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By Gopalakrishna M. Rao

"Several industrial and government laboratories are of the opinion that solar--cell technology will grow into a billion-dollar industry by the year 2000, especially if oil prices rise again. Of the variety of materials that have been investigated as the major component of photovoltaic systems, silicon appears to have an outstanding advantage. The cost factor is the primary importance in photovoltaic development, since the technology to make silicon cells of acceptable efficiency and life time has existed since the early stage of the space program. Electrometallurgy is one of the low--cost processes for the production of silicon, since it allows direct, single-stage production from some abundant, inexpensive source materials such as silica and fluorosilicates. Among several systems, two are given particular attention, using inorganic baths with Si0 2 or K2SiF6 as the source of silicon respectively. They appear capable of development to commercial production. Conceptual designs of a commercial--scale cell for silicon production at temperatures above its melting point, and of a pilot' plant for plating silicon from an all-fluoride bath are presented. Energy ProspectsThe major changes in the world energy since the first energy crisis in 1970 have impacted on our community. When oil was $40 a barrel in the mid-1970s, we became obsessed with the energy conservation and a search for alternate energies. Even though the crude oil fell below $15 a barrel during the last several years, our energy security fears continue to haunt us. This time it is not the scarcity, but the abundance of foreign oil and the decline in the domestic production.The prospects of energy depends on the demand and supply of energy. These, in turn, depend on future energy prices, which are linked to economic factors, political events, and unforeseen circumstances. Although no one can predict the future with certainty, three energy consumption patterns used by the Ford Foundation are as shown in Fig. 1."

Jan 1, 1988

By Joon H. Jang

At a selected pH, hydrothermal oxidation of chalcopyrite was carried out under controlled F+,, at elevated pressures and temperatures (172-200°C) by balancing the rate of oxygen injection against the rate of consumption. Chalcopyrite was converted to covellite (CuS) and digenite (CU1.8S) with rejection of iron and sulfur to the solution. Covellite forms in the first stage, followed by nucleation and growth of digenite in the second stage. The effects of rapid and slow injection of stoichiometric quantities of oxygen are compared. Both the covellite and digenite form a porous layer occupying the same volume as the original chalcopyrite grain. An electrochemical kinetic model is presented to correlate the observed results.

Jan 1, 1993

By Daniel K. Kim

The charge for the copper refinery is a mixture of anodes produced at San Manuel from BHP source concentrate and copper purchased from external sources. Control of unwanted impurities in the tankhouse - is very important and beneficial. Currently available removal/recovery technologies were reviewed for the control of bismuth and antimony levels in the electrolyte. Recent studies have focused on solvent extraction (SX) technology and generated successful results for the removal and subsequent recovery of bismuth and antimony. The SX system employs the reagent, ACORGA SBX-50, in conjunction with a patented high chloride stripping system. The latter enables recycle of the eluant, avoiding the high costs associated with conventional systems, such as regeneration of resin. Concerns over potential transfer of organics and chloride ion to the electrolyte were readily addressed, solved and demonstrated using conventional, established technology. This paper describes the benefits of electrolyte purification, the flexibility afforded by the SX system, the operational practices necessary for maintaining adequate control of bismuth and antimony impurities in the electrorefining environment and possibilities for future development /exploitation of the Zeneca SX system at the San Manuel refinery.

Jan 1, 1998

By S. J. Buckler

Many chemical and metallurgical processes use submerged gas injection to increase contact area between gas and liquid phases in order to promote faster overall reaction or refining rates. The total interfacial area produced by gas injection through lances, nozzles or tuyeres is both an important design parameter for new vessels and a measurement for estimating the maximum processing capacity of existing equipment. Estimating total interfacial area from submerged injection into industrial pyrometallurgical vessels from existing knowledge is a problem with two aspects. The first difficulty is the difference in behaviour of cold (aqueous) and hot (molten metal) systems, implying that existing models and correlations of gas-liquid behaviour developed in low temperature systems are not necessarily appropriate for estimation of high temperature behaviour. The second difficulty is the issue of scale-up of correlations from laboratory to industrial sized vessels. The work presented in this paper is part of an ongoing experimental investigation, at the GK Williams CRC for Extractive Metallurgy, to quantify the total gas-liquid interfacial area available in pyrometallurgical vessels using chemical measurement methods. The effects of three operating variables, injected gas flow rate, nozzle diameter and nozzle submergence, on total interfacial area are quantified in a IOOL aqueous system - the first stage of a three stage process in examining the implications for scale-up of high temperature, medium-scale results are discussed. The results of work at high, injected gas flow rates (up to 500/min) show that the submerged Froude number is not sufficient for use as the sole variable in a predictive model of total interfacial area. Further work is being undertaken to identify other dimensionless variables that will better represent the gas-liquid characteristics in submerged injection that influence the formation of total interfacial area. The second and third stages of the experimental investigation involve measuring the total interfacial area in a large-scale (1000L) aqueous sodium sulphite and small-medium scale molten metal baths.

Jan 1, 2002

By Jinrong (Patrick) Mang

Three of the most challenging problems in phosphate beneficiation are discussed: flotation efficiency, resource conservation and environmental impact. Some new flotation machines offer the opportunity of reducing power and reagent consumption significantly, while increasing specific capacity many fold. Efficiency might also be improved dramatically by replacing the "double float" process with a single-collector scheme. Model based software control is a powerful tool for improving overall plant efficiency. Recovery of phosphate values from the phosphatic clays could extend phosphorus reserve life significantly. phosphate recovery from the slimes might be achieved by sizing-flotation, selective flocculation and bioleaching. Reducing the volume of phosphatic clays produced is another key stop to minimizing phoephate logs. Such a reduction may be realized by floating at finer cut size. Although an ideal' dolomite separation process is yet to be developed, a cationic flotation process may prove to 'be economically feasible. Loss of phosphate in the desliming stage is the major problem with most of the flotation schemes for removing dolomite.

Jan 1, 1995

By A. S. Rao

In the original roast-leach-electrowin (RLE) circuit at the Chambishi Cobalt Plant, commissioned in 1978, the separation of nickel and zinc from cobalt in aqueous streams was achieved by successive stages of precipitation using lime. However, this technique was not able to meet the increasingly stringent metal quality requirements of customers whilst maintaining acceptable process recoveries. Intensive process development work was carried out and, in July 1988, an ion exchange circuit for nickel removal was commissioned using DOW XFS 4195 resin and for the first time Z.C.C.M. produced high purity cobalt metal containing less than 0.10% nickel. Following further work, a solvent extraction circuit for zinc removal, using DZEHPA, was commissioned in February 1991 in order to enhance cobalt recovery by reducing co-precipitated cobalt losses. This paper outlines the process development, design, commissioning and subsequent operation of these nickel ion exchange and zinc solvent extraction circuits.

Jan 1, 1993

By A. Treverrow, G. A. Brooks, H. K. Worner

"The work by H.K Worner and co-workers at CRA in the 1960s, and early 1970s, established that molten metals could be refined continuously utilising counter current flow of metal and slag. Womer also demonstrated that counter current refining could produce highly refined metal products. These developments coincided with the advent of high intensity metallurgical reactors in both the ferrous and non-ferrous industries (e.g. BOS, Q-BOP and later Sirosmelt) that utilised high levels of gas injection to produce rapid stirring and very fast reaction. These new generation of high intensity metallurgical reactors allowed high tonnage rates through relatively small volume vessels.Whilst, it is well known that the counter current flow of reacting phases offers the potential of efficient mass transfer and high purity products, the application of counter current reactors to molten metal/slag systems has been criticized on the basis that they suffer from either low intensity or, alternately, from poor refining due to excessive dispersion. These criticisms relate to the balance between intensity and the refining capacity of a reactor. That is, whilst high levels of mixing transversely to the direction of flow promotes high mass transfer, longitudinal mixing (dispersion) is detrimental to refining. Of course, mixing in one direction invariably leads to mixing in other directions, thus creating a playoff between high mass transfer and excessive dispersion.This balance between intensity and refining has been the subject of recent studies overseas, and at"" the University of Wollongong, using cold modelling techniques to evaluate the effect of mixing on dispersion in a counter current refining launder. These studies have shown that for a given geometry and mixing regime, dispersion decreases with increasing flow of liquid phases. This means that whilst high mass transfer cannot be achieved in a refining launder without sacrificing the degree of refinement, there is no impediment to achieving high productivity through such a system, in fact, high through puts may favour good refining. Thus, it may be possible to match a high productivity smelting operation with a equally productive counter current refining stage."

Jan 1, 1996

By C. S. Simons

This paper presents a review of the extractive processes used in the production of nickel, with emphasis on developments since the beginning of the Second World War. Attention is given to the factors, many outside the nickel industry itself, which determined the direction of process research and strongly influenced the ultimate commitments to industrialize the resulting developments. An example of such a factor is the sudden surge in demand, far exceeding the then available nickel production capacity, that was caused by the advent of World War II; the result was the first serious consideration ever given to low- grade laterites as a viable source of primary nickel. Other factors discussed include such items as process development in the extraction of other metals - particularly copper; the availability of increasingly sophisticated materials of const- ruction; the advent of the "environmentalist" and related political developments; the massive escalation in the price of energy - particularly oil. The paper concludes with an attempt to forecast the nature of the most effective nickel process of the future, based on extrapolation from the economic and political situation that exists today.

Jan 1, 1988

By D. Papazoglou

This work was undertaken to investigate the thermodynamic and kinetic feasibility of using hot sulfur dioxide bearing gases from smelting processes to selectively sulfate the nickel in nickel laterite ores for subsequent extraction in water. The environmental benefits ofthis approach, as opposed to releasing the gas to the atmosphere, and the economic benefit of directly utilizing the S02 rather than converting it to sulfuric acid are strong drivers for such a process. A thermodynamic analysis indicated that selective sulfation of the nickel could be feasible under appropriate conditions and these were explored through a series of laboratory scale experiments. Laterite samples were reacted at temperatures between 500 and 800°C with an equilibrated mixture of sulfur dioxide, oxygen and nitrogen in a fixed bed reactor. Tests were conducted on saprolitic ore from Bulong, Western Australia, limonitic ore from New Caledonia and garnieritic ore from Indonesia. Nickel extractions were highest from the limonite and relatively low from the other ores. The maximum selective extraction of nickel from the limonite in a single stage sulfation was 73%. Sulfation of other elements present in the laterites was also examined. A two-stage process was also identified which involved sulfation using a strong sulfation potential followed by weaker sulfation potential to attempt to convert ferric sulfate formed in the first stage to ferric oxide. This increased the extraction for the limonite ore to around 84% Ni, 95% Co and 2% Fe. Direct sulfation of laterite could be feasible in locations where sulfide smelting or roasting operations are relatively close to laterite deposits.

Jan 1, 2003

By G. R. Palmer

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

Jan 1, 1994

By Broggi Andrea

Condensates produced by SiO(g) and CO(g) have a crucial importance in silicon production. Condensation will follow the reactions 3 SiOðgÞ+COðgÞ→ 2 SiO2 + SiC and 2 SiO ðgÞ→Si+SiO2. Solid compounds generated during silicon production contain Si, SiO2 and SiC in different microstructures and amounts. In industrial systems, condensates limit the SiO(g) escape to the off-gas system. On the other hand, they can block the gas flowing from the high temperature zone, hence the necessity of studying an optimized condensation process. This review discusses SiO(g) condensation and its interaction with CO(g). The report gives an overview of the condensates found both at laboratory and at industrial scale. The two main compounds are the Si–SiO2 and the SiOx–SiC mixtures. The hypothesis on the mechanism of formation of SiC–SiOx condensates is presented through a wide selection of performed works. The advantages and disadvantages of the former experimental procedures are discussed.

By Richard B. Diver, Mark D. Allendorf, Daniel E. Dedrick, James E. Miller, Roy E. Hogan, Andrea Ambrosini, Eric N. Coker, Anthony H. McDaniel, Nathan P. Siegel, Gary L. Kellogg

"Converting carbon dioxide and water to hydrocarbons is an attractive option for storing solar energy and, coupled with appropriate CO2 capture technology, for recycling carbon and impacting atmospheric CO2 concentrations. For any process, high solar-to-fuel efficiency is necessary for large scale viability and favorable economics. Thermochemical approaches for solar-to-fuel conversion are potentially highly efficient as they avoid the inherent limitations of photosynthesis and also sidestep the solar-to-electric conversion necessary to drive electrolytic reactions. Solar-driven two-step metal-oxide-based thermochemical cycles for producing the components of syngas, CO and H2, from CO2 and H2O are the basis of the “Sunshine to Petrol” project. Multi-cycle production of both H2 and CO has been demonstrated over several iron- and cerium-based compositions fabricated into monolithic pieces both in the laboratory and at the National Solar Thermal Test Facility. These compositions are being developed for deployment in a unique and continuous solar-driven reactor prototype, the counter-rotating-ring receiver reactor recuperator or CR5.IntroductionThe interconnected challenges posed by increasing global competition for petroleum and the increasing concentration of atmospheric carbon dioxide are now widely recognized. Meeting these challenges requires recognition that although hydrocarbon fuels are ideal energy carriers, they can no longer be thought of as primary energy sources. It is necessary to take the realistic view that our conventional fossil fuels are in fact “stored sunlight” in the form of “sequestered carbon.” This view leads to a search for options to use and store sunlight more directly.Sunshine to PetrolIn combusting hydrocarbons we unlock the energy for utilization, but we also release the carbon to the atmosphere. However, nature teaches us that with an appropriate persistent energy source, e.g. solar irradiation, it is possible to effectively reverse the combustion process and “reenergize” CO2 and H2O back into hydrocarbon form."

Jan 1, 2010

By Derek J. Fray

"In order to extend the application of fused salts in\the electrowinning and electrorefining of metals, it is necessary to maximise the current density, minimise the voltage drop and greatly increase the area of electrode surface so as to compete with the space-time yield of pyrometallurgical reactions. The various designs of electrowinning cell are reviewed and it is shown that by the application of a modest centrifugal field it is possible to reduce the anode to cathode interelectrode spacing to 4 mm whilst still maintaining a current efficiency of 85-90%.The thermodynamic potential for electrorefining is far less than for electrowinning yet fused salt electrorefining is only applied in limited cases. The reasons for this are discussed and the important design parameters evaluated. It is concluded that by using packed bed electrodes, separated by a diaphragm, the possibility of electrorefining with very low energy consumption can be achieved. Carbothermically-produced metals are always cheaper than those produced by electrolysis but suffer from the disadvantage of low purity. It is proposed that fused salt electrorefining may offer an energy efficient way of upgrading the metal. IntroductionThe majority of metals can be deposited from fused salts (1,2) but as commercial production is restricted to the more reactive elements, it is worthwhile considering the advantages and disadvantages of fused salt electrolysis as' compared to smelting and aqueous electrolysis. The advantages over aqueous extraction are as follows:1) the much higher conductivities and diffusivities result in much lower IR losses and higher current densities can be achieved at modest voltages;2) the elevated temperatures of operation result in larger exchange currents which give rapid kinetics and lower activation polarisation for the electrode reactions;3) the absence of water as a solvent means that it is not necessary to consider the evolution of hydrogen as a competing cathodic reaction. Furthermore, alkali halide salts, often used as solvents in fused salt electrolytes, have high deposition potentials;4) molten salts generally are mutually soluble and, therefore, concentration polarisation effects are minimised."

Jan 1, 1988

By Noel A. Warner

Modern steelmaking is based on direct use of oxygen in high intensity batch reactors. A totally new approach is proposed in this paper, based on the view that pursuit of high intensity is unlikely to lead to successful coal-based continuous steelmaking. By substituting carbon dioxide and water vapor as the oxidants rather than using oxygen directly, the intensity is greatly reduced. Accordingly. subsurface formation of carbon monoxide bubbles can be avoided by careful manipulation of the three participating rate processes, gaseous diffusion, interfacial chemical kinetics and liquid phase mass transfer. Steelmaking can then be carried out without explosive ejection of molten droplets and the generation of micro-spray but rather in a controlled and fumeless fashion. The vital component is the introduction of generic melt circulation technology. Three melt circulation loops in series are envisaged. Starting with a composite feed of iron ore fines, pulverized coal and lime flux, a metallized solid raft floating on molten iron is propelled out of the ironmaking loop onto the first of two downstream steelmaking loops. In the first, a liquid slag is formed, primary decarburization is undertaken not with oxygen but rather with CO2 and H2O and the melt is desulfurized. The semi-product stream enters the third melt circulation loop, where open-channel decarburization is effected along with dephosphorization to yield a low carbon steel product. Alternatively, the melt leaves the last loop to irrigate a packed tower countercurrent to argon at around 100 mbar to continuously produce ultra-low carbon (ULC) steel.

Jan 1, 2003

By Godwin J. Igwe

For soil remediation technology to be effective, a thorough understanding of the interactions between a targeted contaminant and the soil matrix is crucial. Proper selection of remediation technology, based on understanding the bonding/binding characteristics of the soil and contaminant, can often result in significant remediation cost savings. Contaminated soil cleanup is complicated by both the physical nature of the soil formation and the behavior of contaminants introduced into the formation. Contaminants can exist in the subsurface in different phase attached to the soil surfaces, dissolved in the ground water, or occupying pore spaces as a separate gaseous or liquid phase. Contaminants properties and how they exist in the subsurface influence their toxicity, mobility and treatability with different remediation technologies A soil characterization study was performed to provide information for remediation technology selection for an inorganic lead contaminated soil. The soil pH, TCLP analysis, thermogravimetric analysis, the soluble anions and cations present, equilibrium leaching tests, analysis by x-ray fluorescence, sequential extractions and speciation analysis using scanning electron microscopy, were all used. Results provided many insights into contaminant behavior in the soil, indicating ultimately whether soil washing or solidification/ stabilization remediation technologies were applicable.

Jan 1, 1994

By F. Elgersma

Hydrometallurgical zinc winning processes ?are frequently based on iron containing concentrates which yield a goethite, jarosite or hematite residue. Jarosite or goethite are mostly stored in waste ponds which ,are lined with foil. Water percolating through the pond is withdrawn from the deposit ,and decontaminated before discharge. Despite these measures, more and more pressure is put upon zinc companies to treat their (historical) residues and to produce environmentally acceptable residues. The criterion which determines this acceptability is the potentiality of leaching out hazardous elements by natural processes. This paper provides the comparison of five different process designs for integrated jarosite treatment in a hydrometallurgical zinc winning plant leading to environmentally acceptable residues. The processes are esigned for producing 200 ktons/yr zinc and for treating 80 ktonslyr historical jarosite. Mass and energy balances are used to determme parameters such as: the energy use per ton waste treated and the amount and composition of final residues. The conclusion of the work is that. pyrometallurgical jarosite treatment integrated in hydrometallurgical zinc winning is preferable to hydrometallurgical jarosite treatment. Integrated pyrometallurgical processes lead to a ?smaller quantity of remaining hazardous residues and require less energy.

Jan 1, 1992

By Jürgen Antrekowitsch, Thomas Griessacher

The recovery of valuable metals from residues like dusts and sludges is nowadays state of the art. Depending on the complex constitution, a recovery of different metals can – in the majority of cases – only be performed with considerable energy input in high temperature processes together with insufficient yields and newly generated residues. Often, the behavior of the dust or sludge in the process during melting or reduction is unknown. In this work, a detailed characterization of selected residues like steel mill filter dusts, cupola furnace dusts and leaching residues is done. The different steps of getting from solid particles into a homogenous liquid phase were investigated. Although high temperature processing leads to high reaction speeds, the complexity of residues keeps the system away from thermodynamic equilibrium. With this research program, some basics are generated to understand smelting and reduction and the gap between thermodynamical calculations and real behavior can be explained.

Jan 1, 2008

By Jr. Robison

"Aluminothermic (""thermite"") smelting became commercial with the development of tonnage aluminum, and prospered producing metals and alloys with higher cleanliness, consistency and elemental control than competing technologies. We explore the scope of thermite smelting, and metallothermic smelting in general; the thermochemistry of the process; and its advantages and limitations as applied to industrial production. We review currently-produced products of thermite smelting in several forms and a wide range of heat sizes. As these products serve several industries, we relate the demands of those industries to the requirements imposed on the thermite process, leading to process dynamics and mechanisms to control/alter those dynamics. We review ways to lower the process costs by altering process stoichiometry, using other energy sources and utilizing less costly materials while considering effects on product quality and customer requirements. Finally, we examine overall emissions control and waste disposal.IntroductionAluminothermic smelting is the reduction of various oxides by aluminum to produce metals or alloys with varying levels of residual aluminum. One of the earliest uses of the process was the production of liquid iron to weld railroad rails, later modified in ""thermite grenades"" used to ""spike"" artillery pieces in World War II. Then during the 50's, 60's and 70's the growth of jet aircraft created a demand for new superalloys and titanium alloys, both requiring master alloys for efficient production. Aluminothermic smelting grew with the aerospace industry and with the expansion of microalloyed steels. It is very much a niche industry, dependent on the specialized demands of the specialty steel, superalloy and titanium industries. In this paper we introduce the characteristics of aluminothermic smelting, the scope of smelting operations, the markets served, and the environmental aspects of the process, as seen through the eyes of a company using aluminothermic smelting for over fifty years"

Jan 1, 2012

By Chai Li-yuan

Anodizing behaviors of magnesium alloys AZ31 at constant applied current, based on the electrolyte solution free of chromate or fluoride, were investigated. The anodizing process was influenced by constituents of electrolyte greatly. Therein, the oxylate salts, which led to the occurrence of the two totally different processes, played a determinant role in anodizing. They were stable and sparking process respectively. The morphology of anodizing film was observed by SEM and the structure of film was analyzed by XRD. During the stable process, a brown thin film was formed, however the sparking process led to the formation of white hard thick film. The functions of some kinds of additives, such as ammonia, glyceryl alcohol and PVP etc were also studied. Some of them had great effect on surface morphology of anodic film and some of them affected stability of anodizing process significantly.

Jan 1, 2006

By T. L. Baum

External oxidation during in-line heat treatment of TRIP steels can cause problems for the subsequent coating process. This research aims to elucidate the kinetic rates of internal oxidation, external oxidation and decarburization and their interdependence under different gas atmospheres and temperatures. A rolled steel sample chemistry of 0.14 wt.% C, 1.8 wt% Mn, 0.6 wt.% Si and 1 wt.% Al is used as a case study. Thermogravimetric techniques are used to examine the net mass change in a sample during heat treatment and the results show an initial mass decrease and later an increase for particular partial pressures of H2O. SEM-EDS, optical microscopy and glancing-angle x-ray are used to quantify the microstructure. The cross-section of the samples have 4 distinct zones: (i) an external scale, rich in fayalite, (ii) an internally oxidized region with Al, Si and Mn oxides in an Fe matrix, (iii) a decarburized steel region, characterized by large ferrite grains and low carbon content, and (iv) a relatively unaffected steel core with a structure similar to the starting material.

Jan 1, 2006