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By C. Kathryn Sole

The close proximity of cobalt and nickel on the Periodic Table and their frequent occurrence together in nature means that their separation in primary hydrometallurgical flowsheets is not only often necessary, but requires the use of innovative chemistry to achieve high selectivity. Today, increasingly stringent demands for the high-purity cobalt and nickel salts required for battery applications in consumer electronics, electric vehicles, and solar applications are again challenging the state of the art. The evolution of cobalt–nickel separations is traced from the basic precipitation technologies employed in 1960s, through commissioning of the first cobalt solvent-extraction plant in South Africa in 1974, to the commercialisation of organophosphinic-acid extractants (which provided a step-change improvement in selectivity) and their eventual widespread use in the 1980s and ’90s. This was followed later by their sulphur analogue, which enabled different possibilities for laterite processing in the new millennium. Separations in chloride media, which take advantage of the different speciation chemistries, and nickel extraction by oximes in ammoniacal systems are also discussed. More recently, chelating and solvent-impregnated resins have added further dimensions to the possibilities for flowsheet design and enabled higher purity products to be attained from both primary and secondary sources. Selected case studies and flowsheets are described.

By Yun Li

An innovative lead recycling process from scrap lead-acid battery paste is presented. The novelty in the process is avoiding SO2 generation and emission by using reductive sulfur-fixing technique. Iron-bearing secondary wastes produced from metallurgical industry were utilized as sulfur-fixing agent to capture sulfur in the form of FeS (s) instead of generation of SO2 (g). Na2CO3 molten salt was added to the smelting system to speed the reactions and improve valuable metals’ recovery and sulfur-fixation efficiency. Furthermore, this process can simultaneously co-treat various lead and iron-bearing wastes. At the same time, some precious metals, such as Au and Ag, contained in iron-bearing wastes can be recovered. The feasibility and reliability of this process was investigated thermodynamically and experimentally with the help of HSC 9.0 database and XRD and SEM-EDS analysis. A possible reaction mechanism and path in PbSO4–Fe2O3–Na2CO3–C smelting system was also clarified.

By Graham J. C. Carpenter, Marc Charest, Jason Lo

"The method of producing magnesium-based composites with silicon carbide (SiC) particulates embedded in the matrix of magnesium AZ9I D alloy by the squeeze-casting technique are described. This method involves the fabrication of a SiC particulate preform and the subsequent squeezing of molten magnesium into the preform. In this study, alumina, aluminum phosphate and a proprietary binder were used for the fabrication of SiC particulate preforms. The procedures employed in the fabrication of SiC! AZ9ID composites are presented, together with the results of characterization of the composites using optical and transmission electron microscopy. Special attention is given to the reaction products in the bulk alloy and at the interfaces between SiC particles and the AZ9ID matrix alloy.1. IntroductionInterfacial, microstructural and metallurgical characteristics play an important role in determining the mechanical properties of a composite. In theory, reinforcing magnesium with SiC particulates should provide an improvement in strength and modulus of the composite over the unreinforced counterpart. However, many factors resulting from the fabrication process can cause degradation rather than improvements to the mechanical properties. In particular, the interfacial characteristics are known to critically influence the properties of composites [1]. Before evaluating the mechanical properties of a composite, it is always useful to examine the microstructure, which is closely related to the mechanical behavior. This helps to reduce the labor-intensive steps of sample preparation for mechanical property evaluation, which can be particularly difficult as a result of the high hardness of composite materials, as well as providing a wealth of information on the microstructural and interfacial characteristics, particularly the reaction products caused by processing. This information is also pertinent in understanding the factors governing the mechanical properties of the composites.There are many factors which determine the nature of the interfacial characteristics of a SiClMg composites. Qualitative estimations of the interfacial bonding have been performed based on thermodynamics, electronic and electrostatic concepts. In addition, the kinetic conditions during the fabrication play an important role. From an interfacial energy standpoint, the driving force for the formation of a metal/ceramic interface is the decrease in free energy that occurs when intimate contact is established between metal and ceramic surfaces. The simple representation of the energy change per unit area of interface formed (~G) is given by Dupre equation [2]:"

Jan 1, 1996

By I. Gaballah

Cadmium is toxic to plant, animals and humans. The council directive of the European Communities No 8315 13lEEC has fixed an upper limit of 200 ppb for the release of cadmium in industrial effluents. The conventional method of neutralization/prccipitation ( NIP ) is inefficient to reach this limit. The objective of this study is to test the efficiency of the trees modified bark to remove cadmium cations from industrial effluents after the conventional treatment by NIP. Laboratory scale tests with synthetic solutions show that the cadmium removal depends upon pH and initial concentration. About 99.9 %, 99 % and 96 % of the metal are removed from synthetic solutions containing 10, 100 and 1000 ppm respectively. Pilot plant trials ( 1 m3 ) with an industrial effluent bearing about 500 ppb of cadmium lead to the almost complete elimination of the cadmium ( final concentration is lower than the analytical detection limits < 20 ppb ).

Jan 1, 1994

By W. Kunda

Silver nitrate solution is a very common product in hydrometallurgical processes involving the treatment of various silver bearing materials. Silver is recovered by electrolysis. The alternative method for the recovery of silver from aqueous solutions is the precipitation by hydrogen at elevated temperature and pressure. A previous study by the authors revealed the feasibility of this technique for the silver ammine sulfate system. Further study showed different behavior for silver in the silver ammine nitrate system and a systematic study was initiated to establish the optimum conditions for the process. The study showed that the process can be controlled by (1) composition of the feed solution, (2) temperature and (3) hydrogen pressure. The recovered silver product was in the form of very fine powder.

Jan 1, 1989

By J. E. Hoffman

The operation of the U .S Metals Refining Company, USMR Co. is defined below by the description of a variety of unit processes and operations the author encountered during his tenure with the operation, 1955 - 1978. The operations discussed include: sampling and sweating of radiators, processing of Indian Coin, treatment of insulated wire, baghouse and converter dust treatment, blast furnace and converter operation, the electric arc furnace, antimony control, selenium and tellurium products, electrolyte liberation with soluble anodes, and the precious metals refinery. These operations, although peripheral to the primary copper production circuit, were critical to the company's technological and economic base.

Jan 1, 2000

By Brajendra Mishra

Molten Salt electrolytic processes offer unique opportunities to extract and refine metals where gaseous or metallothemlic reduction, hydrometallurgical extraction and aqueous electrolytic methods are thermodynamically constrained. Production of aluminum and magnesium by molten salt electrolysis are well known commercial processes. Several other reactive metals, such as lanthanides and actinides, as well as beryllium and calcium, make use of molten salt processing for extraction and refining. This presentation describes the science of molten salt chemistry and electrochemistry for winning and refining of several metals. In addition, recovery of metals from waste process salts by molten salt reduction as well as oxidation have been discussed. Material issues in design of molten salt reactors have been included. Various applications have been presented through case studies. Experimental data have been included to justify the suitability as well as limitations of these specific processes.

Jan 1, 2003

By A. J. Maselli, E. C. Cemak

Hartford Steel Technologies (HST) has a pyrometallurgical and hydrometaliurgical process capable of reclaiming valuable metals from a hazardous waste· stream such as EAF Dust. The HST Process effectively addresses the growing environmental concerns surrounding the increasing production of EAF Dust without producing any hazardous waste material as byproducts. Currently EAF Dust production levels are exceeding the 1,000,000 metric tons per year mark. The HST Process is designed to separate iron, zinc, lead, cadmium, copper, and silver metals using a two-phased process. The Pyrometallurgical side of the Process utilizes a Rotary Hearth Furnace to separate the iron metal from the remaining metals. These remaining metals are further separated, using a Hydrometallurgical Process, in a series of digestion tanks. The individual metals are then collected in saleable form.

Jan 1, 2000

By K. Alibhai

Greek laterites, which generally had nickel concentrations of < 1 %, are amenable to chemical leaching,. although there is considerable variability in the ease of leaching with different ore types. With low grade ores(< 1 % Ni content); >70% of the nickel was leached in columns with a strong selectivity for nickel over iron. Heterotrophic microbially assisted leaching could be a viable alternative to classical hydrometallurgical and/or pyrometallurgical techniques, with a very high recovery (greater than 80% ) being found with some of these mineral microbial interactions. Critic acid was probably the effective chelating agent.

Jan 1, 1991

By Mark R. Jolly, Jean-Christophe Gebelin, Aleksander Cendrowicz

"Injection of wax patterns is the first stage of the multi-stage process of investment casting. The quality of the final casting and its dimensional accuracy is highly dependent on this stage of the process. Pattern waxes used in the industry behave in a complex visco-elastic-plastic manner. The modelling of such material behaviour is therefore not simple.In this paper a number of configurations of die will be shown in which the injection of the wax has been carried out for a range of processing conditions. Some of the dies are transparent and the movements of wax front observed can be compared with those predicted by simulation. Surface defects in final components will also be shown and compared with the location predicted by simulation software. Some discussion will be presented on the limitations of the software used and the time-scales achieved for practical use as a design tool within the foundry environment. IntroductionThis paper presents the research activities carried out at the University of Birmingham on the modelling and prediction of the behaviour of industrial investment casting waxes during the injection of wax patterns. These research activities are done in the context of a more global study of the fundamental aspects of the investment casting process, the FOCAST project. Regarding the wax injection process, the aim of the project is to achieve a better understanding of the key factors that will lead to better castings. The filling of the die during the injection has been studied. Some other phenomena such as shrinkage/warpage or creep under residual stresses are also studied, but not presented here. Two commercial investment casting waxes have been characterised in order to model their behaviour and predict mould filling and subsequent defects.This paper will present the models that have been used in our work, the simulation packages used, the experiments carried out to validate the modelling and exhibit the defects due to bad filling, and finally the numerical simulation results."

Jan 1, 2001

By G. C. Gullo, H. Wabusseg, P. J. Uggowitzer, H. Kaufmann

"The basic concept of New Rheocasting (NRC) is described and the application of wrought alloys with this process is discussed. Practical experiments with the aluminium alloy AIMgSi I are explained. For this alloy the proper NRC - casting temperature was determined by using Thermo Cale - computer software and DT A and the essential processing conditions are shown. In the experiments the melt was taken from an aluminium holding furnace and cast into NRC steel cups. After controlled cooling the resulting slurries were cast into a 4-step die on an UBE HVSC 350 Squeeze Casting machine. The characteristic microstructural values such as grain size and shape factor were measured and compared with classical casting alloys. The influence of the wall thickness of the step part (6 mm, 10 mm and 14 mm) on the microstructure is described. Tensile properties in different heat treatment states are compared with characteristic prope1ties of the same alloys in forged condition. The ew Rheocasting - process CNRC)The NRC process is a recently developed new semi-solid processing method which allows the production of pore-free, pressure tight components.In the NRC process a fu lly liquid, but only slightly superheated melt is taken from a holding furnace and poured into specially designed steel crucibles, which are placed on a carousel next to the Vertical Squeeze Casting machine. In this ,NULL,slurry maker'· globul ar a-Al grains grow, following forced homogeneous nucleation at the cup wall [ 1, 2]. In the few minutes during which the melt is cooled to sem i-so lid processing temperature, a stable ske leton of a-Al phase forms. The resulting slug keeps a cylindrical shape during its slide into the sleeve of the Vertical Squeeze Casting machine, where it is cast into shape."

Jan 1, 2000

By Jiann-Yang Hwang, Ying Qin, Shu-Jing Zhu

Metallurgical Oil Sludge (MOS) is a byproduct created in the process of steelmaking. More than a million tons of MOS are generated each year throughout the world. The material contains hazardous components such as heavy metals and pathogenic organics, which can cause serious environmental problems and health issues. Landfill, combustion, and pyrolysis have been investigated for the disposal of MOS. However, these methods are unsatisfactory since they are unable to reach the clean environment goal. In this study, we investigate the possibility of using MOS as a reductant in a high temperature metallurgical process. The results are reported and discussed.

Jan 1, 2015

By Zhang Hengzhong

Based on thermodynamics of surfaces and a proposed two-dimensional state equation for surfaces, the relationship between the surface tension (Y) of a solution and the activity (a1) of its component (i) was derived: (1/Y)r2-.¬E (ai/Yl) The derived equation was verified with reported experimental data of water-alcohol systems and water-acetone system, the calculated results showed astonishing coincidence with experimental. Applications of the equation to the five matte systems Cu2S-FeS, Ni3S2-FeS, FeS-PbS, Cu2S-PbS and FeS-Cu22S-PbS also demonstrated that at given matte compositions the calculated surface tensions agreed with experimental fairy well.

Jan 1, 1993

By Finlay Campbell

Nickel laterite pressure acid leach plants and reduction roast plants have had a checkered history in their engineering, construction, startup and operational reliability. Many potential projects have been the subject of detailed studies over the last thirty to forty years but relatively few have advanced to commercial production. Four reduction roast plants are currently operating, an additional one was partially constructed but never completed, and another was started up in 1974 and shut down after 12 years operation. Three acid leach plants have been built and commissioned in the last five years, trying to follow the example of the Moa Nickel plant in Cuba. An additional acid leach plant project is currently on hold, following limited construction work, its future subject to review by the owner because of potential cost over-runs. This paper attempts to discuss difficulties that may be encountered as a project is developed and will address factors which may affect production ramp-up schedule, long term production performance and overall production success. Comparisons are made with ramp-up performance at other large metallurgical plants that employ some comparable unit operations. Keywords: Caron, PAL, nickel laterite ore, ramp-up, reliability, process development, equipment design, step-out, commissioning, startup.

Jan 1, 2004

By C. Landolt

Inco&apos;s Copper Cliff Smelter Complex produces some 11 5,000 tonnes per year of nickel and 120,000 tonnes per year of copper. The Smelter flowsheet has changed a number of times over the years. The most recent changes were effected in the mid-1980&apos;s in response to new realities in metal markets and heightened awareness about the workplace environment. By 1994, the flowsheet will undergo yet another metamorphosis as part of Inco&apos;s SO2 Abatement Program. The paper discusses the improvements implemented during the 1980&apos;s and projects the processing in the Smelter through 1994.

Jan 1, 1993

By Koji Matsubara, Yoshiaki Iguchi, Shoji Hayashi

Iron ore particles of a limonite iron ore were reduced completely with H2 at 1023K to 1273K in a fluidized bed. Then, at 973K, the formed iron was exposed to HrH2S mixtures (sulfur activity, as=0.5) for 3.6ks and carbidized with CO-H2-H2S· mixtures at 0.1 MPa. During the carbidization, the particles of about 150mg were sampled at every 600s interval. The sampled particles were analyzed by XRD and chemical analysis for C and S to evaluate the content of Fe3C, Fe5C2, Fe and free carbon. The reaction extent is defined as fo=Xfc3C +xFc5c2; x is the molar fraction of Fe in Fe3C. The carbidization curves can be fitted very well to -ln(l-f0)=g(pb T)t; g(p; T) is the carbidization rate, i.e. the carburization rate on the pore surface of reduced iron. The rate is found to be nearly proportional to the specific surface area of reduced iron, a P 0 , which decreases with increasing the reduction temperature. The value of a P 0 does not change by the carbidization and the stability of the iron carbide product in the atmosphere increases with the temperature.

Jan 1, 2000

By J. C. Agarwal

Slags produced by modern smelting furnaces contain copper values which are unacceptably high for discard. The electric arc furnace is employed commercially to clean copper from flash furnace slags but the addition of highly oxidized converter slags to an electric furnace has created operational problems. Highly oxidized Noranda Reactor slags have not been processed successfully in a pyrometallurgical process. These slags, which contain large concentrations of copper (5 to 10 per cent), are treated in slag concentrators (controlled cooling, crushing and milling, and flotation) which produce a copper concentrate that must be resmelted. Though commercially operable, it will be shown that the slag concentrator has important process and cost disadvantages as compared to a pyrometallurgical process. In this paper an economic comparison is made between a pyrometallurgical process and the slag concentrator. For the analysis, five hypothetical smelting plants are considered. Each plant treats 1200 tons of copper concentrate per day and produces 109,000 tons of copper annually. The plant configurations used in this study are:

Jan 1, 1976

By Vladimiros G. Papangelakis

During the past five years, chemical modelling work at the University of Toronto has elucidated the role of soluble magnesium on the autoclave acidity and has demonstrated why feeds rich in magnesium, and other divalent metals, require more than the stoichiometric requirements in acid to produce a leaching performance comparable to that of low magnesium feeds. This understanding has allowed the calculation of acid additions to the pressure acid leach (PAL) on a less empirical basis. Optimizing acid additions to the PAL confers savings in neutralization costs, ensures high productivity and minimises corrosion problems. Hence, our picture of the solution chemistry inside the autoclave during the PAL process has been substantially improved and is reviewed here. Experimental techniques based on solubility and direct acidity measurements that support the theoretical predictions are presented. Concepts of chemical modelling of electrolyte systems at high temperature and software issues are also discussed. Finally, a better understanding of the solution chemistry at temperature has led to better kinetics models because all metal dissolution and precipitation reactions are acid driven and controlled. . Therefore, reactor modelling efforts by our group are also presented and a reactor model with very good performance, as compared to pilot-plant data, is also made here. Finally, in spite of the above success in PAL solution chemistry and reactor modelling, significant challenges lie ahead in theoretical data gaps and instrumentation; these are also discussed in this paper. Keywords: Laterites, process modelling, pressure acid leach, solution chemistry, chemical modelling, reactor simulation

Jan 1, 2004

By D. B. Dreisinger, V. van der Pas

Zinc sulphate electrolyte used for zinc electrowinning must be purified for cObalt ions. The cobalt is removed in a cementation stage by the addition of zinc dust. Copper arid antimony are frequently used additives which enhance the cementation of cobalt. This paper aims at a better understanding of how copper and antimony promote the removal of cobalt. Initial experiments were done in a batch cementation reactor. Copper and antimony precipitated in the early stages of cementation indicating that a preferential substrate was formed. The individual role of copper and antimony was further investigated in an electrochemical cell. On a microsca1e, the , growth process, morphology and the composition of the precipitates were examined with SEM and XRD. It was found that cobalt could not be deposited in its pure form but as a cobalt-zinc alloy with zinc as the prime constituent. Copper increases the cathodic surface area of zinc dust by precipitating as numerous dendrites. Antimony acts as a cathodic surface onto which a cobalt-zinc alloy with an increased cobalt content is deposited.

Jan 1, 1997

By Mark Tsirlin

Kinetics of the initial oxidation stages of diffusive silicide coatings on 8 molybdenum and niobium at 1100 - 1700 and under the pressure of 400 and 1330 Pa has been studied using methods of gravimetry and gas phase analysis of oxygen, as well as by SEK, XRD and EDMA methods. The first oxidation stage described by asymptotic equation in case of NbSi coating changed over to the stage described by parabolic equation. The asymptotic law was shown to depend on non - stationary conditions on the oxide layer boundaries. Interconnection between silicides and quartz structures, on the one hand, and peculiarities of oxidation kinetics, on the other, is [discussed. The possibility of estimation oxygen atom jump frequency in quartz and fractions of oxygen reacting with metal and with silicon proceeding from the analysis of the kinetic data was ascertained. Conditions of oxidation kine- tics transfer from asymptotic (or parabolic) stage to a non - protective "linear" stage, associated with volatile ~roduct formation, are also discussed.

Jan 1, 1995