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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

By M. D. Strachan

Technical & Procurement Services Limited (TECHPRO) in Ashford, Kent, UK, have been appointed as Project Managers for the major rehabilitation of the Copper Smelting complex of Nkana Division, Zambia Consolidated Copper Mines Limited, (ZCCM) Zambia. In outline, the overall scope covers three main areas: a) Transfer and implementation of new technology into Zambia for the production of primary copper. b) Replacement of gas collection and gas treatment circuits to guarantee high quality feed to the acid plants. c) Completion of a number of minor projects in the copper smelter and associated utility plants to complement changes in the primary smelting technique. This paper describes the Project Management methodology and style used by TECHPRO to tackle typical problems that arise in retrofit projects of this type. Reference is made specific aspects of the smelter projects to illustrate solutions to the problems. The subjects. addressed highlight the complexities not only of having a -Client 5,000 miles from the Project Office, but also the difficulty of co-ordinating and controlling the performance of min sub-contractors who are also geographically distant.

Jan 1, 1991

By A. J. Duncan, S. Viswanathan, Q. Han

"Measurements of liquid permeability in the mushy zones of Al-15.42% Cu and Al-8.68% Cu alloy samples have been performed isothermally just above the eutectic temperature, using eutectic liquid as the fluid. A modified method has been developed to determine the specific permeability, Ks, as a function of time during the test from the data collected on these alloys. Factors affecting permeability measurements are discussed. Permeabilties are observed to vary throughout the experiment. This is attributed to rnicrostructural coarsening and channeling that occurs in the sample during the experiment. The permeability is related to the rnicrostructure of the sample using the Kozeny-Carman equation. The correlation between the measured Ks, liquid fraction, gL and the specific solid surface area, Sv, improves markedly when compared to previous studies in which rnicrostructural coarsening was ignored.IntroductionThe permeability of interdendritic liquids flowing through dendritic structures ·is an important parameter needed to predict the level of porosity in castings. The permeability is a component of Darcy's Law, used to estimate the pressure drop due to the resistance to the flow of interdendritic fluid to feed shrinkage. Therefore, much research has focused on measuring the permeability of alloys in the mushy zone (1-10). The Kozeny-Carman equation for liquid permeability in the mushy zones of alloys may be written as"

Jan 1, 1999

By Kikuo Okuyama, I. Wuled Lenggoro, Manabu Shimada

"Aerosol processing of materials such as (i) gas-to-particle conversion process (e.g., Chemical Vapor Deposition (CVD) method) and (ii) liquid (or droplet)-to-particle conversion process (e.g., spray pyrolysis) has become of major interest to produce novel submicron- or nanometer-sized particulate material used in electronic and chemical industries. After reviewing recent theoretical and experimental researches on the evaluation of properties and morphology of fine particles by the CVD and spray pyrolysis methods, the importance of the process engineering approach· for aerosol processing of materials and the use of advanced aerosol measurement technology have been pointed out.IntroductionMaterial synthesis via aerosol processing offers a route to producing nanometer-sized and submicrometer-sized particles of high purity with specifically tailored chemical and physical properties. Especially, single nanometer-sized particles (nanoparticle materials) are considered to play an important role in the synthesis of nanostructured materials as well as in nanotechnology in 21st century due to their quantum effect and so on.However, the transformation of gaseous or liquid precursors to the final functional particulate matters consists of various complex chemical and physical processes. In order to control the size distribution and morphology of produced particles, it is important to analyze and model various phenomena, such as gas-phase or liquid-phase chemical reaction, nucleation, condensation, agglomeration and sintering that occur simultaneously in aerosol material processing. By introducing the Aerosol Science and Materials Science, the authors have been trying to model the changes in particle properties and morphology by gas-to-particle conversion and droplet-to-particle conversion processes. The authors have also been trying to obtain the experimental data on the particles properties as accurate as possible."

Jan 1, 2000

By Rauf Hurman Eric

The high temperature liquid miscibility gap in the Ag-Ag2S pseudobinary portion of the Ag-S system has been redetermined by very carefully conducted equilibration-quenching experiments. Samples were contained in evacuated and sealed silica capsules. The stratified liquid phase compositions were obtained by chemical analysis. The miscibility gap extends from 14 to 32.3 atomic percent at the monotectic temperature of 906°C and closes at around 1320°C.Thermodynamic properties of the liquid solutions, including the limiting activity coefficient of sulfur in molten silver were expressed analytically by using the sub-regular solution model which proved to be in excellent agreement with the experimental findings.

Jan 1, 2006

The merging of flash smelting with spray converting in one single furnace is proposed as a continuous copper making process. The proposed process is expected to produce blister copper, clean slag and gas with high sulfur dioxide concentration. Some high grade matte is an intermediate product recycled within the proposed furnace, spray-atomized and converted. The thermodynamic equilibria of the simultaneous oxidations which take place during copper smelting and converting are discussed in order to establish the gradient of oxygen potential along the furnace required for smooth operation. The proposed process is a dynamic system designed to reach equilibrium only close to the slag skimming end of the furnace. The process feasibility is based on the predesigned significant difference between the rates of converting reactions in a finely dispersed system and the rates of deconverting reactions between immiscible liquid phases of restricted interface area. The converting of small stationary droplets of matte, in a silica saturated system, was studied in the laboratory for extremely short oxidation times (10 to 120 seconds). These experiments led to some interesting observations on reaction mechanisms and kinetic trends. The droplet size and the matte grade affected very strongly the oxidation rate and the proportion of the different products obtained.

Jan 1, 1976

By Simon Lekakh

Direct reduction of Cu,Ni,W,VandMo oxides from various industrial wastes the melting of iron and steel in different furnaces was studied by thermodynamic computation and experimental methods. Thermodynamics was used to compute the final partition of the alloying additions between iron-carbon melts and oxides contained in the slag. It was shown that the sequence of the reduction reactions depended on the melt composition as well as temperature. Kinetic factors limited recovery in induction melting, while experimentally measured final partition coefficients were close to equilibrium during EAF melting. The possibility of the partial substitution of expensive ferroalloys, by different industrial wastes containing nonferrous oxides, was evaluated in foundry and mini-mill conditions.

Jan 1, 2006

By Derek J. Fray

The need for on-line sensors is outlined and it is demonstrated that the control of many processes is prevented by the availability of these devices. The use of solid electrolytes is described for the sensing of elements in molten pyrometallurgical phases. In the cases where there is no suitable electrolyte, the addition of a second phase of a compound containing both the element to be measured and the element whose ion is mobile in the electrolyte can be used. For the measurement of high concentrations of an element a method based on current measurement is proposed.

Jan 1, 1994

By V. Kamavaram

Ionic liquids are novel salts used as potential non-aqueous electrolytes for aluminum electrolysis at low temperatures. In the current research di-alkylimidazolium chloride ionic liquids such as 1-butyl-3-methylimidazolium chloride ([BMIM]Cl) and 1-hexyl-3-methylimidazolium chloride ([HMIM]Cl) were investigated for aluminum electrolysis. Melt formed by mixing ionic liquid with AlCl3 is termed as chloroaluminate and is composed of several polymeric chloroaluminate anions. Ionic liquids are studied as electrolytes for aluminum electrowinning and electrorefining of aluminum based materials (A356, A360, & Al-MMC) at low temperatures. Mechanism of aluminum electrodeposition in these chloroaluminate ionic liquid electrolytes was investigated using electroanalytical techniques such as cyclic-voltammetry and chronoamperometry. Aluminum electrodeposition on pure copper substrate in AlCl3-[BMIM]Cl (1.5:1.0) electrolyte at 30°C melts was found to be quasi-reversible process with a charge transfer coefficient ( of 0.40. Chronoamperograms obtained at different voltages in the range (-0.1 to -1.0 V) revealed that the initial stages of aluminum deposition in AlCl3-[BMIM]Cl melts was instantaneous nucleation followed by diffusion controlled growth of three-dimensional aluminum nuclei. The diffusion coefficient of electroactive species Al2Cl7¯ in AlCl3-[BMIM]Cl melts was found to be 6.5×10-7 cm2 s-1 from Cottrell?s equation and 3.9×10-7 cm2 s-1 from the dimensionless current-time transients.

Jan 1, 2006

By Claude Lorenson

"The Spyrometer™ imaging pyrometer brings new dimension of imaging capabilities to temperature measurement technology by combining a high temperature video camera with scanning optical pyrometry. This gives the operators the ability to observe process conditions while measuring the temperature of virtually any object or region in the field of view. Since the lens tube of the camera can be air or water cooled, it is possible to see inside furnaces giving a very good view of many different types of metallurgical processes. Specific benefits in process knowledge and maintenance tasks for furnaces in different types of metal industries are discussed.1-Principles of Imaging PyrometryLens tube, camera and processorImaging pyrometry is the combination of video imaging and computer-driven pyrometry that measures the temperature of certain zones (selected by the operator) within the image viewed on the monitor screen. To obtain a detailed image of the metallurgical process under observance, it is necessary to place the optical objective of the camera close to the process. The Spyrometer™ (which is Quadtek's tradename for its imaging pyrometer) objective is housed in a lens tube that is cooled and permits insertion inside the vessel of interest. The length of the lens tube is chosen on the basis of making sure that the tip of the tube is just beyond the refractories lining the inside of the furnace. In most pyrometallurgical processes, we have found that the most reliable system set-up uses a water cooled shroud to cool the lens tube optics. A sapphire window provides maximum protection from the environment. Even in the case of the water cooled version, there is an air purge for the lens that keeps the objective clean and protects against hot metal splashes."

Jan 1, 1997

By M. -L. Metsärinta, J. Nyberg, A. Roine

The Kokkola roasting plant uses more than 20 different zinc concentrates every year. During recent years there has been an increase in the variation in concentrate quality; in particular, the amount of fine-grained and low-grade concentrates has increased. Therefore, a great deal of development work has been carried out to improve the operational flexibility, online availability, production capacity and calcine quality of the roasting plant. This work consisted of a heat and material balance model of the roasting based on HSC Chemistry software, a new water admixture system for the concentrate feed, a new oxygen feed system for the process air line, improved cooling of the furnace and boiler and improved operational practices, dust removal and concentrate mixing. These new process control tools and other improvements, as well as some test results, will be described in this paper. The oxygen feed may be used to improve production capacity and to decrease the sulfide content of the calcine. The water feed may be used with fine concentrates to decrease both dust carry-over and the temperature in the top part of the furnace. Improved cooling of the furnace and boiler helps to increase production capacity.

Jan 1, 2000

By G. Springer

The identification of lost mineral values in mill tailings frequently requires the inspection of hundreds of thousands to millions of particles. The search of these particles can be made automatic by using an electron microprobe. A standard instrument (Cambridge Mark V) was modified by the addition of stepping motors to advance the specimen stage in a controlled manner. The X-ray Signal is monitored continuously by a computer interfaced to the instrument with an analog-to-digital converter. 400,000 particles of a tailings sample can be scanned in about 3 hours. Particles as small as 2 um and containing as little as 3% of a particular element can be detected.

Jan 1, 1982

By C. Dresen

This paper discussed the reaction kinetics of the reduction of industrial phosphate pellets for P4 production. In the reduction process of various phosphate ores, the following parameters were investigated: Diffusion of the phosphorus oxide and other gaseous products from the reaction mixture after having been reduced on the reductant (coke) surface. Influence of silica on reaction kinetics. Temperature influence. Influence of mineralogy and morphology (different ores). Particle size influence of silica and coke. Experiments were carried out in a vertical tube furnace with 2 ores, 2 types of silica and one type of coke. Selected experimental conditions simulated furnace conditions. The following conclusions could be made: Reaction rate increases with the addition of SiO2 into the pellet. The reaction rate increases above 1350°C (melting temperature of the slag). Mixing different ore types in the pellets leads to differences in reduction kinetics. Particle size of the coke particles influence reduction kinetics. The amount of slag formation is influenced by silica addition, coke size and temperature.

Jan 1, 2002

By V. Baltazar

The behaviour of arsenic and antimony during copper electrorefining was studied in order to identify the conditions under which good quality copper cathodes could be produced from anodes with high levels of these impurities. Examination of the effect of current density over the range 21 to 37 mA/cm2 indicated that the relative amounts of As and Sb entering the electrolyte affected the onset of passivation. When the ratio of As/Sb entering the electrolyte was greater than 2, the anodes showed no sign of passivation even at the highest current density; when the ratio was less than 2, the anodes passivated at 37 mA/cm2. Cathode analyses showed that anodes with an As/Sb dissolution ratio less than 2.0 tend to produce cathodes of inferior quality even at normal current densities (25.7 mA/cm2). The criterion of a minimum As/Sb dissolution ratio of 2.0, and mathematical correlations for the distribution of As and Sb between the electrolyte and slime developed in a previous study, allow the calculation of the maximum allowable Sb level in en anode for a given As concentration. Analyses of plant data at the CCR Division of Noranda Inc. for the last four years of operation have demonstrated that the use of this as a quality control tool has allowed the quality of copper cathodes to be maintained despite a significant increase in the average Sb levels in anode receipts.

Jan 1, 1987

By J. J. Moore

The application of plasma technology to process metallurgy is briefly discussed. Experiments involving in-flight reduction of minerals (taconite, chromite, in particular) with a solid-based carbon reductant are described. The resultant metallic and slag product analysis is discussed with respect to thermodynamic and kinetic considerations.

Jan 1, 1985

By E. J. Peuraniemi

Recently commissioned Kennecott-Outokumpu flash converting was developed to replace the approved but environmentally outdated Peirce-Smith -converting to satisfy the globally tightening emission regulations. In the present study, dust formation and reaction mechanisms of two copper mattes with different experimental parameters were studied in lean suspension conditions. Both mattes had very high copper content of approximately 75 wt% and low iron content of 4.5 wt% and 1.2 wt% Fe. A laboratory scale, vertical laminar-flow furnace with a low feeding rate was used to simulate the phenomena taking place in the reaction shaft of a flash converter. Experimental conditions included temperature of 1300 °C with reaction gas oxygen contents of 20 vol%, 50 vol%, and 75 vol%. In the experiments, sieved particle fractions were fed to the furnace and sampled after short reaction time intervals by quenching them into a water film. Collected particles were analysed chemically for their main elements to define their removal rates. Also, optical and scanning electron microscopy with EDS-analyser were applied to determine phenomena occurring during reactions. Kinetics of oxidation as well as ignition of particles are discussed. Changes in particle morphology, size, and composition are reviewed to describe dust formation and reaction mechanisms.

Jan 1, 1999

By H. K. Lin

Pyrite oxidation in chloride solutions was investigated with cyclic voltammetry, ac impedance and potential step techniques. The pyrite oxidation in quiescent electrolytes is irreversible and controlled by diffusion. Depression of the semi-circle in the complex plane plot has been explained mathematically based on the concept of the equivalent circuit. When the semi-circle is depressed, the mathematical formula indicates that the reaction resistance should be obtained from the intersection of the semi-circle with Z-axis instead of the semi- circle diameter. The peak charging current densities at 1.10 and 0.90 V vs. SHE obtained from the equivalent circuit coupled with the ac impedance measurements match the peak current densities obtained with the potential step measurements.

Jan 1, 1997

By Toru Taniguchi

In the Mitsubishi smelting furnace, copper concentrate, silica sand and water granulated slag from the converting furnace are injected through the process lances, together with oxygen enriched air, into the melt. Because bath smelting is used, the rates of particles/melt and gas/melt reactions are high enough and therefore tine grinding of the solid materials is' not necessary. Among these reactions, the dissolution rate of silica sand is the slowest and limits the overall reactions in the smelting furnace. Information on the dissolution rate of silica sand plays an important role for design of a new furnace. Theoretical calculations of the dissolution rate .of silica particles have been reported elsewhere. The authors conducted cold model experiments and could verify the calculation. In this paper, the dependence of dissolution rates of particles on the gas blowing rate, particle size and solid penetration depth in the bath is discussed.

Jan 1, 2002

By Shabnam Sabah, Geoffrey Brooks

In oxygen steelmaking, splashing and droplet formation play a key role in the kinetics of the process. Though splashing has been studied by previous investigators, there is only limited understanding of how different cavity modes affect splashing. Therefore, a cold model study (at various lance heights and gas flow rates) has been carried out focusing on the issue of cavity modes and how it affects splashing phenomenon. Analysis using Fast Fourier Transform (FFT) was carried out on cavity oscillation that showed that frequency and amplitude of oscillation was highest in penetrating mode. Measurements of splashing over a range of conditions showed splashing greatly reduced when cavities went from splashing to penetrating mode. The results were validated and compared with plant data and previous model investigations.

Jan 1, 2014

By Yang Tian-zu

Sodium pyroantimonate which is widely used as the clarifier in the glass industry and as the synergist in anti-flaming industry respectively has a production history of about 30 years in China. At present there is the production capacity of about 20,000 tons per year in China and China is chief producer of sodium pyroantimonate. In this work the production processes adopted by the producers of China, the operation conditions and the product qualities of sodium pyroantimonate prepared by different preparation methods have been summarized, and on the basis of comparing the advantages and disadvantages for each process the most advanced method - the air-oxidation method was introduced in detail. The production processes of sodium pyroantimonate mainly include the method of oxidation by sodium nitrate, the oxidation method of hydrogen peroxide, the potash salt method, the chlorination method and the air-oxidation method etc. The method of oxidation by sodium nitrate in which the crude antimony oxide, sodium carbonate and sodium nitrate are separately used as the raw material, the flux agent and the oxidant, has the advantage of short and simple technological process, but low grade quality of sodium pyroantimonate and bringing about serious environmental pollution are the disadvantages and this method has been substituted by other methods. Sodium pyroantimonate can be directly prepared by the hydrogen peroxide oxidation method with the advantages of simple technological process, high grade quality of the product and little environmental pollution. High grade quality of sodium pyroantimonate can be also synthesized by the potash salt method, in which industrial antimony white, the hydrogen peroxide, potassium hydroxide and sodium hydroxide are applied as the starting material. The disadvantages of these two preparation methods are high production cost and high requirements on the raw materials. The chlorination method with the crude antimony oxide, hydrochloric acid and chlorine as the raw material has the advantages of low production cost and high grade quality of the product. However complex process, high requirement of anti-corrosion for the equipments and producing plenty of waste water limit its application. The air-oxidation method with stibnite/jamesonite concentrate, sodium sulfide, and sodium hydroxide as the raw material and atmosphere as the oxidant is a newly developed method and its advantages are low production cost and the complex raw material can be treated by this method and its disadvantage is that the quality of sodium pyroantimonate is lower than that prepared by the oxidation method of hydrogen peroxide and the potash salt method.

Jan 1, 2006