminum beads generated after the decomposition of AlCl(g). It implied the mechanism of alumina carbothermic reduction-chlorination process in vacuum involves three steps as follows: the carbothermic reduction of A}z03 to produce Al4C3, the chlorination of Al4C3 by AlCh(g) to produce AlCl(g), and the decomposition of AlCl(g) to produce Al(l).IntroductionAluminum is the basic raw material for many industries [1], and it is used extensively because of various excellent properties such as light weight, good malleability, high strength, excellent thermal conduction, high corrosion resistance and so on [2]. Industrial production of aluminum currently includes refining alumina and electrolytic aluminum processes. However, its development has been effected by some factors such as high energy consumption and heavy environmental burdens [3]. In the past several decades, there had been numerous attempts to produce aluminum by new methods. Extracting aluminum from alumina or bauxite directly by carbothermic reduction-chlorination process had been studied [ 4-6]. Although the alumina carbothermic reduction process [7~9] had been studied, the mechanism of the carbothermic reduction-chlorination process had not been systematically elucidated.In order to investigate the mechanism of the carbothermic reduction-chlorination process in vacuum, GC, XRD and SEM techniques will be used to determine the CO content and to characterize the surface morphology and composition of the slags at various temperatures."

Jan 1, 2011

By J. A. Bakken

Thermal plasmas are interesting for a wide range of metallurgical and chemical processing applications. The 300 kW experimental reactor PRESS, which has been in use since 1987, is operated in the transferred arc mode with three or one plasma torches . Tests include remelting of silicon fines and production of ultrafine silica. Work on a novel three stage process for production of silicon metal is under way. A 1:1 model of the plasma reactor is used to measure the wall heat flux distribution calorimetrically. The cold walls of this model are divided into several water-cooled sections. The same plasma torches as in the real hot-wall reactor are used. In parallel to the experiments and calorimetric measurements theoretical work is done on numerical modelling of one and three transferred arcs. A modified version of the flow simulation program FLUENT from Creare Ltd. is used.

Jan 1, 1991