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By Xiaobing Yang, Abhishek Lahiri, Animesh Jha

"In the FFC-Cambridge process, the cathodic dissociation of oxide and CO/CO2 production on carbon anode is the basis for metal production in a CaCl2 bath. By using an inert intermetallic anode, the CO2 evolution can be eliminated altogether with acceleration in the electro-reduction kinetics. At present the process suffers from slow reduction kinetics of TiO2 to Ti metal, which can be enhanced significantly by the incorporation of alkali species in the TiO2 pellet at the cathode and in the CaCl2 bath in the presence of an intermetallic inert anode. Nearly full metallization with greater than 99% of Ti metal containing 1500 ppm of oxygen is possible to achieve in less than 16 hours of electro-reduction. Analyses of phase composition and the microstructures morphology in fully metallized pellets revealed the presence of localized solidified Ti layer, indicating that fast reduction process also involved formation of liquid phase as middle stage reaction. In addition, in situ creation of porosity and maintain higher current level during electrolysis process were two key factors to fully reduction of TiO2.IntroductionDuring cathodic dissociation of TiO2 in a CaCl2 bath and anodic evolution of CO2 on a carbon anode, which is the basis for the FFC Cambridge process [1], the rate of metallization slows down due to the formation of CaTiO3 at the reaction interface. Calcium and alkaline earth perovskites are known for their poor electrical conductivity which adversely affects the overall electro-reduction. One of the ways to increase the porosity is via the addition of polyethylene precursors in the pellet or by directly starting from perovskite [2, 3]. The experimental evidences shown in the literature confirm although the speed of reaction increases, but a complete or near complete metallization is not possible by enhancing the in-situ porosity alone, as the insulating perovskite is very slow to decompose under the equilibrium that prevails in the cell. Plethoric evidences on carbon anode show with the current decrease gradually, and finally stabilize at a very low value between 0.2 and 0.4 A, which is a testimony of the presence of perovskite insulating barrier in the current path. Our aim in this paper is to demonstrate the mechanism of enhanced electro-reduction when alkali ions are present in the oxide pellet at cathode and in the bath. We also show for the first time the use of an intermetallic anode for Ti-metal production using the FFC Cambridge process."

Jan 1, 2009

By S. Gopalan, J. D. Milshtein, S. N. Basu

Production of syngas is proposed utilizing the W/W03 redox system and employing a solarpowered two-step thermochemical cycle. Three chemical reactions occur in two chambers. Assisted by a solar concentrator, a high temperature reaction reduces W03 powder to metallic tungsten in both chambers. Subsequently, the temperature in one of the chambers is lowered and H2(g) is produced via re-oxidation of the tungsten powder using steam. The temperature in the other chamber is simultaneously lowered to an intermediate temperature and CO(g) is produced via oxidation of the tungsten powder using C02(g)· The gas streams coming out of the two chambers result in the syngas production. A complete thermodynamic analysis of the system is described. The W/W03 redox cycle offers greater gravimetric fuel productivity compared to previously proposed systems, and the entire cycle can be operated below 1273K.

Jan 1, 2013

By L. W. Beckstead

In a conventional zinc refinery plant, zinc concentrates were roasted at 950°C. The calcine was ground and leached in a series of leaching vessels using sulfuric acid. The pH in the first leaching vessel was maintained at 2.5, while the pH of the solution exiting the last vessel was about 5.4. The leached residue typically contained (in percent) 0.1 Ag, 0.2 As, 0.7 Cd, 2 Cu, 15 Fe, 10 Pb, and 15 Zn, and it was classified as hazardous material according to the EP-toxicity test. In order to make the residue non-hazardous, and to recover most of the metal values from the residue, a brine leach process was developed. The process consisted of leaching the zinc leach residue in CaCI, brine solution at pH 2 for 1 hour at 90°C. Silver extraction was about 95 percent, while lead, copper, cadmium, zinc, and iron extractions were about 80, 50, 50, 30, and less than 0.5 percent, respectively. More extreme conditions of acidity could have been used in the leaching stage to increase zinc dissolution, but iron dissolution would have significantly increased which would have complicated subsequent recovery steps. The leached and washed residue passed the EP-toxicity leach test and could be disposed as non-hazardous. Silver, copper, and lead in the leach solution were recovered by zinc cementation, while zinc and cadmium were recovered by sulfide precipitation. The resulting solution can be recycled in the process after magnesium precipitation.

Jan 1, 1993

By Chunlin Chen

Nickel-sulfide minerals are normally associated with copper and iron sulfides and often contain a minor amount of valuable metals such as cobalt and detrimental impurities such as arsenic. Metal losses in slag vary from process to process during the pyrometallurgical production of nickel and, depend on the feed composition, slag chemistry and operating conditions. Maximiz the metal recovery is one of major considerations to optimize operating condition for nickel smelting/ converting processes. At the same time, the deportment of minor elements between various phases during nickel smelting is of great importance by smelter operators. The Multi-Phase Equilibrium (MPE) is a thermodynamic package developed by CSIRO for simulating reactions between phases in multi-component and multi-phase systems [1]. Over the years the capability of the MPE model has been extended to cover the behavior of a large number of elements in high temperature systems. The sulfide smelting module of the MPE, which covers the minor elements such as As, Bi, Sb, Pb, Se, Te, Sn, Co and Zn, is capable of modeling the deportment of major and minor elements between various phases during nickel smelting. In this article the application of the MPE model in modelling the nickel smelting process is presented. The modelling results on the majors and minors are compared with the plant data. The deportment behaviour of arsenic in nickel smelting was analysed and the impact of slag chemistry on slag properties was modelled. These results can assist process metallurgists in exploring the optimum fluxing strategy for smooth operation and the potential practices for improving arsenic removal.

By Caryn Wendt, Donna Post Guillen, Armando McDonald, Erik R. Coats, Chaston Ellis, Kevin Feris

Dairy operations constitute ~2.5% of annual U.S. greenhouse gas (GHG) emissions, making dairies one of the largest sources of industrial GHG emissions. We are developing a novel, integrated system to achieve a net reduction in dairy GHGs while producing value-added materials and products. This integrated manure-to-commodities system converts dairy manure to bioenergy, sequesters carbon by converting volatile fatty acid-rich fermenter supernatant to bioplastics, and utilizes anaerobic digester (AD) and polyhydroxyalkanoate (PHA) reactor effluents to produce algae that can be harvested and internally recycled to enhance PHA production and sequester carbon. A decision-making tool is being developed for the integrated system that quantifies net GHG reduction, carbon sequestration, nutrient management and economics.

Jan 1, 2016

By M. J. Adam

The U.S. Bureau of Mines has investigated the partitioning of complex minerals to simpler phases using sulfidation reactions for selective extraction of mineral values. This report describes research in which thermal processing of the complex Ti-bearing mineral ilmenite (FeTi03) resulted in partitioning of the valuable Ti metal to the simpler compound rutile (TiO2). Samples of ilmenite were blended with elemental S for thermal treatment at various temperatures under controlled atmospheres in an effort to dissociate the Fe from the ilmenite complex. Product characterization revealed that the Fe was partitioned 'from the ilmenite, forming a rim of pyrrhotite/pyrite (FeS/FeS2) on a rut il e core. The products were agate milled and then subjected to cursory magnetic and flotation techniques in an attempt to physically separate the partitioned phases. Partitioning results and phase concentration data are reported relative to thermal treatment variables and physical separation techniques.

Jan 1, 1991

By G Hope, C Young, R. N. Gow

"The presence of enargite (Cu3AsS4) is problematic in gold processing as it is refractory, increasing cyanide and oxygen consumption, and enviromnentally hazardous. Selective leaching and treatment of the arsenic would prove advantageous to conventional gold leaching methods. The reactivity of enargite samples from Montana, US and Quiruvilca, Peru were studied under alkaline conditions, pH range of 8-13, using a cyclic voltammetry corrosion cell setup. Raman spectra of the surface were taken during and after cycling to compare surface species against theoretical predominance diagrams. Under slightly oxidizing conditions, covellite (CuS) peaks were found on the surface in a short matter of time, above - 200m V vs SHE for pH 9-13, suggesting arsenic leaching, but for longer conditioning times, elemental sulfur peaks were also found, which created a passivating surface layer. By operating above pH 12, under reducing conditions, ~-500mV vs SHE, arsenic can be leached as a thioarsenate (AsS4-xOx3-), without sulfur formation.IntroductionEnviromnental limitations on pyrometallurgical processing of arsenic has pushed the desire to process enargite-, Cu3AsS4, bearing concentrates towards a hydrometallurgical solution. Attempts to process can be broken down into two categories - the co-dissolution of arsenic and copper under acidic conditions or the selective leaching of arsenic under basic conditions. The selective leaching of arsenic would preferably leave behind a chalcocite, Cu2S, or covellite, CuS, phase that would be more amenable to conventional processing methods of the copper and gold industries. These methods employ bi- or poly-sulfides to leach arsenic as Assl· [1-4], hypochlorite leaching [5-7], ammoniacal leaching [8] or fine grinding to mechanically activate the enargite surface and increase normally slow reaction kinetics[9]. This study looked into the surface formations of an enargite electrode under alkaline conditions, in a pH range from 8-13, as it cycled from -1000 mV to 1000 mV vs SHE. The understanding of the formations and under what conditions they form will be helpful in further development of any of the aforementioned processes."

Jan 1, 2012

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 James T. Skoch

With the ongoing pressure on the secondary aluminum business to limit the amount of waste generated from processing aluminum dross, it becomes very advantageous to preprocess the dross to reduce waste. The advantage of preprocessing is that it significantly reduces the oxides and salt cake generated when melted. Various products can be produced from the oxides for the steel industry. The following paper will demonstrate that removal of oxide fines before melting will result in large volumes of material not being landfilled. We will show that the end result of this technology is to significantly reduce the amount of salt cake sent to a landfill while maximizing the recyclability of the aluminum dross.

Jan 1, 1995

By S. Abe

Various copper anodes to be electrorefined were subjected to a heat treatment comprising annealing at a temperature in the range of 700 °c to 1,000 °c followed by a slow cooling preferably on the order of about 150 °c, and using these heat treated anodes , a series of dissolution experiments were conducted under conventional electrorefining conditions. The results obtained have indicated that the above annealing/slow cooling process dramatically improves the dissolution activity regardless of the type of anodes. As an example, passivation times of l to 3 minutes in a standard test have been increased to more than 80 minutes by this innovated heat treatment. Other advantages sterning from the improved anodic activity include reduced electrical short circuiting which results in substantial labor effort in the tankhouse, reduced energy requirement, and reduced cost of processing anode slimes because the amount of anode slimes is reduced. In addition, this process gives rise to a dramatic change in the nature of anode slime layer formed in such a way that a comparable final cathode copper product can be achieved even from high-impurity copper starting material.

Jan 1, 1987

By lonkion M. Font

Due to the known disadvantages of the use of iron silicate slag in the nickel converting stage, i.e., high metal losses, high magnetite content, and low fixation of impurities in the slag, the development of the new proposed "ferrous calcium silicate slag" for smelting and converting processes of nickel is very promising. Hence, considering the successful experimental results of using CaO base slag for the nickel smelting process, a study based on a detailed comparison for the phase equilibrium, and the minor elements distribution between the NilS2-FeS matte with either FeOx-CaO or FeOx-Si02 base slag was investigated. The main results are summarized as: no difference in the nickel losses between both slags was found at high nickel content in the matte, and the fractional distribution analysis for arsenic and antimony pointed out their preferential fixation in the calcium ferrite slag rather than in the iron silicate slag. Considering the energy and pollution issues, the technical feasibility of using calcium ferrite slag in a converting process of the Bessemer matte will have a prominent future for the nickel industry.

Jan 1, 2003

By Cong Wang, Kexin Jiao, Yongan Zhao, Haibin Zuo, Jianliang Zhang

Traditional refractory materials for blast furnace hearth lining are mainly composed of carbon bricks and the ceramic cup. However, these materials can’t meet the demands for long service life design of blast furnaces. In this paper, a new refractory called carbon composite brick (CCB) was introduced, which combined the advantages of carbon bricks and the ceramic cup. In this case, the resistance of the CCB against corrosion was equal to the ceramic cup and the thermal conductivity of the CCB was equal to carbon bricks. From the results of more than 20 blast furnaces, the CCB could be well used in small blast furnaces and large blast furnaces. In the bad condition of low grade burden and high smelting intensity, the CCB gave full play to the role of cooling system, and effectively resisted the erosion of hot metal to improve the service life of blast furnaces.

Jan 1, 2015

By Richard J. Abitz

Thennodynamic geochemical models have been applied to assess the relative effectiveness of a variety of reagents added to aqueous waste streams for the removal of radioactive elements. Two aqueous waste streams were examined: effluent derived from the processing of uranium ore and irradiated uranium fuel rods. Simulations of the treatment train were performed to estimate the mass of reagents needed per kilogram of solution, identify pH regions corresponding to solubility minimums, and predict the identity and quantity of precipitated solids. Results generated by the simulations include figures that chart the chemical evolution of the waste stream as reagents are added and summary tables that list mass balances for all reagents and radioactive elements of concern. Model results were used to set initial reagent levels for the treatment trains, minimizing the number of bench-scale tests required to bring the treatment train up to full-scale operation. Additionally, presentation of modeling results at public meetings helps to establish good faith between the federal government, industry, concerned citizens, and media groups.

Jan 1, 1996

By José Carlos Abreu

This work presents a kinetics study covering the effects of temperature over the reduction rates of a carbon composite briquette, aiming its use as burden in some of the new alternate ironmaking technologies, such as the Tecnored process. It is reported that increases in the temperature increases the reaction rate. Additionally, the morphology of the iron phase generated during the reduction of these briquettes is presented. It was possible to verify that three types of iron morphology occurred during the process: an external, dense and continuous iron layer, the presence of iron globules at the center of the briquettes and whiskers at the briquette's core. The measurement of the carbon content on the globules and the external iron layer is also presented.

Jan 1, 2003

By Francois Barthelat, Sam Goroshin, David Frost, Alexander Cappozi, Atefeh Nabavi

"In this study, a novel chromium–chromium sulfide cermet was produced by self-propagating high-temperature synthesis (SHS). Conventional techniques for manufacturing metal sulfides are complex, environmentally harmful, and not suitable for producing complex-shape articles. To overcome these disadvantages, a new method for the preparation of the metal-sulfur precursor charge is proposed, which can be described as reactive casting. The first cermet samples produced with the SHS process were found to be very porous, brittle, and have low mechanical strength. The possible sources for the generation of porosity were identified and analyzed and the process for manufacturing the cermet was modified. By improving the manufacturing process, the porosity inside the produced cermets was reduced from 70% to 12%.IntroductionMetal sulfide composites are in high demand in the chemical, metallurgical, and electrical industries because of their valuable characteristics such as hardness, semi-conductivity, electroluminescence, infrared transparency and catalytic properties. Current manufacturing methods for metal sulfides usually involve one of two different principal methods, including a complex multistage wet chemical process involving the precipitation of the corresponding salts from an aqueous solution with hydrogen sulfide, or hot sintering of the respective elemental reactant powders in a resistive furnace in a high-pressure inert or hydrogen-sulfide atmosphere [1, 2]. These conventional methods for synthesizing ceramic metal composites are complex, extremely time and energy consuming, environmentally harmful, and rarely able to manufacture articles with complex shapes. Therefore, in order to overcome these disadvantages, self-propagating high-temperature synthesis (SHS) was considered as an alternative method that offers significant improvements over the traditional cermet manufacturing methods [3]. SHS, which is a relatively new and attractive method for producing a wide range of advanced materials, is based on the self-sustaining feature of the highly exothermic reactions of the reactants. The SHS process results in high product purity, since the high temperatures generatedin the reaction cause any impurities to volatilize [4, 5]. SHS has low energy consumption and doesn’t require an external energy source and complex equipment, and it is self-contained [1, 5]. Since combustion synthesis has low power requirements, it is one of the few methods of materials synthesis that is feasible in outer space. Also, the process has a low cost and is capable of directly synthesizing articles with the desired shape, size and structure [5, 6]. The chemical reactions associated with SHS are typically completed in a few seconds leading to the formation of the condensed product. The high reaction rates and relatively rapid cooling in SHS reactions can avoid undesirable grain growth in products which often occurs with the conventional sintering method [3, 5, 7]. The traditional method for sample preparation in the SHS technique is to compact the reactant mixture powders in a steel die by a press to a typical density of about 80% of the theoretical maximum value, before igniting the mixture [8]. This method requires a large compression force to increase the green density and to minimize any pores in the green compact. To overcome these disadvantages, a new method for the preparation of the precursor charge in metal-sulfur by SHS is proposed which can be described as melt casting of a reactive mixture, or reactive casting in short."

Jan 1, 2012

By J. D. Ecuyer, L&apos

he microstructure of galvanneal coatings formed on extra low carbon and interstitial free steel substrates has been characterized using electron microscopy (TEM and SEM) and x-ray diffraction. The coatings are found to consist of a mixture of gamma, delta and zeta phases, of which delta is the main constituent. The amounts of each phase influences the powdering resistance of the coating which was evaluated using reverse Olsen testing and 60" bending. For the three heat input conditions considered, IF coatings were always found to contain a significant amount of gamma and only those which retained zeta phase on the surface exhibited a satisfactory powdering resistance. In much the same way, ELC coatings with relatively thick gamma layers performed satisfactorily only when some zeta was retained. It was also found, however, that coatings with minimal zeta and gamma had an excellent powdering resistance. The latter coatings were produced under galvannealing conditions of lower relative heat input. These results indicate that in addition to the zinc bath composition, coating weight and galvanneal thermal cycle, the base steel chemistry also has an effect on the coating microstructure. Knowledge and control of all aspects of galvannealing is therefore essential to consistently produce acceptable coatings.

Jan 1, 1992

By Jingyuan Wang, Hengyi Zhang, Peng Lan, Ruitian Zhang, Jiaquan Zhang, Yang Li

"For the determination of mould taper and wall thickness, a 3-D numerical model of ingot-mould-hot top system has been made to evaluate the related ingot solidification process and the final soundness. The effect of mould wall thickness and the taper of its hot faces on the thermal history and the as cast structure of steel ingot has been revealed through the numerical simulation. It is shown that the ingot soundness can be improved remarkably by increasing the mould wall thickness, which is possibly beneficial to the mould life as well owning to an improved mould thermal state. The mould taper is vital to the ingot soundness but much less coherent to the mould temperature profiles. Under given casting situations, a larger mould taper can lead to a less intensity of the shrinkage porosities at the top part of ingot.IntroductionIngot casting is still one of important processes for steel production, which is adopted especially for the supply of large-sized semi-products of high quality special steels. The understanding to the solidification process is vital to both the yield improvement of casting production and the quality control of steel ingots, such as their soundness and homogeneity.The ingot processing and service performance are closely related to its defects, such as porosities and pipes[1,2], which are the most common but serious defects during ingots casting. In the late 1960s, Mahadevan and Murthy et al.[3], Irani and Kondic[4] began to analyze criteria for the prediction of shrinkage porosities in light metal casting. In 1980s, Niyama and Uchida[5], Hansen and Sahm[6,7] et al have successfully presented some related porosities and pipes criteria for steel casting. At the same time, numerical solidification simulation was well developed and applied to ingot quality studies[8-10]. However, due to the quick development of continuous casting, less emphasis has been given to the further study on ingot casting process. There leaves much work to be made for the comprehensive understanding to ingot quality improvement and the mould design by the aid of modern solidification technology[11, 12]. In this paper, the effects of mould taper and wall thickness on its thermal history, ingot solidification and the final soundness are numerically studied through solidification simulation, which has been adopted in mould design and industrial production of both the mould and its steel ingot."

Jan 1, 2012

By R. H. Crist

Reactive components of algal cell walls include uronic and alginic acids: In addition, many marine species have half ester sulfate groups which function as fixed anions. Associated metals vary with the media, eg., Ca and Mg in fresh water (FV) and Na, Ca, Mg in seawater. . These metals readily exchange with aqueous phase protons or metal cations. A plot of the total amount of metal cations displaced by protons vs .. pH shows one inflection at pH 4 for FV algae and' in addition a second inflection at pH 2, 3 for marine algae. The first inflection is interpreted as. Indicating the cations associated with carboxyl groups ,and the ,second with half ester ?Sulfate groups. The exchange capacities of various aigal ,species vary widely. When FV algae is placed in a Pb2+ solution,- the amount of Pb2"' deposited on the algae is. Equivalent to the. Total Ca2?, Mg2, and H+ displaced? thereby confirming the ion exchange mechanism. Ion exchange equilibrium constants are reported for the displacement of ca2+ from Vaucheria. With Mg2+, sr2+, Cd2+, Pb2+_ and Na+ as well as the reverse reactions. Cd2+ can .be removed partially from algae by precipitating it as CdS or Cd(OH) 2 Pb2+ and Cu2+ are also partially removed as the hydroxides. Rates of reaction for various alkali hydroxides decrease with increasing .unhydrated cation radius. It is concluded that theory is useful in predicting viable applications for algae in pollution abatement.

Jan 1, 1991

By Minh H. Pham

This paper presents a technique for imaging the extent of solidification of molten metal flowing in a cooled pipe based on the concept of eddy currents. A 3D mathematical model, which relates the geometry of solidification to the scattered field induced in a solenoid external to the pipe, is derived. The model is described by a set of integral equations which are solved numerically using the moments method. An iterative algorithm is developed to reconstruct the solidification distribution image. Experimental measurements have shown that the eddy current technique is sufficiently sensitive for practical purposes.

Jan 1, 2001

By J. A. Holmes

Due to varying and complex mineralogy, the flotation tailings from the Chingola Concentrator have, for some years, contained upwards of 0.4% acid soluble copper. In 1968, an investigation was initiated, to determine a method for recovering this acid soluble copper. This initial investigation concluded with a recommendation to install a leach-solvent extraction-electrowinning plant at Chingola, to treat up to 900 000 tonnes of material per month, for an additional copper production of some 4 500 tonnes per month. The process consists basically of six stages :- Materials reclamation handling and preparation, acid leaching in air agitated pachucas, solid-liquid separation by countercurrent washing in thickeners, solution concentration and purification by solvent extraction, copper recovery by electrowinning, and residue neutralisation and disposal. This paper describes the development of the main parameters for design of each of the six sections, and gives details of the final plant design. Problems encountered in commissioning and initial operations are commented on, particularly insofar as they indicated any errors or misjudgements in the design. The choice of materials of construction is commented on in some detail.

Jan 1, 1976