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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 Anna Franzkowiak, Dean Gregurek, Alfred Spanring, Angelika Ressler

In order to determine the most suitable refractory products and improve the lining lifetime for the diverse furnaces used in the nonferrous metal industry, corrosion tests are performed at RHI’s Technology Center. The practical facilities include the cup test, induction furnace, rotary kiln, and drip slag test described in this paper, which enable a comprehensive understanding of the chemo-thermal brick wear on a pilot scale. The corrosion trials are performed with actual slags generated during operations at a customer’s plant. To determine the highest influencing wear parameter, every single test is combined with a detailed mineralogical investigation and thermochemical calculations performed using FactSage. Based on the results, tailored refractory solutions for the nonferrous metal industry can be provided in combination with trials conducted at the customer’s site.

Jan 1, 2014

By R. Burkhard

Recovery of metals from complex mixed wastes is a challenging task of modem material and waste management strategies. Thermal methods are an important tool in this respect. Plasma turned out to be particularly useful for treatment of complex or toxic wastes and residuals. In order to study plasma processes at reasonable costs, a pilot plasma plant has been used and wastes like ~pent Raney-Nickel catalysts, copper and ah.:lminum drosses, and. other metal containing wastes were investigated. The paper summarizes the most significant findings

Jan 1, 1995

By E. Dendy Sloan

An overview of hydrate properties is given, with emphasis on unusual deviations from ice, the most common solid water form. Reliable sample preparation and reproduction of in situ hydrates provide the foundation for all hydrate science and engineering. Relations are given to connect the three domains in the title: (1) micro-scopic properties measured with Raman, NMR, and diffraction spectroscopy, (2) meso-scopic properties measured with single crystals, and (3) macro-scopic properties measured with pressures, temperatures, volumes, etc. A principal illustration relates micro-scopic and macro-scopic domains. Experiments provides the basis for improving statistical thermodynamics model for these compounds. To date, this model is one of the most commonly used industrial statistical thermodynamics applications, based upon the classical model of van der Waals and Platteeuw (1959). Microscopic measurements and simulations indicate model assumption improvements, resulting in the next generation of the statistical thermodynamics for improved macroscopic property prediction.

Jan 1, 2002

By Zemin Ma

A novel chromate [Cr(VI)] reducing bacterium was isolated from chromite ore processing residue disposal site of China and identified as a Leucobacter sp. by 16S rRNA gene sequence homology. The minimum inhibitory concentration of strain CRB1 was 820 mg l-1 of Cr(VI). The reduction of Cr(VI) occurred only under aerobic conditions. With an initial concentration of 2.5×108 cells ml-1, 1800 mg l-1 of Cr(VI) was reduced entirely within 38 h under the optimum conditions, at 30 °C and pH 9.0. Increasing Cr(VI) concentrations prolonged reduction process and higher cell densities meant quicker reduction. A blue precipitate was produced during chromate reduction of strain CRB1, which was binding to the surface of bacterial cells and determined as trivalent chromium with electron paramagnetic resonance (EPR) spectrometry. The conspicuous chromate reduction ability of Leucobacter sp. CRB1 suggested a potential for bioremediation of Cr(VI) containing wastes.

Jan 1, 2008

By Ram V. Ramachandran

As an industry with major potential impacts (both good and bad) on water resources and due to the rising costs of process water, the mining and metallurgical processing industry has a key responsibility to contribute to the overall goal of preserving both the quantity and quality of water available within the watersheds they operate in. As we plan for new and existing mining and metallurgical projects, we need to consider a hierarchy of options to minimize our impact within the watersheds we operate; keeping clean water clean by diverting around our operations; reduction in the amount of water we use; reuse of water wherever possible, and improvements to water quality for recycling and/or release to environment. Technology is needed to treat water to improve its quality for reuse or release to the original watershed. While lime precipitation followed by sulfide polishing is effective for removal of most of the metals, it does little or nothing to remove ammonium ions and anions such as chloride, nitrate, molybdate, arsenate and selenite/selenite. Regulations on sulfate limits in treated discharge water has drawn close attention to the treatment of acid mine drainage (AMD). Management of brine and salt disposal is also posing a problem due to strict regulations and cost of disposal. This paper will: (a) address issues associated with managing water with the objective of maintaining water sheds—status quo-during and after operation (b) discuss potential technologies for advanced water treatment plants.

By R. M. Taylor

Lime addition to acid mine drainage (AMD) leads to precipitation, predominantly of metal hydroxides and calcium sulfate, and is the benchmark for remediation by precipitation. Geo2 Limited of Melbourne, Australia has developed and patented a novel alternative precipitation scheme based on the formation of mixed valency, M(I1)-M(III), hydroxide sulfate salts. When the composition of AMD is appropriate, the Green Precipitate Process provides a useful and more effective alternative to conventional liming. The characteristics and utility of the Green Precipitate Process are described in terms of the underlying chemistry, and a case study where the Green Precipitate process outperforms conventional liming. A mobile pilot pipe reactor rig which was built by Geo2 to demonstrate the process, and used successfully in both Australia and the United States, is described.

Jan 1, 1998

By Xie Zhang, Jiang Diao, Xiaojun Li, Bing Xie

"Vanadium is widely utilized as an important element to improve the quality of alloyed steels in iron and steel industry. Moreover, the crystallization process of V-containing spinels plays a significant role due to the aim of achieving a fairly larger size of spinel crystals in vanadium extraction. Thus, a comprehensive exploration and discussion on the competitive precipitation and growth of vanadium, chromium and titanium spinel crystals in vanadium slag during a cooling process were carried out in the present study on the basis of a crystallization kinetic model. To be more specific, the abilities of forming crystal, precipitation order and suitable temperature range for crystallization of the three kinds of spinels were discussed with both theoretical and experimental methods.IntroductionVanadium is an important element which is used almost exclusively in ferrous and non-ferrous alloys due to its excellent physical properties such as high tensile strength, hardness, and fatigue resistance [1]. Various kinds of processes of vanadium extraction from V-containing hot metal are available at present. However, only four processes which are the Highveld process (South Africa), the Pan-steel process (China), the NTMK duplex process (Russia) and the New Zealand steel process (New Zealand) take the dominant positions [2, 3]. Although the type of reactor and the initial vanadium content in hot metal are different in these techniques, they share the same principle that vanadium is oxidized by oxygen into vanadium slag."

Jan 1, 2012

By Tomás Vargas

The catalytic role of Thiobacillus ferrooxidans in the dissolution of chalcopyrite was studied by leaching pure massive samples of this sulfide with a pure strain of Thiobacillus ferrooxidans (ATCC 19859). Monitoring of the bacterial activity showed that an important fraction of the total bacteria generated during leaching remained attached to the chalcopyrite surface. Bacteria grown in the system, which were the offspring of bacteria adhered to chalcopyrite, was well explained as the result of the utilization of ferrous ion and sulfur as energy sources. The potential for indirect and direct action was fully utilized by the existing bacteria and the leaching process was controlled by the kinetics of chalcopyrite dissolution.

Jan 1, 1990

By Janusz Majta

The aim of this work is to investigate the control of microstructure evolution through variation of particular deformation parameters in the two-phase (intercritical) region. Niobium-microalloyed and low-carbon steels were investigated. A detailed examination of the factors affecting the ferrite microstructures of tested steels indicated that there were distinct advantages of finishing at temperatures in the austenite-ferrite region. The various results of deformation in the two-phase region are presented. Consequently, the influence of the most important process parameters on the microstructure evolution and mechanical response of the material is determined. The prime objective of the realized research work is the determination of relationship between the history of deformation and final product quality i.e. texture and mechanical properties. To reach the objective, the constitutive equations are proposed for modeling the effects of the hot-deformation process occurring in the austenite and austenite-ferrite region of low carbon and microalloyed steels on the mechanical properties of the resulting product. These models link advanced, finite element approaches simulating metal flow and heat transfer during hot-plastic deformation with constitutive equations describing microstructural processes and mechanical properties.

Jan 1, 2003

By Stephen Gale, David Clarry, Edmund Smith, Jon Feldman

"In 2006, a Canadian steel maker embarked on an ambitious initiative to become “Best in Class in Energy Management”. This initiative provides the framework for this paper, with some augmentation from other energy management projects carried out by Hatch. The initiative focused on identifying energy/GHG management improvements leading to low-cost implementation of energy savings or GHG emission reduction. The key components of the approach were:• Review site energy management practices and benchmark internationally.• Review best technical practices and benchmark against public energy intensity data.• Conducted a site-wide Energy Assessment and physical review of operating areas.• Facilitation of on site-workshops with staff to prioritize savings opportunities, as well as identify and remove implementation barriers.• Development of an Energy Management Action Plan for implementation of improvements.Most organizations can produce, with relative ease, a list of ideas for saving energy, implementing them is the challenge. This paper addresses these issues as well as the profitability of the energy efficiency improvements and the consequences for GHG emissions.IntroductionWhen one of the authors was an undergraduate engineering student at the University of Cape Town in South Africa, the technical drawing instructor made a statement that was both humorous, and mildly profound. He claimed that the most successful engineer is one who is both lazy and diligent. Lazy, in the sense that the engineer is constantly on the lookout for an easier, more efficient, way to do something. Diligent, in the sense that the engineer will work tirelessly to come up with a good technical solution for the easier way. This paper, somewhat of an anomaly in a compilation of technical proceedings, hopes to break the mould a little, and to show a “lazy-diligent” way of reducing the carbon emissions from an industrial facility, using a steel plant as an example."

Jan 1, 2008

By Dong Joon Min, Joo Hyun Park, Mi Sun Choi, Jae Hong Shin

Sublimation of ZrCl4 is important for the production of nuclear grade metallic Zr in Kroll’s process. The sublimation kinetics of ZrCl4 was investigated by TGA under both isothermal and non-isothermal conditions. The sublimation rate of ZrCl4 increased with increasing temperature under isothermal conditions. ZrCl4 sublimation was confirmed to be a zero-order process under isothermal conditions, whereas it was first-order kinetics under non-isothermal conditions. The activation energy of ZrCl4 sublimation under isothermal conditions was 21.7 kJ/mol. The activation energy for non-isothermal sublimation was 101.4 kJ/mol and 108.1 kJ/mol with the Kissinger method and Flynn- Wall-Ozawa method, respectively. These non-isothermal activation energies were very close to the heat of sublimation (103.3 kJ/mol). Sublimation occurs by two elementary steps: surface reaction and desorption. Therefore, the overall activation energy of ZrCl4 sublimation is 104.8(±3.4) kJ/mol. The activation energy of the surface reaction and desorption steps are proposed to be 83.1 kJ/mol and 21.7 kJ/mol, respectively.

Jan 1, 2014

By A. Rawat

The removal of oxyanions of arsenic present in mine process water and drinking water to a regulatory level is a challenging problem. Recently a patented adsorbent lanthanum oxide has been developed which has shown strong specificity for the anions of arsenic. In this paper the kinetic and thermodynamic aspects of arsenic adsorption on to lanthanum oxide are discussed. Adsorption tests were performed at different temperatures using synthetic solutions of arsenic of varying concentrations. From the kinetic data and adsorption isotherms thermodynamic properties such as Gibb's free energy, standard enthalpy of adsorption, standard entropy, isosteric heat of adsorption and activation energy were determined. The results showed that temperature had a positive effect on the rate and degree of adsorption:The activation energy decreased with increase in the initial concentration thus indicating solute-solute interactions in the system. Also, the isosteric heat was found to decrease with increase in the adsorption density implying a heterogeneous adsorbent surface.

Jan 1, 1998

By Elias Rigopoulos

In the present study the reductive behavior of dust from the rotary kilns (RK), in ferronickel production from nickeliferous Greek laterites, is investigated. The study concerns dust of various origins (washing towers, electrostatic filters, polycyclones) and pellets made from the dust. Reducibility was studied in the temperature range of 700 °C to 850 °C in a laboratory tube furnace. Experimental results showed that reduction degree increases with temperature up to about 800 °C. The rate of reduction is great during the first minutes, giving a reduction degree R% equal to about 25%, in only a few minutes. After this, the rate is decreasing until it diminishes to zero after about 10-20 minutes of reaction. Maximum reduction degree achieved is 26 to 28%. Rates and reduction degrees at various temperatures are higher for the dust samples than those of the respective pellet samples. Keywords: Ferronickel, metallurgy, laterites, pellets, reduction

Jan 1, 2004

By Frame Ritzert, Dennis Keller, Vijay Vasudevan, David Arenas

"An investigation was conducted to describe topologically close packed (TCP) phase instability as' a function of composition in the advanced ·Ni-base superalloy Rene N6. TCP phases are detrimental to overfill high-temperature performance of Ni-base superalloys because of their brittle nature and because they deplete the Ni-rich matrix of potent solid solution strengthening elements. Thirty-four variations of polycrystalline .Rene N6 determined from a design-of-experiments approach were cast and homogenized at 13 l5°C for 80 hours followed by exposure at 1093°C for 400 hours to promote TCP formation. The alloys had the following composition ranges in atomic percent: cobalt 10.61 to 16.73, Mo 0.32 to 1.34%, W 1.85 to 2.52%, Re 1.80 to 2.11%, Ta 2.36 to 3.02%, Al 11.90 to 14.75%, and Cr 3.57 to 6.23%. Physical and chemical characteristics of all microstructures obtained were described using various analytical techniques. From these observations, a mathematical description of TCP occurrence (s and P phase) was generated for polycrystalline Rene N6.IntroductionNi-base superalloy single crystals represent the state-of-the-art for turbine engine airfoil application as they offer the best balance of properties to allow for the high operating temperatures required: for efficient engine operation.1 Current trends in alloy design take advantage of improved creep rupture strength with the addition .of higher levels of refractory elements. 2 In .particular, the addition of significantly higher levels of Re in third generation superalloys is key for both microstructural stability and creep rupture strength. 3 While the presence of the refractories is thought to provide strength benefits from solid solution hardening, a tendency for alloy instability in the form of topologically-close-packed (TCP) phases or secondary reaction· zone (SRZ) ·phenomena accompanies the high refractory content. 3 The formation of these phases in sufficient amount is detrimental to the overall high temperature performance of Ni-base superalloys because of their brittle nature and because they deplete the Ni-rich matrix of potent solid solution strengthening elements.4 The tendency for a particular composition to form TCP may not be immediately known since the precipitation of TCP phases in Ni-base superalloys is nucleation controlled, thereby requiring long times at elevated temperatures to precipitate. 5 They preferentially nucleate along the octahedral planes of the Ni-base superalloys, usually in areas of refractory metal enrichment at grain boundaries or inside dendrites.5-6 In Rene N6, two closely related TCP phases, a and P, have been observed.2"

Jan 1, 1998

By T. T. Chen

Raw anode slimes consisting primarily of PbSO4, AgCuSe, Cu3Se2, Cu2-x Se, Cu2O, CuSO4.5H2O, Sn arsenate and Sb-Bi-As oxide are batch-leached with electrolyte-O2 to dissolve Cu. During this process, Cu2O and CuSO4.5H2O are solubilized and the Cu in the selenides is leached with the formation of Ag2Se and Se. A small amount of Cu remains in the Ag2Se, Sn arsenate and Sb-Bi-As oxide. The decopperized slimes are repulped in Na2CO3 solution to convert most of the PbSO4 to NaPb2(CO3)2(OH). The Sn arsenate and Sb-Bi-As oxide partly react, but the Ag2Se is not significantly affected by the Na2CO3 solution. The NaPb2(CO3)2(OH) intermediate phase is dissolved in acetic acid to leave a final product consisting of Ag2Se, Se, Sn arsenate and Sb-Bi-As oxide, together with small amounts of PbSO4, NaPb2(CO3)2(OH) and various gangue constituents.

Jan 1, 1993

By Vaughan R. Voller

"Over the last ten years an increasing number of heat and mass transfer models of solidification processes have been presented in the literature. A key component in these models is the coupling between thermal and solute fields. This is achieved by developing relationships based on the behavior at the microscopic scale in the casting (typically a secondary dendrite arm space). An important class of models in this respect are models that describe the local scale redistribution of solute alloy components-collectively referred to as microsegregation models. This paper explores this class of models.IntroductionModeling takes a key role in processing materials for properties. This is particularly time in solidification processes where current computer techniques allow for a detailed treatment of the critical macroscopic phenomena. Typically these macro scale models consist ·of three main coupled components.1. A model of flow in the melt and solid + liquid mushy region.2. A model of heat transfer.3. A model of solute transport.The focus of this paper is the solute transport component, in particular the manner in which process scale transport is coupled to transport ·at the local scale of the solid-liquid interface. This step requires a modeling of the redistribution of solutes at the scale of the secondary arm spaces in the dendritic mushy region-a process referred to as microsegregation. Basic microsegregation models use the limit assumptions of no mass diffusion in the solid (Gulliver-Scheil [l]) or complete diffusion in the solid (equilibrium lever rule) in a fixed and space. Recently, however, more sophisticated microsegregation models that account for finite mass diffusion and coarsening of the arm space have been developed [2-19]. In this paper governing equations for a general microsegregation model for a multi-component alloy in a coarsening and spacing _are introduced. From these general equations various models for a binary system are developed and tested"

Jan 1, 2000

By P. Peczak

A Monte Carlo simulation technique has been used to study dynamic recrystallization in polycrystals. A continuum microstructure of the polycrystal is modeled employing a discrete lattice. The response of the material to hot deformation is simulated by adding stored energy and recrystallization nuclei continuously with time. The experimentally observed nonuniform character of deformation substructures is modeled by employing a phenomenological expression for inhomogeneous distribution of the stored energy. All simulations were performed on HP-Apollo 9000 Series 700 workstations. A program written in FORTRAN with use of PHIGS graphics library calls was used to interactively monitor the current state of the matrix and all relevant parameters: deformation stress, average grain size and effective nucleation rate. Visual analysis of the simulated microstructure allows a better understanding of the data developed by averaging over a number of very long Monte Carlo runs. Since the essential features of dynamic recrystallization are accurately reproduced by the model, it is used to discuss the role of the controlling mechanisms of the dynamic recrystallization in real polycrystal.

Jan 1, 1993

By S. M. Hay

The zinc content of blast furnace and basic oxygen furnace dusts is low compared with electric arc furnace dusts and it is generally not economical to treat the dusts to recover zinc. However, they have a high iron content and removal of the zinc would allow recovery of the iron values. A literature review and thermodynamic analysis was undertaken and, as a result, several smelting options were identified. This paper describes experiments undertaken to develop understanding of metallurgical aspects of these processes which are not amenable to theoretical analysis. Dusts from an Australian steelworks were characterised in order to determine their mineralogical make-up and the form of the iron. The processing aspects investigated in the laboratory were slag-metal equilibrium and solid-state pre-reduction using reducing gases of compositions expected from bath-smelting processes. Particular attention. was paid to the deportment of zinc, sodium, potassium, phosphorous and sulfur between the phases formed during smelting and pre-reduction. The smelting results indicate that less than 10% of the zinc, sulphur, sodium and potassium report to the metal. About 99% of the zinc and potassium and about 80% of the sodium could be volatilised from the dusts by reducing them at 1,000°C with mixtures of CO, CO2, H2 and H2O even when metallic iron was not formed. The experiments indicate that smelting of blast furnace and basic oxygen furnace dusts should produce hot-metal of a composition which can be blended into the main stream of hot-metal in the steelworks.

Jan 1, 1994

By Florian Aurelian, Mihai Popescu

"It will be tested four types of “geochemical barriers”. All those mixtures were contacted with mine waters containing uranium, radium and heavy metals. The loading capacity was determined. The optimum mixture was determined and its efficiency was tested within an uranium areal, where the activity was stopped. It was determined the possibility to recover the radioactive elements and the heavy metals from the investigated barriers.IntroductionThe paper presents the results concerning the performances of some “geochemical barriers” used for the decontamination of mine waters from uranium mining sites, which were tested in lab and in situ.ExperimentalThe research activity was carried out in lab and on the site.In the lab a module was constructed in order to follow up the uptake capacity of the “permeable reactive geochemical barriers” used to remove the radiolelements from the contaminated waters originated from the uranium mining industry. The barriers, which were used, are made of cheap natural materials, which can be easily got (wood chips, peat coal, sawdust, iron span, steel and zeolitic tuff). The following types of barriers were tested:•, 1st barrier: peat coal, sawdust, zeolite on weight ratio of 1/1/1;•, 2nd barrier: bentonite, sand, wood chips, peat coal on weight ratio of 1/1/1/1;•, 3rd barrier: iron span, steel, sawdust, peat coal on weight ratio of 2/1/1;•, 4th barrier: iron span, steel, sand, firry wood chips on weight ratio of 1/1/1.Lab researches concerning the uranium uptake capacity of the above described “reactive barriers” pointed out that the 3rd mixture (iron span, steel, sawdust, peat coal on a ratio of 2/1/1) didn’t reach the maximum uranium uptake capacity not even after eleven contact stages (the uptake capacity being of 70.6 mg U/ kg of mixture) and the mixture of peat coal, sawdust and zeolite has an uranium uptake capacity of 26.6 mg U/kg of mixture and becomes saturated after four contact stages.Each one of the components involved in physical-chemical processes of sorption, reduction and precipitation, will determine the diminution of uranium and other metals contents upstream the permeable reactive barrier."

Jan 1, 2008