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By Hassan Saalman, Mahmoud Mahmoud, Omneya El Hussaini

The Ferruginous sandstone ore was obtained from Ramlet Hemeyir area, Southwestern Sinai, Egypt, was found to contain 10% rare earth elements (REE). A representative sample has been subjected to sulfuric acid agitation leaching. About 93% of the REE content was released by mixing the ground sample to -100 mesh with concentrated H2SO4 at solid/liquid (S/L) ratio of 1/2 for 5h at a temperature ranged from 250 to 300o C. The REE was precipitated from the prepared sulfate leach liquor of pH 1.0 by adding 35% oxalic acid at 25o C. The precipitation yielded 98% REE. For selective separation of yttrium, the rare earth cake was leached with 31.5% nitric acid. Next, the aqueous solution was contacted with di-(2-ethylhexyl) phosphoric acid (D2EHPA) where 98% yttrium extraction was achieved. Stripping was done with hot H2O (80o C). Finally, a precipitation with oxalic acid was done followed by ignition at 950o C. A yield of 95% yttrium oxide was produced.

Jan 1, 2014

By M. A. Gimenes

The utilization of chlorination in extractive metallurgy and advanced ceramics areas has been widely investigated as a preparative route in order to obtain intermetallic compounds, which are used as precursors in the development of new materials and process. The major processes of decomposition of rare-earth ores use sulfuric acid and sodium hydroxide at high temperatures, however there is not much work concerning chlorination. In this work, a systematic study of the reaction between xenotime (REPO4), chlorine and carbon has been performed. Particular emphasis was on kinetic studies to establish optimized conditions for the reaction. The kinetics of chlorination of xenotime raw material by rare-earth elements/compounds has been studied over a temperature range from 600°C to 950°C. The influence on the rate of conversion of xenotime to RECl3 on temperature, partial pressure of chlorine, carbon content, and particle size were investigated. A global rate equation that includes these parameters has been developed. The results show that the process follows the unreacted core-shrinking model with a formation of a porous product layer. The powder X ray-diffraction technique corroborated this model showing clearly the patterns related to the formation of yttrium oxychloride (YOCl), indicating that the reaction mechanism involves the presence ofan intermediate step before the formation of lanthanide chloride.

Jan 1, 2000

By C. O. Bounds

Management of emission control dust from electric? arc furnace (EAF) steelmaking as an RCRA-EPA listed hazardous waste places economic and environmental pressures on the steelmaking industry. Horsehead Resource Development Company, Inc. (HRD) serves the industry by recovering nonferrous metals from the dust in rotary kiln plants in Palmerton, PA and Chicago, IL, and has demonstrated the commercial viability of its patented coal-fired FLAME REACTOR Process. However, because of location and/or regulation, many steelmakers could be more economically served via on-site processing of its dust. Therefore, in 198-7, through a contract with the Gas Research Institute, HRD embarked on a program to develop a gas-fired reactor and test a prototype unit. The development program has successfully proven the environmental, technical and economic performance of the concept. Consistently high zinc, lead and cadmium recovery to an oxide concentrate as well as production of a nonhazardous, delistable slag have routinely been achieved. The gas-fired FLAME REACTOR field experiment results and the economic performance of on-site or smaller regional plants will be highlighted.

Jan 1, 1990

By H. Y. Sohn

The purpose of this article is to analyze critically and quantitatively the effect of chemical equilibrium on the overall rates of fluid-solid reactions. It is shown through a mathematical analysis that a reaction with a small equilibrium constant (a positive standard free energy of reaction) is more likely to be rate-controlled by pore diffusion or mass transfer than a reaction with a large equilibrium constant. The overall reaction rate of the former also tends to be slow. Furthermore, the apparent activation energy of such a reaction approaches the standard enthalpy of reaction (M-f'), rather than the true activation energy of the chemical reaction. The Law of Additive Reaction Times developed by the author is shown to apply to equilibrium-limited fluid-solid reactions and to be useful in quantitatively analyzing the behavior of such reactions.

Jan 1, 2003

By M. L. Cunha

The lack of control of As and Sb compounds from copper smelters and converters has rendered some chalcopyrite containing arsenopyrite, stibnite and tetrahedrite minerals unusable for metal extraction. In the present investigation, we have studied the carbothennic reduction of Portuguese chalcopyrite mineral concentrate in the presence of lime/CaS04 and CaS04/Si02. Thermodynamic equilibrium calculations were performed to study the distribution of As and Sb between metal and the CaO-Si02-FeO slag phase. The phase equilibrium calculations also show the effect of oxygen partial pressure on the increase in the volume of the slag phase, which helps in lowering the copper metal formation temperature and facilitates a better separation between metal, matte and slag. The reduction reaction kinetics was studied between 850°C and 1100 °C, and the phases formed were identified by X-ray powder diffraction and scanning electron microscopy techniques. The importance of this research for using recycled matte, lean and rich minerals with As and Sb is also explained.

Jan 1, 2001

By G. Granata

In this work, we studied the recovery of copper from AMD by cementation with iron powder. To control the size of copper particles within the nanoscale range, we tested the use of the anionic surfactant sodium dodecyl sulfate (SDS). We tested three concentration levels (0.2, 0.4 and 0.6 M) and temperatures (25, 50 and 75 °C). The activation energy of cementation was also assessed by fitting the experimental data with the Arrhenius equation. Under all investigated conditions, the cementation reaction was found to be a diffusion-controlled process. Without surfactant, the activation energy was 19.9 kJ/mol. In the presence of SDS the activation energy increased up to about 35 kJ/mol. With or without SDS, the particle size of the copper product was strongly affected by the cementation temperature. Without SDS, the cemented product aggregated into micro-sized clusters of about 15 μm at 25 °C, 2–3 μm at 50 °C and 1 μm at 75 °C. The addition of SDS resulted in a dramatic decrease of copper particle size up down to the nanoscale range. Under the best operating conditions, the particle size of copper was <100 nm.

By William Petruk

A fully automatic image analysis system that consists of a microprobe, an energy dispersive x-ray analyzer, and an image analyzer was developed at CANME:I&apos; to determine mineral behaviour that affects beneficiation. The interlacing between the instruments permits automatic identification and characterization of minerals in samples of unbroken ore pieces and of mill products. Different types of information are obtained for minerals in samples of unbroken ore pieces than in samples of mill products, and are used differently. For unbroken ore pieces size distributions are determined for discrete mineral grains to predict a grind at which they might be liberated, and other measurements are Irade to predict the percentage of mineral that occurs as nonrecoverable grains. For mill products the minerals are analysed to determine percentages that (1) are free, (2) are likely to be recovered in concentrates, (3) are likely to be lost to tailings, and (4) could be liberated with regrinding. The image analysis data for mill products are processed by a mineral-metals balance program to determine the distributions of free and unliberated mineral grains at each point in a concentrator, pilot plant or bench test. For samples containing trace minerals, such as gold, an automatic search technique is used to scan the entire area of the polished section for the trace mineral grains. The identified trace mineral grains are characterized with regard to size, liberation, and other properties.

Jan 1, 1988

By H. Y. Sohn

The purpose of this article is to analyze critically and quantitatively the effect of chemical equilibrium on the overall rates of fluid-solid reactions. It is shown through a mathematical analysis that a reaction with a small equilibrium constant (a positive standard free energy of reaction) is more likely to be rate-controlled by pore diffusion or mass transfer than a reaction with a large equilibrium constant. The overall reaction rate of the former also tends to be slow. Furthermore, the apparent activation energy of such a reaction approaches the standard enthalpy of reaction (Mf&apos;), rather than the true activation energy of the chemical reaction. The Law of Additive Reaction Times developed by the author is shown to apply to equilibrium-limited fluid-solid reactions and to be useful in quantitatively analyzing the behavior of such reactions.

Jan 1, 2003

By Yuan Zeping

This paper describes the distribution and removal of the main impurities in the pyrometallurgical process ?at the Guixi Smelter. The paper discusses in detail our converting schedule?of3S-SB and injecting deeply a mixture ofNa2CO) and CaO flux into the converters to enhance impurity removal.

Jan 1, 1998

By Sheng-li Wu, Guo-liang Zhang, Bo Su

One of the major challenges for the Canadian Gen IV Super-Critical Water-cooled Reactor (SCWR) concept is the selection of fuel cladding materials. The Canadian SCWR concept will operate at a core outlet temperature of 625 oC and 25 MPa of pressure with peak cladding temperature reaching as high as 800 oC. Corrosion resistance is an important factor for material selection. Austenitic stainless steels that contain Cr contents greater than 18 wt.% are generally considered to provide adequate corrosion resistance. In this work, the pressure dependence of the corrosion of austenitic stainless steel 310 containing 24 wt% Cr is assessed at 625 C for exposures of 1000 hours to evaluate the suitability of superheated steam as a surrogate for supercritical water at 25 MPa. Transmission Electron Microscopy (TEM) revealed that 310 exposed to different pressure conditions at 625 oC. (i.e., 0.1, 8 and 29 MPa) had generally the same type of the oxide structure, i.e., a Cr-rich oxide with the spinel structure on outer surface adjacent to the water phase. The material exposed at 8 and 29 MPa had a double layer oxide structure, with the outer oxide layer having a much larger grain size, while the samples exposed at 0.1 MPa showed only a single spinel-phase oxide layer. Cr-depleted recrystallized austenite grains were found underneath the spinel phase oxide. The adjacent large-grained austenite substrate had M23C6 carbides in the grain interior. The implications of these results are discussed.

Jan 1, 2015

By C. A. Nogueira, F. Margarido

"A research work has being carried out annmg at evaluating the possibility of treating simultaneously several electrochemical systems of spent batteries using the same process, in order to overcome the high costs and difficulties of selective collection and sorting. Zn-Mn02 systems, representing more than 75% of portable battery market, shall be treated in dedicated processes. The treatment assessment using a single hydrometallurgical process of the other major systems (NiCd, NiMH and Li-ion), having Ni and Co as main metals, was the aim of the research work here reported. Sulfuric acid leaching was demonstrated to be adequate for dissolving more than 90% of the metals of interest contained in batteries. The subsequent separation of metals by solvent extraction, using organophosphorous extractants like DEHPA and Cyanex 272, allowed the production of pure solutions of rare earths, cadmium/manganese, cobalt, nickel and lithium, enabling their further recovering.IntroductionRecycling is the best approach for end-of-life management of spent batteries mainly by environmental reasons but also motivated by resources conservation and, in some cases, by economic profits. Most relevant electrochemical systems of portable cells are Zn-Mn02 (ZMB, alkaline and saline), nickel-cadmium (NiCd), nickel-metal hydride (NiMH) and lithium-ion (LIB). These batteries are collected, sorted and usually treated separately, applying for pyrometallurgical or hydrometallurgical technologies, the former being the most common.Several processes have been developed and some of them industrially applied, as described in some available review papers [l, 2]. In Europe for ZMB systems the oldest processes are Batrec [3] and Citron [4]. Although having differences in details, both are based on pyrometallurgical recovery of zinc by distillation, in metallic or oxide forms, being manganese retained in the slag together with iron. Hydrometallurgical alternatives are also available, like Zincex [5] and Recupyl [ 6] processes, both using sulfuric acid solutions as leachant. The application of the existing technologies to battery recycling, instead of using dedicated processes, is other alternative already tested, being the Waeltz furnace or the Imperial Smelting some examples."

Jan 1, 2012

By K. J. Cathro

A hydrometallurgical process is described for the recovery of copper from chalcopyrite concentrates. The process is based on a cupric chloride leach, the concentrate having first been "activated" by heating it with sulphur at a temperature near 400°C. This activation process converts most of the iron of the chalcopyrite to pyrite, which is insoluble in the cupric chloride leachant. The copper is converted to the mineral idaite, which dissolves readily in hot cupric chloride: at 106°C, 98% of the copper is extracted in a three-stage countercurrent leach, the leaching tirqe being 1 hour per stage. The sulphur of the chalcopyrite appears as elemental sulphur, which is recycled for the activation of further concentrate, the final leach residue consisting of pyrite, plus the gangue present in the original concentrate. The copper extracted can be recovered by electrowinning, using a diaphragm cell. Current efficiency (one-electron basis) is about 70% but the cell voltage is only about 1 V, so that power consumption is three times lower than for the conventional sulphate electrowinning process. The leachant is simultaneously regenerated in the anode compartment. The behaviour of minor elements in the concentrate has also been studied.

Jan 1, 1976

By Katia Vutova, Vania Vassileva

Investigations and results on the refining of tungsten scrap applying electron beam melting (EBM) in vacuum are presented and discussed. In this work EB melting experiments were performed in single or double-melt operations with different power inputs and refining times for tungsten purification and recovery of multiple metals (including refractory and other metals such as Mo, Nb, Cu, Zn, etc.), which are alloyed elements or impurities with high concentrations in the initial materials. Evaluations for extraction of some valuable metals, generated in the condensate at their removal from the liquid metal during the refining process are provided. Efficient technological regimes for e-beam melting and refining that enable the simultaneous production of pure metal ingots and condensates that can be used directly or can be used for subsequent extraction of expensive and valuable metals are presented.

Jan 1, 2016

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 Kevin L. Gering

A detection method and apparatus have been developed to perform real-time measurement of aqueous free cyanide, C-. A laboratory prototype can measure cyanide ranging from 5 micrograms ,per liter to 100 milligrams per ?liter for analysis times as short as 2 minutes per measurement. Sample size per measurement is typically only a few mI, thus? minimizing the waste volume produced from spent samples. The basis for this detection device is a quantifiable, stable affinity between the electrode material and free cyanide in the sample; The electrode exhibits piezoelectric behavior, allowing it to be used as a microbalance. This technology &apos;has experienced two generations of laboratory prototypes, and has been thoroughly tested to determine the operational sensitivity toward process variables such as pH, competing reactions, etc. The speed and ,accuracy of this method make it superior to conventional wet chemistry methods used for quantifying cyanide levels in water. A device based on this technology could be useful in areas involving process monitoring and environmental compliance, .particularly in the cyanide-based leach mining industry. Interest for this detector has been shown by the gold mining industry and others. Patent application is in progress.

Jan 1, 1998

By Z. M. Zheng

Cyclic voltammetry, potential step, and ac impedance techniques were applied to study the electrochemical reaction of arsenopyrite in chloride solutions. The relationship between anodic current density and time in potential step measurements indicates that the oxidation of arsenopyrite is irreversible. The results of the constant potential coulometry show that the stoichiometric factor of the total electron involved in the overall reaction is 14. It is proposed that the dissolution of arsenopyrite is retarded by coverage of sulfur produced in the reaction as an intermediate product. The measured results of ac impedance strongly support the proposition. The proposed reaction mechanism also explains satisfactorily the charging current density and Tafel slopes measured in potential step measurements.

Jan 1, 1995

By Bingchen Chen, Zhitong Sui, Junwei Ma

"In the blast furnace slag, titanium disseminated in various mineral phases Titanium could be concentrated mainly in perovskite, which could be selectively precipitated and grown by optimizing the operation factors like the slag composition, temperature of heat treatment and additive agents. This study aims at establishing the titanium slag mineralogy and its distribution in the treated slag and the as-received slag, as well as the methods of perovskite separation. After heat treatment, the grain size was grown from 5 - 20µm to 80 - 200µm, the distribution of Ti02 in perovskite was increased from 48% to 81 %, the morphology was changed from snow-shaped grain to coarsening dendrites or equiaxed crystals. A concentrate were produced by gravity separation analyzing 35.25% Ti02 with a recovery of 68.28% and a tailing analyzing 9.53% Ti02 , and a possibility of flotation upgrading was discussed. I INTRODUCTION CHINA is rich in mineral resources of titanium, 92.4% of which is vanadium-titanium bearing magnetite. About 53% titanium were in iron concentrate after mineral processing, by which the blast furnace slag containing about 25% TiO2 were produced[11 • The content of TiO2 in such slag is too low to separate titanium dioxide, and it is also too high to produce slag cement[21. It has been accumulated to 50 million tons so far, which is still increasing at a rate of 3 million tons per year, and results in a waste of titanium resources and pollution of environment. Due to the dispersed distribution of titanium component in various mineral phases, very fine grain(<10µm) and complex interfacial combination, it is very difficult to recovery titanium component from the slag by traditional separating technique. In this paper, a novel technique to recovery titanium from the waste slags was proposed [3H4l, on which three continuous processes were involved: selective concentrating, selective growing and selective separating. Perovskite was designed as a titanium-rich phase, in which the most titanium was concentrated promptly, then perovskite could be selectively grown and coarsened by optimizing the heat treatment and the appropriate additives [ 5l[6l. The grain size of perovskite phase was larger than 80 µm, and the crystals appeared as coarsening dendrites or equiaxial grains like lump."

Jan 1, 2000

By Jason H. Nadler, Jason A. Kulpe, Stephanie J. Lin

"A numerical method has been developed to predict the microstructural characteristics of reticulated metal foam. The porosity of this foam is derived from sacrificial template particles of known particle size distribution, which are incorporated with other precursor components. In this approach, a porous structure is numerically generated starting with Powell's sphere packing algorithm. The resulting stochastic structure has characteristics similar to those of corresponding metal foam. Deterministic inter-sphere connections are calculated to more accurately model the pore morphology that evolves during thermochemical synthesis. Estimations of pore morphology and specific surface area of the simulated material are compared to lab-synthesized materials composed of equivalent constituent compositions. In addition, the effect of template particle size, inter-sphere connections, and the geometric constraints on pore morphology and permeability are investigated to refine microstructural evolution and design.IntroductionReticulated foams, characterized by their interconnected pore network, can be obtained by incorporating spherical sacrificial template particles into precursor materials followed by template removal processes. The resulting structure is composed of contiguous spherical pores whose morphologies reflect those of the original templates. Based on some of the unique features of this synthesis approach, a methodology is introduced in this work whereby these foams are digitally constructed using experimental data from the template particle sizes and precursor formulation. Digitally constructed porous structures can then be compared to their laboratory synthesized counterparts through the quantification of structural features such as porosity and surface area per unit volume, which in tum are used to inform the foam's fluid transport propertiesThe spherical template particle packing algorithm developed here is adopted from Powell's work [1], which also includes approaches to obtain percolation and density in random packings [2]. Gervois gives a mathematical development for the stereological sectioning of packed hard spheres [3]. Stereological sectioning facilitates determination of relevant three dimensional morphological properties from two-dimensional data [4]. Studies on the sphere distribution size and the related particle packing density and coordination number results are studied in [5, 6]. Lastly, Kato describes a sintered neck structure, which is used with these packings [7]. This neck structure, as a model of the particle shape following heat treatment, is implemented here in a similar manner. A strong difference between the available literature and the methodology here is that spheres are packed to ultimately represent porous space, not rigid solid space."

Jan 1, 2011

By S. R. Reddy

Thennodynamic properties of several quaternary systems are calculated using our recently modified Margules equations. The modified Margules equations are expressed up to infinite order in the vicinity of solvent. Quaternary system of one solvent and three,solute partials are derived. First order interaction coefficients of binary, ternary and cross -interaction parameters of quaternary system are used to&apos;evaluate the partial functions. In the original fonn of Margules equations,derived partial functions are convergent and same &apos;as Unified ,Interaction Parameter Fonnalism. But considering up to infinite order of the Margules coefficients, the functions are divergent, in order to overcome this restriction, Margules equations are modified to get consistent equations. Derived partial functions are thennodynamica Hy consistent with Maxwell and Gibbs Duhem relations. The derived logarithmic activity coefficient of the solvent and solutes are consistent with the ternary systems. The calculated data, ie., activity coefficient values of nitrogen and interaction coefficients are in good agreement with the data of Fe-Cr-V -N. Fe-Ni-V -N, Fe-Cr-Ta-N and Fe-Ni-Ta-N systems.

Jan 1, 1999

By Tao Zeng, Jianchao Li, Chang Jie, Jieyu Zhang, Jifang Xu, Kuochih Chou

"The densities of the selected quaternary Ca0-5%Mg0-Alz03-Si02 slag with low silica were measured by the Archimedean method in a wide temperature range from l 723K to 1823K. Slag compositions were chosen based on five different levels of Si02 content between 0.00 pct and 11.40 pct. The MgO content was equaled to 5.00 pct. The mass ratio of CaO/Alz03 was varied from 0.67 to 2.14. The effects of temperature, Ca0/Alz03 ratio and optical basicity were studied. It is shown that density decrease approximately linearly with an increase in temperature. With the same Si02 content, the density decreases with increasing of CaO/Alz03 ratio and optical basicity. Based on the experimental data as the boundary of the homogenous phase region predicated by F ACTSAGE software, the mass triangle model is used to calculate the density of selected limited homogenous phase region. The results showed that the mass triangle model is working well.IntroductionIt is of great importance to measure density of slag melt not only to the theory research for melt, which that is directly amenable to the structure correlations of molten slags, but also to the industrial application. Many metallurgy phenomena such as inclusion formation in molten melt and its removing, slag foaming, slag-metal reaction are closely related to the density of slag. Density is also required to estimate other fundamental properties, like surface tension, viscosity, and thermal conductivity from thermal diffusivity so that a relatively complete picture in regard to the behavior of high-temperature molten oxides could be made."

Jan 1, 2013