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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 Chi-Ming Chang

Alloy powders are commonly used in the purification of zinc sulfate solutions for use in standard electrowinning practice. The primary goal of this research was to study the use of zinc-lead alloys for similar reactions in the galvanic stripping of impurities from organic solutions. The effects of various parameters on the electrochemical behavior of commercially produced zinc-lead alloy powders were determined. A qualitative evaluation and summary of the influence of the more pertinent parameters on iron removal from di-(2-ethylhexyl) phosphoric acid (D2EHPA) by galvanic stripping is given. Water concentration, oxygen content and reaction temperature were the principal factors affecting the reaction rate and process efficiency. Activation energies were also calculated and indicated that the reaction changes from chemical to diffusion control .with increasing temperature in the range of 35" to 45°C. The results showed that zinc-lead alloy gave faster reaction rates with less sensitivity to process variables than SHG zinc as a reducing agent for galvanic stripping. The role of lead could be as cathodic sites for the reaction which enhances the zinc dissolution or anodic half reaction. The morphology of the zinc-lead alloy surfaces, before and after the reactions, supports this assumption.

Jan 1, 1998

By Kandipati Sreenivasarao

A promising method for removing heavy metal ions from dilute effluents is ion- or precipitate- flotation, in which a suitable collector is added to form hydrophobic metal-collector complexes or compounds that can be collected as foams. We have successfully removed Cu(II), Cd(II), and Pb(ll) from dilute solutions using sodium dodecylsulfate and ethanol as collector and frother respectively. However the process would not be economically viable unless the collector could be recycled, and the heavy metals recovered in a concentrated, preferably marketable, form from the foams. We investigated four different methods to decompose heavy metal-dodecylsulfate complexes, namely precipitation of hydroxides, precipitation of sulfides, chemical stripping, and electrolysis. We compare the performance of these methods. In each case the observed behavior is related to known thermodynamic data, and potential applications are discussed.

Jan 1, 1995

By R. J. Dippenaar, W. H. Van Niekerk

"An injectable lime-based desulphurization reagent for the treatment of liquid iron was developed. Firstly, selected lime based slags containing small quantities of CaF2 to increase fluidity, and Na20 to increase the basicity, have been evaluated on laboratory scale from a thermodynamic point of view. Subsequently, pilot plant and full scale industrial injection trials were conducted. It was found that lime-based slags, containing Na20 and CaF2, are able to desulphurize liquid iron efficiently. By the injection of a lime based reagent consisting of 60% lime, 25% soda ash and 15% fluorspar at a rate of 7 kg reagent/ton hot metal, the sulphur level in the metal (115kg) was reduced from 0,07% to 0,01 % within 5 minutes. The lime-based reagent developed in this study was successfully injected, both from a metallurgical and from a pneumatic point of view, on an industrial scale. The mathematical model utilised in this study, can be used successfully to predict the course and extent of desulphurization by lime-based slags. IntroductionMainly due to environmental difficulties encountered with pure soda ash, dry slag formation with CaC2 and high cost when Mg are used as desulphurizers, much incentive exists for the development of an inexpensive, environmentally friendlier desulphurization reagent. As a first step in the development of such a reagent, selected lime based slags containing small quantities of CaF2 to increase fluidity, and Na2O to increase the basicity, have been evaluated on laboratory scale from a thermodynamic point of view. This was followed by pilot plant injection experiments in which the kinetics of the relevant desulphurization reactions were evaluated. Finally, full scale industrial trials were conducted. All three phases of the investigation will be discussed with the major emphasis being placed on the kinetic study."

Jan 1, 1996

By Yasumasa Hattori

An extensive study including fluid dynamic calculations, cold model tests, pilot plant tests as well as measurements in a commercial flash furnace was carried out in order to develop a new Sumitomo flash smelting concentrate burner. The pressure measurements in the commercial burner indicated that the premixing of the concentrate and reaction air in a burner was insufficient. Pilot plant tests showed that enhancement of the premixing of the concentrate and reaction air is very effective for improving the burner performance. Using the additional pressure drop of the reaction air as an indicator of the premixing, a new type Sumitomo premixed concentrate burner was developed.

Jan 1, 2003

By R. H. Rubisov

Sulphuric acid pressure leaching of nickeliferous laterites has attracted considerable attention from the nickel industry during the past five years. The process is especially advantageous for limonitic laterites that mostly contain goethite, because iron precipitates releasing acid and thus rendering low acid consumption. It is also applicable to mixtures of limonites and saprolites, although at higher acid consumption due to magnesium. Effective process design requires the solubility of metals that precipitate during the process to be known. In the present work, determination of metal solubilities is based on a simple speciation program that assumes the presence of only one dominant complex for each metal. The thermodynamic data for the precipitation reactions are extracted from high-temperature experiments with monometallic systems published previously. The validity of the approach is then tested against mixed bimetallic systems, and finally applied to calculate the solubility of aluminium, iron and magnesium in laterite leaching effluents "at temperature". In both cases of limonitic feed and limoniticfsaprolitic blends, the prediction closely follows metal solubilities measured experimentally at temperatures from 230 to 270°C and at terminal he acidities ranging from 10 to 75 g/L.

Jan 1, 1999

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

This paper describes developments in ferro-nickel furnace technology, specifically improvements to cooling methods, furnace controls, and high voltage furnace operating regime. The evolution of these technologies is briefly presented, as context for describing the current state of the art that has enabled ferro-nickel furnace operation at over 75 MW and specific energy consumption of less than 400 kWh/t dry ore. Examples from existing operations are used to illustrate present best practices, and potential future trends are discussed: The paper begins with an overview of the fundamental aspects of pyrometallurgical treatment of lateritic ores that drive ferro-nickel furnace design. Furnace wall cooling methods are related to the requirements resulting from specific furnace process conditions, including slag and metal compositions, as well as arc and bath power. The benefits of high productivity and low specific energy consumption resulting from high voltage (shielded-arc) operating practice are discussed, along with the furnace controls and electrical power train that enable such operation even with captive power generation. This paper is an update of that which the authors prepared for the Infacon X ferro-alloys conference.

Jan 1, 2004

By Peter K. Liaw, Charlie R. Brooks, David C. Joy, Wei Zhao

In this paper, effects of oxidation, porosity and fiber-fabric stacking sequence on flexural strength of a continuous silicon carbide fiber (SiCr) fabric-reinforced SiC ceramic-matrix composite (CFCC) were studied. The failure mechanisms were correlated with flexural strengths of CFCC samples, both before and after oxidation. Microstructures and fractography were investigated using scanning electron microscopy (SEM). The chemical change after oxidation, such as Si, C, and 0, and their distributions, were detected by the SEM energy-dispersive X-ray spectroscopy (EDXS) line-scan chemical analysis technique. These effects on the strength of the CFCC can be attributed to following reasons: (i) The decrease in the flexural strength after oxidation is mainly due to degradation of the strength of Nicalon fibers and the damage of fiber/matrix interface both caused by high-temperature chemical reactions, (ii) Porosity is not too important in affecting the strength of the CFCC, when the bonding of the forced flow chemical vapor infiltration (FCVI)-SiC matrix is stronger than that of the fiber/matrix interface. However, a higher porosity content will be harmful, because higher porosity will both decrease the effective elastic modulus of the FCVI-SiC and make pore-linkage easier to occur, which is more likely to cause premature failure, (iii) The variation in the lamina stacking sequence of the CFCC changes the elastic stress distributions along the thickness direction of specimens, the magnitude of ceramic matrix-cracking stress, the effective elastic moduli of the laminate, and different crack initiation sites as well as different failure modes, and thus, leading to the scatter in the flexural strength of the CFCC.

Jan 1, 1998

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 C. Gasparrini

Mineralogy may be applied to the selection of appropriate separation techniques, as well as to assist in the evaluation of problems causing loss of metals and other economically important elements during plant processing. Mineralogic studies may thus help develop techniques to optimize metal recoveries. The present paper describes how such factors as the minerals in which the elements of interest are concentrated, their chemistry, the chemistry of the associated minerals, grain size and textural associations with other minerals in the ore, may affect decisions on separation techniques for the recovery of economic elements. A number of case studies are described in which the mineralogical observation of ore samples has revealed the cause of problems experienced in the extraction of select precious and base metals, or has been decisive in the choice of appropriate techniques for recovery.

Jan 1, 1981

By Berger. P.

The accepted definition of the function of an edge protector fails to specify adequately the several tasks which it must perform to be functionally effective: detailed analysis of these tasks leads to the reasoned conclusion that they cannot satisfactorily be fulfilled by the conventional types of "edge-strips". The true cost of edge protector failure is cumulative: renewal costs are dwarfed by the increased operating expenses and production losses which result from but partial or incipient failure of the edge-strip; yet, the several supposedly improved types, for use with starter-blanks, generally were "built down to a price", prolonging the agony, as it were. Clearly, a fresh appraisal of the problem was overdue, and more especially so with the advent of "permanent" cathodes. As a result, new methods of edge .protection have been developed, including the so-called "EDGEWISE" system in which the present author as patentee *) has a vested interest-which he hereby declares. Due mention is made of recent progress in protecting the edges of aluminium "Jumbo" cathodes in zinc electrowinning operations, although the present Paper is more concerned with edge protection of starter-blanks and permanent cathodes in copper ER/EW processes, where most of the "old" problems now may justifiably be claimed to have been overcome, Mention is also made - albeit at this time necessarily only briefly, and confined to edge protection - of "rigidized" metal blanks and permanent cathodes: a most recent development**) which may prove to represent a "breakthrough": time will tell.

Jan 1, 1987

By P. D. Ferro

The direct oxide reduction (DOR) of plutonium oxide generates significant amounts of contaminated waste. This waste primarily consists of calcium oxide-saturated calcium chloride salt. This investigation explores the possibility of recycling the salt, by the electroreduction of the calcium oxide. Fused salt electrolysis of a simulated salt mix (CaC12 + ~10 wt. pct. CaO) is being carried out to electrowin calcium, and the process is being optimized in terms of the calcium solubility, cell temperature, current density and cell design to maximize the current efficiency. This work identifies the major concerns in the development of a process to electrowin calcium from this simulated salt mix.

Jan 1, 1992

By T. K. Mukcherjee

The importance of the processing of secondary resources such as solid industrial wastes and liquid effluents as well as byroducts for the recovery of the associated metal values hardly needs any elaboration. Such processing contributes in no small measure.towards the augmentation of the availability and the supply position of resources. As an added benefit, it leads to a reduction in environmental pollution caused by the undesirable waste materials. As some typical examples of secondary resources in the Indian scenario, mention' can be made of spent catalysts, metal/alloy scrap, ash, consumed batteries, flue dust, slag, sludge and slime, pickling solutions, spent acids; plating rinse solutions, spent etchants, waste water from synthetic fibre manufacture and from tanneries etc. These wastes constitute a source of a variety of non ferrous metals. In the processing of secondary resources like these, the techniques of hydrometallurgy such as solvent extraction play a pivotal role. This paper outlines the efforts made to use solvent extraction to recover(1) base metals. such as copper, zinc, nickel and cobalt from a number of secondary resources like cake, and sludge(2) refractory metals like molybdenum and vanadium from sulphidic byproducts and spent catalyst and (3:) nuclear metal like uranium from phosphoric acid. In the case of base metals, process flowsheet involving the use of acidic extractants such as DEHPA and PC88A have been optimised. The problem of iron removal from the leach liquor, "which influences the metal recovery process significantly, has drawn a special emphasis. hi the case of refractory metals, basic extractants .like Alamine 336 has been pressed into service to produce kilogramme. quantities of pure salts of molybdenum and vanadium, Finally, the paper gives a brief account of plant experience in recovering uranium from phosphoric acid, using 'a solvent system comosed of DEHPA and TOPO.

Jan 1, 1996

By René Winand

The paper gives a synthesis of research work performed in the department during the last ten years and dealing with cobalt , copper and manganese electrodeposition in chloride aqueous solutions. Special emphasis is given to electrocrystallization. For copper, properties of the electrolyte such as solubility limits, electrical conductivity and complex ions stability are discussed in connection with leaching, purification of the electrolyte, and metal recovery. When possible, kinetic parameters and probable electrode mechanisms are given. Problems that are still to be solved are also listed.

Jan 1, 1985

By P. C. Chaubal

The overall kinetics of oxidation of single partic1es of chalcopyrite have been studied for temperatures up to 1273 K. The experiments were conducted in a stationary bed reactor using a non-isothermal technique. Any mass and heat transfer effects on the kinetics of oxidation were eliminated by using a high-enough gas flowrate. Up to temperatures of 873 K, pore-bl1ocking kinetics were applicable, whereas above 873 K, power-law kinetics gave a satisfactory fit of the data. The activation energy was 215 kJ/mol below 754 Kand 23.7 kJ/mol above 1,060 K. Predominance area diagrams were constructed at various temperatures and used in conjunction with X-ray analyses of partially oxidized samples to determine the intermediate phases formed during the reaction. The analysi1s also provides a justification for the kinetic models used. The results indicate that the reaction rate is first order with respect to oxygen concentration and inversely proportional to the square of the particle size throughout the ranges of temperature studied.

Jan 1, 1985

By Chu Yong Cheng

The solvent extraction (SX) processes of the three pressure acid leach (PAL) nickel plants in Western Australia have been reviewed. The use of intermediate precipitation, solids/liquid separation and re-leach in the three W A nickel plants make these processes complicated and costly in capital and ?operation. The research work carried out by the SX group at the AJ Parker Cooperative Research Centre for Hydrometallurgy I CSIRO Minerals has led to the development of direct solvent extraction (DSX) processes to recover and purify nickel and cobalt from leach solutions. The simplicity of the process flowsheets and the expected savings in capital and operating costs are the major advantages of the new DSX processes over the reviewed processes. By using a new synergistic organic system in semi-continuous tests with a pilot plant leach solution (after iron precipitation) from BHP-BiIliton Stainless Steel Materials, the metal values (Ni and Co) together with zinc and copper were separated from the major impurities (Mn, Mg and Ca, together with Cl) in the first SX circuit. The co-extracted manganese, magnesium and' calcium were easily scrubbed out. After stripping, the metal values (Ni and Co) together with zinc and copper were concentrated, resulting in a much smaller second SX circuit and equipment in the down stream processes. The extraction and stripping kinetics of the metals with the new synergistic organic solution were very fast. The extraction and stripping almost reached steady state within 0.5 minutes. Semi-continuous test work with a synthetic leach solution, 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 Stainless Steel Materials showed that manganese, calcium, copper and zinc can be effectively and efficiently separated from nickel, cobalt and magnesium by extraction, scrubbing and stripping. This led to the development of another DSX process using D2EHPA to recover nickel and cobalt from leach solutions.

Jan 1, 2003

By J. K. Brimacombe, I. V. Samarasekera, B. G. Thomas

"Mathematical models have been developed for the processing of static cast steel ingots and are app1ied to investigate the mechanisms for the formation of panel cracks. Panel cracking is an intermittent but persistent defect that causes affected steel ingots to be scrapped. A two-dimensional, finite-element, heat-transfer model was formulated and employed to calculate the temperature distribution in both large and small steel ingots during the various processing stages from initial casting to the start of rolling, including solidification, cooling in the mold and in air, reheating in the soaking pit, and subsequent air cooling. The stress state in the ingot arising from the calculated temperature variations was then determined. This involved the development of a transient, elasto-visco-plastic, finite element, thermal stress model, including the effects of phase transformation volume changes and kinetics creep, and temperature-dependent, mechanical properties. The results of the mathematical model predictions of temperature and stress were then used to determine the mechanisms and to suggest solutions for two different types of panel crack formation. Mid-face panel cracks apparently form during air cooling when the mid-face surface temperature is between the Arl and 500~C. Off-corner panel cracks appear to initiate internally during the early stages of reheating but do not propagate to the surface until much later. IntroductionPanel crack formation in static-cast steel ingots is a defect that has been plaguing the steel industry for several decades. Although the problem is intermittent, it is also serious since affected ingots must be scrapped. Panel cracks are manifested as two distinct types of cracking problems. ""Mid-face"" panel cracks are found exclusively in small, 2 to 6 ton, medium carbon steel (0.3 to 0.7% C) ingots and usually exhibit a single, continuous, longitudinal crack down the center of one of the ingot faces as shown in Fig. l (l). ""Off-corner"" panel cracks often form roughly oval, discontinuous crack patterns on the wide faces of large, 20 to 30 ton ingots as seen in Fig. 2 (2). They affect only low carbon steels (0. l to 0.2% C) with high manganese content. Both defects affect only aluminum-treated steels and are caused by a combination of intermediate temperature ductility loss involving aluminum-nitride precipitation and thermal stress generation. The ductility problem has received a good deal of attention which was the subject of a recent review (3). The present study was undertaken to investigate the thermal stress aspects of the problem through the development of mathematical models of heat transfer and stress generation in static-cast steel ingots. The ultimate objective was to elucidate the mechanisms of formation for both types of panel crack and to evaluate possible solutions to the problem."

Jan 1, 1986

By João M. S. Rodrigues

The use of sandblasting as a treatment method for conditioning anodes for zinc electro-winning was investigated and compared with conventional fluoride preconditioning. The anodes were made from two different lead-based alloys (Pb-Ag-Ca and Pb-Ag). Laboratory results showed that sandblasting and preconditioning both minimize lead contamination in the zinc and sludge generation. Sandblasting was found to have no aggravating effect on the anode corrosion. The sandblasting treatment was tested on Pb- Ag-Ca anodes on an industrial scale in the celJhouse of a local zinc producer. An unexpected finding of the large-scale tests was that the sandblasting appeared to strengthen the anodes, resulting in reduced warping during handling and operation.

Jan 1, 1996