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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 Norihiro Murayama

The hydrothermal syntheses of zeolites from coal fly ash were carried out using NaOH and KOH as an alkali source. The cation exchange capacity (CEC) and the ion exchange selectivity were investigated for the zeolites synthesized by a hydrothermal treatment. The effective usage of the zeolite as a cation exchanger was considered from the viewpoint of engineering. Zeolite P, HS (hydroxysodalite) and K-CHA (potassium-chabazite) are mainly formed as zeolite species in NaOH or KOH solution at 393K. The zeolite P and K-CHA have a large exchange capacity as a cation exchanger. The cation exchange isotherms of various monovalent and divalent cations with various zeolites are investigated. The order of selectivity of the zeolites is as follows, NH4+> K+> Li+.For the divalent cation, the largest removal amount is obtained for Pb2+ in the low equilibrium concentrations below 0.2mmol/dm3, and almost perfect removal can be achieved for Pd2+. The order of selectivity of zeolites in low concentration is expressed in the following order; Pb2+> Co2+> Cd2+> Ca2+> Mg2+> Ni2+. Ii is considered the zeolites obtained from coal fly ash can be used as an excellent cation exchanger.

Jan 1, 2006

By N. M. Komkov

The main operation of obtaining zinc from sulfide raw materials by hydrometallurgical technologies is the oxidation roasting of zinc concentrates in fluidized bed furnaces. The technical-economic parameters are determined by the parameters of the roasting process, which depend on the composition of the initial raw materials, the temperature of the bed and on other factors. The predetermined roasting temperature is maintained due to the change of specific efficiency as well as to the quantity of the heat removed from the bed. The efficiency of caissons depends at a high degree on the composition and the thickness of the accretion formed on the surface of the caissons. Forecasting the roasting results is impossible unless we know the mechanism of the accretion formation. The aim of the present paper is the thermodynamic analyses of the behavior of the charge compositions under roasting and the determination of the potential mechanism of the accretion formation. The thermodynamic analyses show that under conditions of the oxidation roasting the thermodynamic probability of the formation of zinc sulfate is higher than the probability of the oxide formation until a temperature of 873°K is reached. The thermodynamic probability of the formation of the lead sulfate is higher than the probability of oxide formation in the entire temperature range of roasting. The probability of formation of ferrites and silicates of zinc decreases only insignificantly the sulfate stability. The results of the investigation of the accretions composition formed under roasting of concentrates with particle sizes less than 0.02 um (60%), containing 65% of sphalerite (ZnS), 12% of pyrite and chalcopyrite (FeS2 and CuFeSz2 each, 3% of galenite (PbS), 7% of silica and other non-ore minerals, have shown that the composition of accretion varies depending on the depth of the accretion layer. The accretions on the caissons and the thermo-siphons consist mostly of zinc sulfate (more than 50%). The accretions of forchamber consist mostly of zinc oxide. They also contain ferrites and silicates. The formation of the sulfate zinc accretion in the cold parts of the fluidized bed furnace (the caissons and thermo-siphons) may be explained by a lower temperature on the surface and probably by a catalytic influence of the present oxides in the formation of S02 and sulfates. The nature of the structure of the accretion in the hotter parts of the furnace may supposedly be explained by the formation of elemental vaporous zinc during roasting.

Jan 1, 2003

By George Kazonich

The high costs and environmental problems associated with making iron and steel in the United States is driving the development of new technologies to replace the blast furnace. A prototype reactor incorporating rocket technology was designed and built. This rapid rate reactor was operated successfully and consistently made iron metal. Minus 325-mesh magnetite particles could be reduced to iron metal in less than 50 ms in a high temperature flow through reactor. Iron product was recovered inside the reactor and in a downstream cyclonic separator. The results of typical operation and how parametric changes affected the reduction of iron ore concentrates are discussed.

Jan 1, 1993

By S. Seetharaman, Du Siehen

"In the processing of molten metals, it is extremely important to monitor continuously the concentration levels of various minor elements. In the production of common metals like copper, iron and aluminium electrochemical sensors involving solid as well as liquid electrolytes are being increasingly used to measure the concentrations of minor elements. The present paper deals with the electrochemical principles underlying these measurements and the possible errors involved. One of the major difficulties in the case of the solid electrolytes is to correct for the consequences of the electronic contribution to the conduction of the electrolyte.The application of the electrochemical sensors for molten metals processing involves designing of these probes to withstand the industrial operating conditions. In this respect, significant achievements have been made with respect to the design of oxygen probes for liquid metals in general and liquid copper in particular. Some of the salient design features are discussed in the paper. The application of auxiliary electrodes for impurities in molten metals like phosphorus in copper and silicon in iron are taken up. The development of oxygen sensors for slags is given special attention. Recent developments in the field of sensor technology, as applied to metals processing are highlighted.1. IntroductionThe rapid technological advancement today require precise control of the process parameters and the impurity levels. Most of the molten metals processing in industrialized countries are often steered by suitable computer models, either phenomenological or simulations based on theoretical principles. These models often require that the process parameters are continuously monitored so that the progress is followed and modified suitably as and when required. It is common practice to measure temperatures by incorporating temperature sensors at the various strategic points of the reactor. In the case of monitoring the composition changes in the various phases, the method of sampling followed by routine chemical analysis involves a time lag as well as uncertainties in sampling and analysis. In this respect, electrochemical sensors have the advantage of generating accurate data when properly applied and increasing attention is being paid in the development of electrochemical sensors for various common species in molten metals processing. In the present paper, the developments in this area over the years are outlined and typical process applications are discussed. A greater emphasis will be laid on sensors based on oxygen conducting electrolytes and their application to the production of common metals like iron and copper."

Jan 1, 1996

By N. El-Kaddah, A. D. Patel, T. T. Natarajan

The phenomenon of particle migration in a conducting fluid under an applied electromagnetic force field finds its application in selective sorting of minerals and more recently in the removal of inclusion from molten metal. This paper deals with the analysis of the expulsion force and the flow around a spherical particle in crossed uniform electric and magnetic fields in .infinite and in confined medium. Analytical solutions will be presented for the electrk and magnetic fields as well as the induced flow at the limit of zero Hartmann number. The flow around the particle was investigated numerically at low and high values of Hartmann number. It will be shown the magnetic field has almost no effect on the velocity field when Hartmann number is less than 1.0. At higher Hartmann numbers the damping effect of the magnetic field was pronounced in the direction of the applied current. It is concluded that Hartmann number has little effect on the net force on the sphere particle.

Jan 1, 1999

By Lenny Winkel

With the aim to develop a solar-driven process for the extraction of copper from sulfide concentrates research on the decomposition of copper sulfides under inert atmospheres has been initiated. Thermogravimetric measurements on chalcocite,(Cu2S) revealed that copper is formed already at 1823 K. Chalcopyrite (CuFeS2) also disintegrates at this temperature, although at a lower rate. Copper and iron have been identified in the solid residue. The results confirm the feasibility of copper extraction by direct decomposition of sulfides under atmospheric pressure. The decomposition under inert atmosphere prevents generation of SO2, it also alters the behavior of volatile impurities during decomposition of copper sulfide concentrates. Chemical equilibrium calculations for chalcopyrite contaminated with enargite (Cu3AsS4) have shown that the absence of an oxidic slag allows for a complete evaporation of arsenic and subsequent separation from intermediate sulfides. The need to better assess the potential of direct sulfide decomposition has prompted the development of an experimental setup for studying the decomposition reactions. The experiment has been devised such that data on the decomposition kinetics and on impurity removal can be obtained at temperatures up to 2500 K.

Jan 1, 2003

By K. Tozwa

The electrical conductivity of electrolytes for copper electrorefining and electrowinning processes has been reported by many researchers since 1911. The experimental results show that the conductivity increases with an increase in sulfuric acid concentration and decreascs with an increase in copper concentration. In pure copper sulfate solution, however, the conductivity increases with an increase in the copper concentration. After confirming the conductivity of pure and acidified copper sulfate solutions experimentally, the concentrations of hydrogen ion and free (not hydrated) water in the electrolytes were estimated and it was found that the relation between the conductivity of acidified copper sulfate electrolytes and the products of concentration of hydrogen ion and free water is linear. Accordingly, the conductivity of acidified copper sulfate electrolytes increases with an increase in sulfuric acid concentration and decreases with an increase in copper concentration.

Jan 1, 2003

By Yasuhiro Konishi

Hydrolytic stripping is the process in which metal ions are simultaneously stripped from a loaded cation-exchange solvent extractant and precipitated as oxides or hydroxides. Hydrolytic stripping is usually effected by contacting the loaded organic phase with water at elevated temperatures. The possibility of using hydrolytic stripping to prepare ceramic powders with controlled size and morphology is now being evaluated for different systems, using carboxylic acid extractants. As part of this work, mathematical models were developed to describe the kinetics of nucleation and growth of nickel ferrite particles. This paper describes the development of the models, along with estimation of key parameters appearing in the rate equations from experimental data.

Jan 1, 1990

By J. A. Sekhar

Solidification processing/casting is increasingly being adopted as the preferred manufacturing technique for the fabrication of net shaped complex geometry components. Modeling of solidification processes is important both for design purposes as well as for understanding the physics of morphological evolution of the solidification microstructure. A fundamental aspect of such modeling involves the precise understanding? of heat transfer through the two phase solid/liquid region. A scheme to do this will be presented where the nonlinearity of the fraction liquid with change in temperature can be incorporated into the numerical calculations. The importance of properly accounting for the non-linear mushy zone will be discussed. Typical processes like squeeze casting and electromagnetic stirring will be discussed to illustrate how precise modeling of the solid/liquid region can aid in the calculation of accurate heat transfer coefficients for these processes.

Jan 1, 1990

By John C. Taylor

With growing emphasis on energy conservation and increased concern over the presence of heavy metals in the environment, it is fortunate that most metals are readily recycled. In this respect, metals have a significant advantage over plastics and similar materials used as metal substitutes. For many years a secondary industry has processed scrap copper, nickel, lead and zinc to produce refined metal which has, to varying degrees, influenced the price and displaced the production of primary metal. This paper reviews some of the challenges the industry will face and the changes in process technology which will be required as pressure mounts to increase the amount of metal recycled. In the case of most base metals, this will have an impact on primary metal production; as the tonnage of metal recycled increases, the requirement for primary production, or new metal, will depend more and more on the growth in consumption.

Jan 1, 1993

By R. Winand, M. Degrez, C. Temmerman

"The influence of the copper electro crystallization inhibitors (mainly thiourea, gelatin and chloride ions) is studied in a new fully automatic pilot plan. This paper describes the conception and the building of this plan. The new approach is to reproduce the experimental conditions observed in the industry with the three additives present simultaneously in the electrolyte and secondly to study the influence of a slight modification of the concentration of one inhibitor, the others being present in the electrolyte with their industrial nominalconcentrations.1. INTRODUCTIONDespite the fact that gelatine, thiourea and chloride ions have been used in copper electrorefining for a long time, precise knowledge concerning their influence on the cathode deposit, metallographic structure and associated properties is still lacking.Many authors studied the influence of each additive separately, or of two added at a time. Only a few authors studied the combined influence of the three additives added simultaneously. The general conclusion that can be drawn is that the combined influence is far from that forseen from the influence of each additive separately, or even from two additives used at a time. Moreover most of the experiments described in the literature were performed by adding all additives at once initially. It is however, well known that gelatine looses a great part of its activity during the first half hour due to degradation by sulfuric acid (as shown by the cathode overpotential drop). Thiourea is rapidly replaced by a number of degradation mole,cules and complex ions including cations from the solution, changing even the equilibrium between Cu, Cu(I) and Cu(II).Chloride ions are consumed by precipitation.A number of successive research projects [1-9] led pregressively to the concept that, in order to obtain reproducible results representative of industrial cathodes, it was necessary to simulate as far as possible industrial conditions. It was essential that all additives were added continuously during the electrolysis, with, as consequence, a continuous bleed.The purpose of this paper is to describe the concept of a new fully automatic pilot plan for copper electrorefining and to present the first results."

Jan 1, 1997

By Francis Vanbellen

Umicore Precious Metals Refining operates an integrated precious metals smelting and refining plant in Hoboken, Belgium. Once a smelter and refiner of complex concentrates, the plant today?s feed consists exclusively of industrial and consumer recycled products, making it the world?s largest recycling facility for precious metals. Unlike the fairy tale of the Frog Prince, it took much more than a princess? kiss to successfully realize this makeover. A completely renewed plant has been built over the past decade. The most visible technological innovation was the commissioning of the Pb-Cu smelter. Its flexibility towards very different types of feed makes it perfectly suited as main entry to the Hoboken flow sheet. A new Cu-leaching & electro winning plant and precious metals refinery make up the Precious Metals Operations (PMO) whose targets are fast throughput and maximized yields for gold, silver and the platinum group metals. The Base Metals Operations (BMO), flexibly process the by-products from the PMO, valorizing ?impurities? like indium, tellurium, selenium and others. Off gas and waste water treatments ensure compliance with strict environmental standards. Precious metals recycling is an art that goes beyond mastering a unique flow sheet. Umicore Precious Metals Refining offers a complete recycling service, taking care of sampling and assaying, metals management and logistics. The quality of this integral service is recognized through the attribution of ISO certifications for our operational activities, sampling and the environmental care. And it?s an art that follows Michelangelo?s experience: ?Art is 5% of inspiration and 95% of transpiration.?

Jan 1, 2006

By Tatsuzo Kitamura

The tank house of Tamano refinery, that started its operation in January, 1972, was constructed incorporating the application of Periodic Reverse Current (P.R.C.) from the outset of design works. In 1973, the production of electrolytic copper came up to 8,000 mtpm, a sharp increase ds compared with the designed capacity of 7,000 mtpm, and successful operation has been achieved up to the present. P.R.C. has been employed for the purpose of raising productivity level and reducing copper inventories. Since there were various problems in P.R.C. application to such a large sized cathode as 1 m x 1 m, special attentions were paid to the following items: -Development of a unique bus bar to make an electrolytic current to each electrode as uniform as possible. -Improvement of circulating method of electrolyte. -Application of high-performance equipment to realize a uniform spacing between anode and cathode. Owing to these creative technical developments mentioned above, technical level for operation up to 350 amp per sq m of cathode current density has been established. The quality of electrolytic copper, which was a matter of interest, has been proved to be as excellent as those of conventional electrolysis products through a long term supply to the field of SCR and Dip forming where high levels in quality are required.

Jan 1, 1976

By H. Bai, B. G. Thomas

"A three-dimensional finite difference model has been developed to study the liquid steel-argon bubble two-phase turbulent flow in continuous casting tundish nozzles. Experiments have been performed on a 0.4-scale water model to verify the computational model by comparing its prediction with velocity measurements using PIV (Particle Image Velocimetry) technology. The computational model was developed using CFX and then employed to investigate the effects of various casting process variables. A fast, simple inverse model to quantify relationships between those process variables was developed, based on interpolation of the numerical model results, using Bernoulli's Equation and advanced multivariable curve fitting methods. Predictions using this model compare well with plant measurements. The model has been applied to present trends and observations on the relationship between casting speed, tundish depth, slide gate opening, and argon gas injection rate. The results can also be used to predict .the theoretical steel flow rate through the nozzle, so that clogging conditions can be identified in the plant.IntroductionTundish nozzle geometry is one of the few variables that are both very influential on the casting process and relatively inexpensive to change. Designing an effective nozzle requires quantitative knowledge of the relationship between nozzle geometry and other process variables on the influential characteristics of the flow exiting the nozzle. This relationship depends on the flow pattern within the nozzle components. Most previous modeling studies of flow in the nozzle have focused on single-phase flow [1-4]. Argon injection into nozzle is an efficient and widely employed method to reduce nozzle clogging, even though the real working mechanism(s) are still not fully understood [5]. Argon injection may greatly affect the flow pattern in the nozzle, and subsequently in the mold. Therefore, two-phase flow modeling is needed to improve understanding of fluid flow in the nozzle."

Jan 1, 2000

By Frank M. Kimmerle

Spent Potlining (SPL) contains recoverable chemical elements (C, F, Na and Al) which are lost in stabilization or immobilization processes primarily aimed at eliminating cyanides and reducing leach rates of soluble fluorides prior to landfiling. They can be recovered in a variety of mineral forms for recycling in the aluminum industry and elsewhere. Alcan has developed a cost-effective hydrometallurgical route, combining a number of proven unit processes to destroy cyanides, recycle the chemical values and provide a zero-discharge process. Pilot plant studies of this Low Caustic Leach and Liming (LCL&L) Process prove that the fluoride scan be converted to acid grade fluorspar, while the sodium and aluminum are recovered as a sodium aluminate and caustic feed to the Bayer Plant operations. The remaining brick and carbon fraction constitutes a high ash solid fuel which meets TCLP leach criteria and whose reduced sodium content enhances its value as a chemical reducing agent.

Jan 1, 1994

By Francis Vanbellen

Umicore Precious Metals Refining operates an integrated precious metals smelting and refining plant in Hoboken, Belgium. Once a smelter and refiner of complex concentrates, the plant today?s feed consists exclusively of industrial and consumer recycled products, making it the world?s largest recycling facility for precious metals. Unlike the fairy tale of the Frog Prince, it took much more than a princess? kiss to successfully realize this makeover. A completely renewed plant has been built over the past decade. The most visible technological innovation was the commissioning of the Pb-Cu smelter. Its flexibility towards very different types of feed makes it perfectly suited as main entry to the Hoboken flow sheet. A new Cu-leaching & electro winning plant and precious metals refinery make up the Precious Metals Operations (PMO) whose targets are fast throughput and maximized yields for gold, silver and the platinum group metals. The Base Metals Operations (BMO), flexibly process the by-products from the PMO, valorizing ?impurities? like indium, tellurium, selenium and others. Off gas and waste water treatments ensure compliance with strict environmental standards. Precious metals recycling is an art that goes beyond mastering a unique flow sheet. Umicore Precious Metals Refining offers a complete recycling service, taking care of sampling and assaying, metals management and logistics. The quality of this integral service is recognized through the attribution of ISO certifications for our operational activities, sampling and the environmental care. And it?s an art that follows Michelangelo?s experience: ?Art is 5% of inspiration and 95% of transpiration.?

Jan 1, 2006

By Randall M. Gennan

Generally sintering is focused on the bonding of particles at high temperatures; possibly with simultaneous densification. However, an important aspect of sintering occurs during heating at relatively low temperatures where polymer processing aids are removed via control of the atmosphere, heating rate, or hold time at intennediate temperatures. New insights into burnout processes show impact from the polymenype, particle size, amount of polymer, atmosphere, part geometry, and thermal profile. This presentation focuses on the key parameters to demonstrate improved mechanical property levels are available in traditional powder metallurgy alloys by proper selection of the processing polymer and proper care in its thermal extraction. The focus is on mechanical property, where gains up to 40% are demonstrated due 10 changes in the processing polymer. Further, atmosphere control during polymer burnout provides a benefit by allowing formation of desirable carbonitrides, giving strength levels over 3 GPa (over 400 kpsi). Insight is? gleaned from powder injection molding, where high polymer contents mandate proper processing control.

Jan 1, 1996

By S. C. Flood, J. D. Hunt

"The columnar-equiaxed transition (CET) has been studied numerically under unsteady-state conditions using mathematical models that: (i) include a non-equilibrium undercooling at the columnar front;and(ii) describe the simultaneous evolution of the columnar and equiaxed zones.The results are discussed and compared with those produced by a steady-state analysis.IntroductionThe majority of the previous work on the columnar-equiaxed transition (CET) has concentrated on the production of equiaxed nuclei, regarding this as being the critical step in the formation of an equiaxed zone. Recently, the growth of equiaxed grains has been considered and this is not unreasonable because, for an equiaxed zone to be present, the grains must grow as well as nucleate. Since the growth rate of the grains will be determined by the thermal environment at and ahead of the columnar tips, it was decided to model the liberation and flow of heat during solidification to discover whether the various trends in the columnar range might be explained by their effect on the temperature profile throughout the casting. The models presented here for the solidification of a casting are the first to include the latent heat liberated ahead of the columnar front. Burden and Hunt (1) consider its effect only qualitatively, and although Lipton et al (2) adopt a criterion for the CET which is based on the thermal interaction of the columnar and equiaxed grains, they do not actually include the latent heat in their calculations.It can be argued that the latent heat liberated by the equiaxed grains in the bulk will retard the columnar dendrites in a casting: once the equiaxed grains are sufficiently well-established, the latent heat that they evolve could slow down the columnar growth to such an extent that the equi axed would dominate. Alternatively, the latent heat produced by the equiaxed grains might suppress further equiaxed solidification by raising the bulk temperature. The nature of the thermal interaction between columnar and equiaxed growth is not obvious, and because it is dependent on the material parameters and the dimensions of the system, it cannot be considered effectively in a qualitative way but has to be studied quantitatively: hence the need for the mathematical models discussed in the following pages. The results of the models are discussed in the light of a steady state analysis."

Jan 1, 1986

By Susumu Okabe

Mitsubishi Continuous Copper Converter employs the top blowing lance system for the continuous supply of reaction gases into the molten bath. In order to avoid the excessive refractory wear caused by the melt splash without loss of the reaction efficiency, the furnace design and the blowing condition should be optimized. Empirical equations which correlate the splashing rate on the' side wall with the dimensions of the furnace, lance position, lance size, gas velocity and bath properties were obtained by by the physical model study, and compiled into a computer program. The computer program is effectively utilized for the analysis of the actual operation and for the optimum design of new furnaces.

Jan 1, 1998