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By Grigore Matei

The thermodynamic properties of CuzS-FeS system are important not only in the ease of copper smelting but also in the case of general pyro-metallurgy. However there arc not many reported activity data In this study, activities of FeS and CU2S in the Cu2S-FeS system were calculated using the Darken's method from the activity data of the Cu2S-FeS-Sb2S3 systems measured by the transportation method at 1050°C. The activities of Cu2S and FeS in the Cu2S-FeS system showed negative deviation from the ideal behaviour and satisfied the relation of the Gibbs-Duhem equation.

Jan 1, 2003

By D. A. Milligan

Ammonia leaching of copper sulfide concentrates, matte, scrap or other sources of copper yields copper amnine sulfate solutions which are converted to metal in a two-stage process involving precipitation of inter- mediate sulfites and their thermal decomposition to copper powder of high purity. Processing details and results are given. Considerable simplification in circuitry and cost savings are indicated. Energy requirements are reduced by substitution of copper powder precipitation and ammonium sulfate crystallization for solvent extraction, electrowinning and lime boil.

Jan 1, 1976

By Z. W. Zhang, Songsong Xu, Jinhui Li, Yun Zou, Yu Zhao

High strength low alloy (HSLA) steels with high strength, high toughness, good corrosion resistance and weldability, can be widely used in shipbuilding, automobile, construction, bridging industry, etc. The microstructure evolution and mechanical properties can be influenced by thermomechanical processing. In this study, themomechanical processing is optimized to control the matrix microstructure and nano-scale precipitates in the matrix simultaneously. It is found that the low-temperature toughness and ductility of the steels are significantly the matrix microstructure during enhancing the strength by introducing the nano-scale precipitates. The effects of alloying elements on the microstructure evolution and nano-scale precipitation are also discussed.

Jan 1, 2016

By H. Matsuda, T. Iwashita, H. Awata, H. Liwei, D. Hirabayashi, Y. Saito, S. Ozawa, Y. Goto

"The present study is concerned with investigating the effect of chemical treatment on enhancing the HCl absorption capacities of coal burnt ash and slag. It was found that the HCl absorption capacity of coal burnt ash discharged from fluidized bed combustor was improved by hydration with water and 5% polyethylene glycol solution. This phenomenon was based on an increase of the specific surface area of treated coal burnt ash. The HCl absorption capacity of hydrated ash with polyethylene glycol solution was almost equivalent to that of standard CaO and Ca(OH)2. In particular, the specific surface area of hydrated ash with polyethylene glycol solution was found to be 19 m2/g, which was more than over eight times larger than that of raw sample. Hydrated slag treated with lON sodium hydroxide solution also showed high HCl absorption capacity, with highly improved surface area. It was found that the absorption capacity of slag for HCl depended on the treatment time, showing the maximum absorption capacity for 12 hours of hydration treatment.IntroductionA large amount of coal burnt ash, slag and dust are discharged from such industrial processes as coal combustion and metal refinery etc., and it becomes an serious problem to recover and diminish these solid wastes because of the shortage of dump sites and subsequent metal elution to the environment. Figure 1 shows the present situation of reutilization of coal burnt ash and slag in Japan [1,2]. It is shown in this figure that these solid wastes are recycled as materials in the fields of earthwork, agriculture and forestry etc. A part of these solid wastes, however, is still dumped to landfill. To decrease this dumped amount, the development of environmentally friendly reutilization technique for these solid wastes is of great importance."

Jan 1, 2000

By Xiaobing Yang, Abhishek Lahiri, Animesh Jha

"In the FFC-Cambridge process, the cathodic dissociation of oxide and CO/CO2 production on carbon anode is the basis for metal production in a CaCl2 bath. By using an inert intermetallic anode, the CO2 evolution can be eliminated altogether with acceleration in the electro-reduction kinetics. At present the process suffers from slow reduction kinetics of TiO2 to Ti metal, which can be enhanced significantly by the incorporation of alkali species in the TiO2 pellet at the cathode and in the CaCl2 bath in the presence of an intermetallic inert anode. Nearly full metallization with greater than 99% of Ti metal containing 1500 ppm of oxygen is possible to achieve in less than 16 hours of electro-reduction. Analyses of phase composition and the microstructures morphology in fully metallized pellets revealed the presence of localized solidified Ti layer, indicating that fast reduction process also involved formation of liquid phase as middle stage reaction. In addition, in situ creation of porosity and maintain higher current level during electrolysis process were two key factors to fully reduction of TiO2.IntroductionDuring cathodic dissociation of TiO2 in a CaCl2 bath and anodic evolution of CO2 on a carbon anode, which is the basis for the FFC Cambridge process [1], the rate of metallization slows down due to the formation of CaTiO3 at the reaction interface. Calcium and alkaline earth perovskites are known for their poor electrical conductivity which adversely affects the overall electro-reduction. One of the ways to increase the porosity is via the addition of polyethylene precursors in the pellet or by directly starting from perovskite [2, 3]. The experimental evidences shown in the literature confirm although the speed of reaction increases, but a complete or near complete metallization is not possible by enhancing the in-situ porosity alone, as the insulating perovskite is very slow to decompose under the equilibrium that prevails in the cell. Plethoric evidences on carbon anode show with the current decrease gradually, and finally stabilize at a very low value between 0.2 and 0.4 A, which is a testimony of the presence of perovskite insulating barrier in the current path. Our aim in this paper is to demonstrate the mechanism of enhanced electro-reduction when alkali ions are present in the oxide pellet at cathode and in the bath. We also show for the first time the use of an intermetallic anode for Ti-metal production using the FFC Cambridge process."

Jan 1, 2009

By Alain Jardy, Thibaut Quatravaux, Denis Ablitzer

"A numerical model of the Vacuum Arc Remelting process has been developed and applied to simulate remelting of various metallic materials, such as specialty steels, titanium and zirconium alloys. In practice, electromagnetic stirring is sometimes used, resulting in a complex 3D molten metal flow. After having validated the numerical model for different remelting conditions, we can use it to study the effect of applying a constant or alternated magnetic field on the thermohydrodynamic behaviour of the melt pool. The intensity of flow turbulence, computed with a classical k-E model, is shown to depend strongly on the nature of electromagnetic stirring.IntroductionThe principle of the Vacuum Arc Remelting (VAR) process, illustrated in figure I, consists in melting a consumable metallic electrode of the required grade under a high vacuum, in order to obtain a sound ingot of good structural quality.During remelting, an electric arc is maintained between the tip of the electrode and the top of the secondary ingot, in order to ensure melting of the electrode. The metal droplets fall through the arc plasma and progressively buid up the ingot, which solidifies in contact with the walls of a water-cooled copper crucible. The secondary ingot formed in this way contains three distinct zones, corresponding to the liquid pool, fully solidified metal and intermediate mushy zone. In order to stabilize the arc, it can be confined with the aid of a magnetic field created by an external induction coil. This field can also be used to stir the liquid metal, the rotation induced being in the orthoradial direction. By reversing periodically the coil current, stirring can be alternated."

Jan 1, 2004

By Darryl Lovato, Ramiro Pereyra, Daniel S. Schwartz

"During an annual inventory of nuclear material, a plated steel container which contained plutonium oxide failed. The container had been packaged for temporary storage but had been overlooked and remained in storage for more than 23 years. Although it was determined that the failure occurred through the slip-top rim, a metallurgical evaluation was requested to help to determine the integrity of the container.Optical metallography and scanning electron microscopy were used to analyze the character and degree of corrosion in the container. The depth of corrosion, measured at approximately 10 µm, did not pose a threat to the integrity of the container. However, the corrosion morphology and chemistry did suggest that a galvanic cell had developed between the tin and steel from the condensation of water. The morphology also suggests that the attack of the steel took place over a series of cycles due to changes of the environment.IntroductionMetallographic analysis was requested as part of the investigation into the mechanism of the failure of a slip-top container (#38621) containing plutonium oxide (PuO2) powder. The container had leaked during a special nuclear material (SNM) annual inventory causing contamination and closure of the vault. A photograph of the container and interior container is shown on the right in Figure 1. An initial investigation established that the source of contamination was the consequence of the failure of multiple layers of containment. Initially by the deterioration of the interior plastic bottle and polyvinyl chloride (PVC) bagout bag, and finally through the lid and steel container interface at a location where tape had not adhered properly [1]. Although the source of the breach was established, it was determined that metallographic analysis was important to establish the extent of deterioration of the steel container."

Jan 1, 2008

By Young-Sool Jin, Heung Nam Han, Hong Joon Kim, Jae Kon Lee

A mathematical model was developed considering non-symmetric cooling' and stress distribution in both thickness and width direction of strip on a run-out table of hot strip mill. In order to solve a transient heat transfer equation including the heat evolved from phase transformation, a finite element method coupled with thermodynamic and kinetic analyses was applied. The heat capacity of each phase and heat evolution due to phase transformation were obtained from the thermodynamic analysis of the Fe-C-Mn-Si system based on a sub lattice model. The phase transformation kinetics of the steels was derived by using an inverse additivity technique with continuous cooling experiments. Heat transfer coefficients of strips on the run-out table were, by applying an inverse method, determined from the actual mill data under various cooling conditions. As for the stress analysis, the density change of strip due to cooling and phase transformation, and the transformation superplasticity were considered. A 90nstitutive equation for the transformation superplasticity, which is related to the phase transformation kinetics and the internal stress due to the density change of strip, was applied. A finite element method was adopted to calculate the deformation behaviour of strip on a run-out table of hot strip mill. Using the models, the temperature-phase-deformation history and distribution of a strip on the run-outtable was calculated.

Jan 1, 2001

By Mingming Zhang, Ramana G. Reddy

"Carbon dioxide (CO2) is one of the most common by-products produced during light metals production. It is considered to be the cause of greenhouse effects. Efficient reduction of CO2 can help minimize the rate of global warming and improving energy sufficiency. In this paper, a novel light metal production process was developed using ionic liquid electrolytes. This process has significant advantages compared to the traditional high temperature processes such as zero CO2 and CF4 emission, low energy consumption due to the low temperature operation and nonconsumable electrodes. Two types of anode materials (graphite, extruded carbon) were tested in electrolysis experiment. The results showed that both anode materials were stable (negligible weight loss). However, the extruded carbon was found to be superior to graphite in terms of current density and current efficiency. The calculated energy consumption for aluminum production was less than 10 kWh/kg at current densities up to 300 A/m2.IntroductionGlobal demand for ultra-light, ultra-strong, recyclable metals is growing as the world switches to low-emission vehicles, energy-saving devices and sustainable products. Aluminum demand is forecast to climb by 30 percent; magnesium demand by 200 percent, while for the emerging industrial light metal, titanium, the demand is expected to be at least double in the next decade. However smelting of light metals is the most energy intensive among all the steps of light metals production. For example, on an average it takes about 15.7 kWh of electricity to produce one kilogram of aluminum from alumina [1, 2, 3]. Advancements in energy efficiency have been steady, but slow, and most U.S. aluminum smelting production operates at 95% current efficiency. Besides high energy consumption, another major concern of the light metals smelting process is the emissions of greenhouse gases (GHG). Electrolysis green house gas emissions in the Hall-Héroult process can be split into three groups: 1) reduction reaction emissions, carbon dioxide (CO2) and carbon monoxide (CO); 2) process upset perfluorocarbons emissions; and 3) hydrogen fluoride (HF) formed from the moisture (H2O) present in the raw materials [2, 3]. Hydrogen fluoride gas can be captured and returned to the cells by the alumina dry scrubbing system used in modern facilities. A total of 5.31 kilograms of CO2 is generated from the reduction process for each kilogram of aluminum produced in the average U.S. primary facility. The perfluorocarbon emissions are related to the “anode effect.” If the concentration of alumina in the bath becomes too low, other reactions between the carbon anode and the bath occur and tetrafluoromethane (CF4) and hexafluoroethane (C2F6) are generated. These gases have high global warming potentials (GWP), which is a ratio developed to compare the ability of each greenhouse gas to trap heat in the atmosphere relative to carbon dioxide"

Jan 1, 2008

By Akira Yazawa

The continuous converting has attractive advantages, but further experimental studies on the slag are required, when the process is considered thermodynamically. The summarized experimental results, obtained with iron silicate slag and with ferrite slag and results relating to actual operation are described and discussed in this paper. At first, equilibrium relations at controlled oxygen potentials among three melts of silica-saturated iron silicate slag, white metal and copper are investigated. The results obtained for slag agreed with the thermo-dynamical predictions. Namely, to suppress a magnetite separation, the system should be at high temperature; in the case of the S02 gas of 10 kPa, for example, magnetite did not separate from the slag at 1300°C, but at 1250 and 1200°C the slag was saturated with magnetite even at lower SO2 pressure. Copper losses caused by dissolution of its oxide increased with increasing 5O2 pressure, and were slightly lower than those reported in previous papers without the matte phase. When the continuous converting slag does not contain any appreciable amount of silica - in contrast to the conventional smelting slag ferrite slag would form, but there was no published fundamental work on-ferrite slags. Hence, the melting behavior and activities of the system CaO-Cu2O-Fe2O3 have been investigated. The liquidus diagram in nitrogen atmosphere was, constructed using both thermal analysis and quenching method. The low liquidus temperature region without magnetite separation was found in the part of low content of Cu2O in the section Cu2O-CaO-Fe2O3 and Cu2O?Fe2O3¬CaO?Fe2O3. The activity of Cu2O in the system was also measured. Slags, composed-of CaO, Cu2O and Fe2O3, in platinum crucibles were equilibrated at 1250°C and controlled oxygen pressures. After quenching, the-composition of slag and platinum crucible were determined qualitatively. On the thermo-dynamic analysis of the results, iso-activity lines were drawn, and it was shown that the slag in the converting furnace of the Mitsubishi process exists in an adequate region of the composition triangle.

Jan 1, 1976

By Martin Brueggemann

In 1993, the El Paso Smelter began operation of the first commercial CONTOP copper smelting furnace. The CONTOP process was chosen for the plant modernization due to its low capital cost and the ease that it could be incorporated into a 100 year old existing smelter. After four years of operation, CONTOP has proved itself to be a reliable copper smelting technology. This paper will discuss a brief start-up history, current operation, and future modifications and improvements.

Jan 1, 1998

By Christian Wögerer

For material or process development as well as for quality checking of materials, thermal diffusivity measurement may be the tool of choice in many applications. Especially if diffusivity is measured locally resolved, a lot of information can be read out of such a ?diffusivity image?. This paper explains the method to measure coplanar specimen like plates and lists some interpretations of diffusivity images, like inhomogeneity of sintered materials, structural voids or inclusions. Diffusivity is a material property, describing transportation of heat in solids in spatial and temporal terms. With thermo cameras it is possible, to measure diffusivity of larger areas simultaneously. The result is an area of diffusivity values that may be plotted or displayed like an image. Locations with lower diffusivity values could be caused by the presents of structural differences in the material, by decomposition of the material components or by inclusions of other material like air.

Jan 1, 2009

By S. Kang, D. G. C. Robertson

Slag cleaning furnaces require extensive wall cooling because they involve the use of a superheated slag bath. This is in direct contrast to smelting furnaces, where the wall is usually (but not always) protected by "banks" of solid charge. In order to understand the heat transfer and flow in slag cleaning furnaces a number of model studies have been carried out using molten wax to simulate the slag. Wax is a good model fluid because, like slag, it has a high Prandtl number. Wax models cannot simulate the behavior close to the electrodes (DC arc or AC submerged), but they can and do give a good simulation of the flow and heat transfer at the wall. An understanding of these phenomena is of great importance for the design of cooling panels in the walls of the furnace. Since superheated molten slag will eventually wear away any refractory bricks over time, the wall cooling must be designed to form a frozen layer of slag, referred to as a "freeze lining". The heat flux density (Q/A) required to do this is given by Q/A = h* ?T, where h is the heat transfer coefficient in the slag phase at the wall, and Li T is the superheat (bulk slag temperature - liquidus temperature). Both Q/A and h vary greatly with position and both are usually a maximum at the slag line. In the experimental work, molten wax baths were heated by block heaters to provide similar energy densities to those encountered in commercial slag cleaning furnaces. This procedure was considered to be valid since most of the electrical energy into a furnace bath is dissipated as heat. Gas stirring was used to simulate the gas evolved at the electrode in real furnaces - the quantity of this gas could be estimated from a knowledge of electrode consumption. The similarity criterion was equal gas flow per unit area of surface, in model and prototype. Heat transfer coefficients were measured in the models as a function of power density, gas stirring, superheat, etc., and could be related to the full-scale operations by the use of dimensional analysis.

Jan 1, 1999

By Sergei A. Degterov

A thermodynamic database for the slag, matte and liquid copper phases in the Cu-Ca-Fe-Pb-Zn-Si-O-S system has been developed for the ranges of compositions of importance to the production of copper. When used with the Gibbs energy minimization software and other databases of the F*A*C*T thermodynamic computing system, this database will permit the calculation of matte-slag-copper-gas phase equilibria that take place during copper smelting and converting. The calculations reproduce within experimental error limits all available experimental data on phase diagrams, activities of components, enthalpies of mixing, matte - alloy miscibility gap and tie-lines. The calculated solubilities of Cu in both S-free slag and slag equilibrated with matte are also in good agreement with experiment under all studied conditions, such as at SiO2 saturation, in equilibrium with Fe, Cu or Cu-Au alloys, at fixed oxygen or SO2 partial pressures and at different contents of Pb, Zn and CaO in the slag. Sulfide contents (sulfide capacities) of the slags are predicted within experimental error limits. The distribution of Pb and Zn among matte, slag, copper and gas has been calculated. The calculations are in good agreement with experimental data and predict the distributions under conditions which are difficult to study experimentally, such as at magnetite saturation or under various oxygen partial pressures and iron to silica ratios in the slag.

Jan 1, 1999

By Chu Yong Cheng

Manganese is one of the main impurities in the recovery of base metals from their ores. This is especially true when laterite ores are processed using the pressure acid leach (PAL) process. The use of intermediate precipitation, solids/liquid separation and re-leach in the three Western Australian nickel laterite plants to separate nickel and cobalt from manganese and other impurities makes these processes complicated and costly in capital and operation. The research work carried out by the solvent extraction (SX) group at the A J Parker Cooperative Research Centre for Hydrometallurgy (CSIRO Minerals) has led to the development of direct solvent extraction processes to separate nickel and cobalt from manganese and other impurities. The simplicity of the process flowsheets and the expected savings in capital and operating costs are the major advantages of the new direct solvent extraction processes over the existing processes. By using a new synergistic organic system, Versatic 10 / dccyl-4-pyridinccarboxylatc ester, with a pilot plant leach solution from BHP¬Billiton (after iron precipitation), the metal values (Ni and Co) together with zinc and copper were separated from manganese and other major impurities (Mg, Ca and Cl) in the first SX circuit. The co-extracted manganese, magnesium and calcium were easily scrubbed out. The extraction and stripping kinetics of the metals with the new synergistic organic system were very fast and the synergistic system was found to be chemically stable. pH-extraction isotherms of metals with D2EHPA showed that the extraction order as a function of pH50 was Zn2+ > Ca2+ > Mn2+ > Cu2+ > Co2+> Ni2+> Mg2+. Semi-continuous test work with a cobalt pilot plant leach solution from Peko Rehabilitation Project Pty Ltd and a synthetic solution to simulate a concentrated laterite leach solution from BHP-Billiton showed that manganese, together with calcium, copper and zinc can be separated from nickel, cobalt and magnesium. This led to the development of another direct solvent extraction process to separate manganese and other impurities from nickel and cobalt and to recover nickel and cobalt from leach solutions. A project was initiated by HiTec Energy Ltd to recover manganese from waste laterite leach solutions using SX technology and to further purify it to produce high purity electrolytic manganese dioxide (EMD) for the high quality alkaline battery industry. Batch tests were conducted to select a suitable organic system for the extraction of manganese in terms of selectivity and extraction and stripping kinetics. A total of eight organic systems were tested using waste laterite processing solutions. A Versatie 10 / synergist system showed very promising results. By using the synergistic system, high manganese recovery would be obtained, fewer SX stages would be required and a higher A:O ratio could be used in extraction, resulting in a smaller organic inventory and lower capital costs. The risk of gypsum formation is also minimised with the synergistic system. Keywords: Solvent Extraction, Manganese, Laterite, Synergist

Jan 1, 2004

By Andreas H. Vassiliou

Organic materials are major constituents of the ore in several uranium deposits. Some of these deposits have been described as "urano-organic" because, the organic materials are believed to have provided the dominant control for the accumulation and deposition of uranium and are directly and intimately intermingled with the uranium. The nature of these urano-organic deposits has been problematic in terms of (a) the origin of the associated organic materials and (b) the specific form of' occurrence of uranium. The organic materials in urano-organic deposits have been genetically related to both coal and petroleum or their progenitors or deriva-tives. Analytical data presented here (infrared, chemical. D.T.A.) suggest that coaliferous materials or related plant derivatives represent the main source of the organic fractions in practically all major urano-organic ores analyzed from the Colorado Plateau and other areas. Recognition of the specific form of occurrence of uranium in urano-organic deposits has been problematic mainly because the uranium is usually in an extremely fine-grained and disseminated state in the organic matrix. Electron microprobe and X-ray diffraction analyses presented here show that fine-grained uranium minerals, specifically uraninite or coffinite. are disseminated in the organic matrix as the predominant form of uranium in most major deposits; however. the presence of true organo-uranium compounds is also suggested for some deposits.

Jan 1, 1981

By Thomas M. Harris

To avoid the escalating cost of disposal of metals-containing wastewater and residues, new wastewater treatments will focus on the recovery of the metals. A combination of ion exchange and electrowinning can produce water suitable for discharge and relatively pure metals. The use of a chelating resin can enhance the selectivity of both the removal process and the elution of metals from the resin. A new, simple method of preparing a variety of chelating resins is being developed. The materials produced by this method exhibit interesting, as well as potentially useful, elution behavior. The performance of one test resin is described.

Jan 1, 1992

By Young-Chul Kang

The Onsan Copper Smelter of LG-Nikko Copper Inc. is a unique plant, which has been operating two smelting processes since 1998. The operation of the first one was started in 1979 with a capacity of 80,000tpy of copper in concentrates utilizing Outokumpu flash-smelting technology. The other one was started in 1998 based on Mitsubishi continuous process with a capacity of 160,000 tpy of copper in concentrates. Through several expansion projects, the total smelting capacity of both processes is expected to reach 430,00Otpy of copper in concentrates towards the end of 2002. This article describes operation advantages of having two different processes at one plant and comparative operation results in terms of productivity, impurity distribution, energy consumption and environment issues and etc.

Jan 1, 2003

By Yoshinobu Fukumori, Testuya Watanabe, Futoshi Shikata, Hiroyuki Tokumitsu, Hideki Ichikawa, Masahito Miyamoto

Nano-particulate systems have attracted much attention recently in pharmaceutical field as drug carriers and functional components of pharmaceutical dosage forms. This paper describes our approaches in design and preparation of nano-particulate systems, including lipid nano-emulsions, chitosan nanoparticles and thermosensitive acrylic nanoparticles, for certain pharmaceutical applications mentioned below. The lipid nano-emulsions with their particle size smaller than 100 nm were prepared for gadolinium neutron-capture therapy (Gd-NCT) of cancer by a thin-film hydration method with sonication, and intraperitoneally injected into Greene's melanoma (melanotic No. 179)-bearing Syrian hamsters. This provided such a high gadolinium concentraton in tumor as 107 µg/g tumor (wet basis) at 48 h after administration. As an alternative gadolinium nano-carrier for Gd-NCT, biodegradable and highly gadopentetate-loaded chitosan nanoparticles (Gd-nanoCPs, 426 mTI in particle diameter and 9.3% in Gd content) were prepared by a novel emulsion-droplet coalescence technique. A significant tumor-killing effect could be obtained when Gd-nanoCP suspension was injected intratumorally twice 24 and 8 hours before neutron irradiation into B 16Fl O melanoma-bearing mice and subsequently thermalneutron was irradiated toward tumor site with a flux of 2 x 109 n/cm2/sec for 60 min. As one another application of nanoparticles, a novel acrylic composite latex with a hydrophobic core and a thermosenstively swellable shell was designed for fabricating microcapsules showing thermosensitive mode of drug release. The microcapsules with the composite latex-dispersing membranes exhibited an exceptionally rapid on-off response of drug-release in a thermosensitive manner.

Jan 1, 2000

By John A. Mavrogenes

The Texaco gasification system developed at the Monte Bello pilot plant efficiently bums petroleum-coke thereby producing syn-gas and electricity. This system produces more electricity than conventional burners, yet the only by-products are pharmaceutical grade sulfur and V -rich slag. Vanadium is known to exist in multiple valence states in compounds which possess a wide range of melting points and physical properties. Consequently, it becomes important to carefully regulate oxygen fugacity throughout the system in order to control vanadium valence state. Vanadium phase equilibria is presently poorly understood, in large part because of the multiple oxidation states of vanadium (-I, 0, +2, +3, +4, and +5) and the difficulty of unequivocally identifying the valence state(s) in many compounds. The operation of these gasifiers at approximately 1400°C is well above the melting point of V20S but considerably below the melting temperature of V02 and V 203. If J02 can be regulated to keep the burner within the V 205 field, slag material would more likely remain molten and more easily flow out of the bottom of the burner. In pure V oxides. the oxidation state is readily determined by microprobe analysis. where V20S (V+5) is 56% V, V02 (V+4) is 61.4% V, and V203 (V+3) is 68% V. However, V valence in multi-element phases (especially phases containing other elements of variable valence) cannot be resolved by microprobe analysis alone. Petroleum-coke gasification slags collected from within the gasifier under different oxidation conditions were studied by electron microprobe analysis (EMPA). X-ray diffraction (XRD). X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. Raman spectrometry in conjunction with microprobe analysis was found to resolve the valence of vanadium in the phases of these slags. Raman spectra collected from homogeneous single phase V-oxide standards in vacuum at low temperatures (-150°C) yielded peaks characteristic to each valence state. Gasifier slag samples are, however, much more complicated. Oxidized samples contain: fine grained (Ca. Mg, Fe. V) oxide matrix of variable composition, (Fe. V, Ni) spinel. (Fe, AI, V, Ni, Mg) spinel, V205laths, AI-Si glass blebs and Ni sulfides. Reduced samples contain: crystalline Ca-siIicate matrix, subhedral to euhedral (V, Fe, Mg, AI) spinel, subhedral V02, Fe and Fe-Ni sulfides, Fe-Ni alloys, and complex Ca-oxide matrix. The different spinel assemblages, the characteristic V-oxides and the distinctly different character of the matrices makes the oxidized and reduced slags readily discernible.

Jan 1, 1995