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By K. M. Parida

The kinetics of dissolution of manganese dioxide in dilute sulphuric acid solution have been investigated using iron pyrites as a reductant. The dissolution rate of manganese is independent of the speed stirring but depends upon temperature, particle size, specific surface area of manganese ore, acid concentration, Fe(II) concentration and amount of pyrite. The activation energy is 43.6 KJ/mol and the linear relationship between the rate of dissolution and lido indicates that the reaction is chemically-controlled. The redox reactions of MnO2 with iron pyrites and Fe(II) are the rate-controlling reactions.

Jan 1, 1990

By K. B. McTaggart, G. Owusu, P. J. Merrin

"This study was conducted at Hudson Bay Mining and Smelting's zinc electrowinning tankhouse to determine the effects of varying levels of antimony and continuous gelatin addition on current efficiency. The levels of antimony and gelatin were varied from 0.012 to 0.030 mg/l and 0 to 10 mg/ll2 • 31 respectively, based on neutral ZnS04 electrolyte. A non-linear mathematical model relating current efficiency with antimony and gelatin was produced. The optimum operating point for gelatin was 6.5 mg/l. On the other hand the current efficiency increased with decreasing antimony levels. An interaction term between gelatin and antimony is present but is not significant enough to improve the ability of the tankhouse to handle purification upsets in antimony. Individually, the current efficiency was linear (decreasing) with antimony, and parabolic with gelatin concentration. However, at low antimony concentrations stripping of the cathode sheet was difficult. IntroductionThe zinc electrowinning tankhouse at Hudson Bay Mining and Smelting was designed in the 1930's and consists of 120 rows with each row containing ten cells. This system cascades acid from cell to cell In a row, with neutral zinc sulphate solution added to each cell through manually controlled spigots. Animal glue additions are made manually three times per day by operations personnel. The problem with this type of cell design and operation is that feed solution flows and composition can vary from cell to cell and from row to row due to the large number of manual control points. A new system which reduces the number of manual control points was designed and tested to determine if improvement in control of cell conditions would affect current efficiency. This system mixes spent acid, neutral ZnS04 electrolyte and reagents (gelatin, antimony and strontium carbonate) in a separate mix tank, ensuring that all cells receive a uniform feed solution. Gelatin was used in the test system instead of animal glue (which is presently used) because of the poor solubility and supply of industrial animal glue. The study reported here is the first in a series of experiments designed to justify the need to modify the present cascading cell feed system (Figure 1) to the proposed feed system (figure 2)."

Jan 1, 1997

By Xiao-hui Fan, Xu-ling Chen, Zhi-yuan Yu1, Guanghui Li, Min Gan, Yun-song Huang, Tao Jiang

Compared with the traditional de-NOx processes by cleaning the waste gas, a new approach for reducing the formation of NOx during sintering process is proposed. Since more than 90vol% of NOx comes from the fuel combustion, the influence of sintering coke breeze pretreated by CO(NH2)2 additive on the NOx emission is researched. As adding CO(NH2)2, the reduction agents (NHi) are generated during the pyrolysis of CO(NH2)2, which reinforce the NOx reduction, And the appropriate content of CO(NH2)2 is 1.0 mass% of coke breeze.

Jan 1, 2015

By Guanyong Shi, Zhihe Dou, Cong Wang, Ting'an Zhang, Hongyan Zhang

We prepared the CuCr alloy by thermit reduction-electromagnetic casting. But there are the defects such as stomata and oxide inclusions in CuCr alloy. In this paper, the existing state and distribution of inclusions and stomata in CuCr alloy are systematically analyzed. The alloy was characterized via SEM, EDS and metallographic microscope, in which the existing state and micro-structural defects of inclusions are analyzed. The results show that: there are three distinct areas: copper-rich areas, chromium-rich areas and the inclusion areas. Inclusions are mainly in the form of stomata and Al2O3 phase, mainly locating in the copper-rich phase and the interface area of chromium-rich phase and the copper-rich phase. Then, the composition of phases of the smelting slags and alloy were characterized via XRD. The results show that: the slag consists of Al2O3 and a little of Cr, the alloy consists of Cr, Cu and a little of Al2O3.

Jan 1, 2015

By Kenneth C. Mills

Interfacial phenomena can have a dramatic effect on the separation of phases. Furthermore, since they involve surface-active materials, concentrations at ppm levels are enough to cause dramatic effects on separation processes. The effects of (i) emulsification, (ii) contact angle and wettability and (iii) Marangoni flows on phase separation are reviewed.

Jan 1, 1999

By Chuanfu Zhang, Liwei Liang, Yanxin Wu, Jinliang Wang

"According to the reaction shaft operation characteristics during the flash smelting process, 15 groups of slag samples containing high Fe3O4 were prepared by some chemical reagents, and then the slag viscosities were measured using a RTW-10 type synthetic test instrument for melt physical property by the rotating cylinder method. The effects of Fe/SiO2 ratio (mFe/mSiO2), Fe3O4 content (wFe3O4), Cu2o), MgO content (WMgO) and Cao content (wCaO) on the slag viscosity were also studied. Results show that slag viscosity is decreased with the increase of temperature, mFe/mSiO2, wCu2o, wMgO and wCao, and with the decrease of wFe3O4, under the range of slag contents: mFe/mSiO2 1.36~1.78, wFe3O4 17.83%~21.18%, wCu2o 3.51%~8.34%m wNgI 2.21%~6.57%m w/caI 6.22%~9.387% and temperature range if 1250 o/c~1450 oC. Only wFe3O4m and w/caO have great influence on the slag viscosity when temperatures as high as 1400 oC. Only wFe3O4 and wCaO have great influence on the slag viscosity when temperatures as high as 1400 oC or so. To form a freeze slag with higher viscosity inside the reaction shaft, wFe3O4 should be more than 20% and wCaO should be less then 6%.IntroductionSince its appearance in 1949, Outokumpu flash smelting technology has making continuous innovation and has become the most competitive intensified smelting technology [1], widely considered to be the standard clean smelting process [2]. At present, flash smelting technology is adopted to newly build or reconstruct most of the world's copper or nickel smelting enterprise [3]. Reaction shaft is the most important part of the flash smelting furnace. During the flash smelting process, reaction shaft must be able to withstand the following harsh conditions at the same time: 1) high temperature varying from 1400 °C to 1500 °C. 2) strong oxidative atmosphere containing 50% - 80% oxygen. 3) solid particles and melt with speed up to l00 m/s. 4) high acidic or basic slag with strong chemical corrosiveness. 5) smelting gas containing 50% - 80% SO2. 6) matte with strong dissolution."

Jan 1, 2012

By Antoine Allanore, Luis A. Ortiz, Donald R. Sadoway

"The steelmaking industry has drastically reduced its energy consumption in the last fifty years, and today’s technologies are considered to operate at their optimal efficiency with respect to energy needs. To cope with new constraints related to greenhouse gas (GHG) emissions, a change of paradigm is necessary. One of the promising technologies that could be deployed to help reach CO2 mitigation targets relies on the intensive use of electricity: molten oxide electrolysis (MOE). This paper presents the key process parameters that need to be tuned to address the practical needs for both high productivity in a steelmaking reactor and for an energy efficient process. Herein we show that contrary to common perception, the electrolysis process for ironmaking requires less energy than today’s chemical reduction route. Furthermore, we prove that most of the energy that must be provided to operate the electrolytic iron production cell is thermal energy which is readily generated by joule heating during electrolysis due to large currents being passed through the electrolyte. The energy consumption of the electrolysis cell is therefore shown to be highly dependent on the cell configuration and the chemistry of the electrolyte. As a consequence, the CO2-impact of the technology strongly depends on both the power production mode and the technological choices for design of the process, including cell configuration. Surprisingly enough, even when the electricity generation is not carbon-free, MOE still appears to be viable from the perspective of reducing GHG emissions providing sound reactor design considerations are made.IntroductionIn the context of greenhouse gas (GHG) emissions mitigation, the steelmaking industry is considering several techniques that could sustain the efforts and progress achieved by this sector in the last decades [1]. A recent report [2] on potential routes for low-CO2 steelmaking highlighted for all techniques both the strong dependency of CO2 emissions on electric power production mode and the need for a decrease in energy consumption per tonne of steel. Incited to innovate with respect to this last criterion, the steel industry considers electrolysis to be a promising technological solution, and in particular the molten oxide electrolysis (MOE) process. This process conducts electrolysis in a mixture of oxides that dissolve the iron oxide feed, which by the action of electric current is decomposed into liquid iron and oxygen gas. The opportunity for reduction in energy consumption during steelmaking by MOE is commonly attributed to the “direct” pathway from iron oxide to liquid metal offered by the use of a molten oxide melt and operation at a temperature above the melting point of iron, ideally 1600°C, to provide enough superheat for tapping the molten iron product:"

Jan 1, 2011

By Rudolf Keller

In the electrolysis of neodymium oxide from a molten fluoride electrolyte, anode effects may occur at the carbon anodes, interfering with smooth cell operation. In laboratory experiments, we attempted to circumvent this problem by selecting electrolytes with a high oxide concentration, possibly at relatively low rare earth content, but cathodic deposition was not satisfactory. A regime at higher cell voltage was discovered to yield good cell performance, but evolution of considerable amounts of fluorocarbon compounds suggested that a reactive treatment of the off-gases would be necessary for environmental acceptability. Subsequent experimentation at low cell voltage revealed conditions for satisfactory operation without occurrence of anode effects and without formation of any CF4 or C2F8.

Jan 1, 1997

By Hans Hein

In its early stage of copper solvent extraction development, SX plants were designed in a series configuration and gradually the copper industry reduced staging and trains for keeping capital investments reasonably low. At a later date of its development, series parallel configuration was applied in some copper SX plants, particularly for increasing copper production at low copper tenor in pregnant leach solution. A gap between series and series parallel configuration had been observed for years. Conventional SX plants in series configuration frequently do not have the flexibility for maintaining designed or expected production level, whenever copper concentrations in pregnant leach solutions are getting low, whereas series parallel flow schemes almost require to double SX feed flows for achieving optimum results. A combined SX configuration breaks the gap and its application potentials are explained.

Jan 1, 2003

By Yuan Zeping

The distributions of impurities in the copper melt, the slag and the gas phase in copper flash smelting process were under study in the Guixi smelter, particularly during operating conditions of high oxygen enrichment with production of high grade matte. Several methods for the removal of impurities such as As, Sb and Bi in the copper smelting process were developed and implemented at the Guixi smelter. This paper described the effects of high oxygen enrichment, elevated matte grade, high temperature and high production rate on the distribution of impurities, methods adopted at the smelter for the removal of impurities, and the associated benefits in the utilization of these removal techniques which include the mathematical model for material blending, high thermal intensity operation at the flash furnace, extended converter blowing, and injection of slag modifiers consisting of Na2CO3 and CaO powder mixture to the converters and anode furnaces.

Jan 1, 1999

By Wenjun Duan, Kun Wang, Qingbo Yu, Qin Qin

"A novel oxygen production technology noted chemical looping air separation (CLAS) was introduced and properties of Cu-based oxygen carriers used were investigated. The oxygen carriers were prepared by mechanical mixing. Al2O3, Fe2O3, ZrO2, TiO2 and SiO2 were used as binders during the preparation. XRD patterns show that spine! oxides are formed using Al2O3 and Fe2O3 as binders. Phases of CuO and binders keep stable using ZrO2, TiO2 and SiO2 as binders. BET values of oxygen carriers increase in the order of ZrO2>TiO2>SiO2>Fe2O3>Al2O3. The effects of temperatures, binders, particle sizes and flow rates on reduction/oxidation reaction rates were studied in TG experiments. The reduction reaction rate increases in the order of ZrO2>TiO2>SiO2. The effect of binders on the reactivity of oxidation is not obvious. The reduction and oxidation reaction rates both have the tendencies of increasing with the temperature increasing and with gas flow decreasing. However, the effects of gas flow and particle size are little.IntroductionChemical looping air separation (CLAS) is a novel oxygen production technology. The oxygen carriers used in CLAS release oxygen in reduction reactor and regenerate in the oxidation reactor. Selecting suitable oxygen carriers is the key for CLAS. Oxides of CuO, Mn2O3, Co3O4, Pb3O4, CrO2, SrO2, PdO2 and CeO2 have the property of releasing oxygen at suitable temperature and oxygen partial pressure [1]. Among these oxides, CuO, Mn2O3, Co3O4 are the most common compositions used to prepared oxygen carriers for chemical looping combustion (CLC) or chemical looping with oxygen uncoupling (CLOU) [2-5]. Moreover, thermodynamic calculations and preliminary experiments were carried out on oxides of Cu (CuO/Cu2O), Mn (Mn2O3/Mn3O4) and Co (Co3OJCoO) by Moghtaderi to ascertain their feasibility for CLAS process [6]. CuO has the highest oxygen transport capacity (0.1 g 02/g CuO compared to 0.03 g 02/g Mn2O3 and 0.06 g 02/g Co3O4). However, agglomeration is the biggest issue for copper oxides used at high temperature because of its low melting point (l 450°C for CuO, 1235°C for Cu2O and 1075°C for the mixture of CuO and Cu2O) [7]. In order to improve the capability of anti-sintering and stability ofCuO, binders (ZrO2, MgAl2O4, TiO2, SiO2, Fe2O3, Al2O3, cement) are added during the preparation of Cu-based oxygen carriers [8]. In this paper, the Cu-based oxygen carriers were prepared by mechanical mixing method. TiO2, Al2O3, Fe2O3, ZrO2 and SiO2 were selected as binder. XRD, BET and SEM were used to analyze the phase, surface area and surface morphology of oxygen carrier prepared. The reactivity of oxygen reduction and oxidation of oxygen carriers prepared were investigated in STA409PC thermal analyzer."

Jan 1, 2014

By Kazuya Koyama

We are studying the hydrometallurgical recycling process of indium from an Indium-Tin-Oxide(ITO) target. For this process, it is necessary to remove Sn(IV) ions from the aqueous hydrochloric acid solutions containing In(III). In this study, the removal of Sn(IV) ions by a potentiostatic electrolysis method was examined. The polarization measurements and potentiostatic electrolyses were carried out under a nitrogen atmosphere. In the Sn(IV) solution, current begins to rise at the cathode potential of -0.26 V vs. SHE, and increases with a reduction in the cathode potential. In the In(III) solution, current begins to rise at a cathode potential of -0.43 V vs. SHE. Metallic tin was electrodeposited without indium electrodeposition at the cathode potentials of -0.30 and -0.40V vs. SHE. More than 98% of the Sn(IV) was removed at the cathode potential of -0.40 V after the electrolysis for 3hrs. Both tin and indium were electrodeposited at the cathode potential of -0.50V vs. SHE.

Jan 1, 2006

By Klaus-Markus Peters, Robert M. Cravens, James G. Hemrick

"Degradation of refractories in molten aluminum applications leads to energy inefficiencies, both in terms of increased energy consumption during use as well as due to frequent and premature production shutdowns. Therefore, the ability to enhance and extend the performance of refractory systems will improve the energy efficiency through out the service life. TCON_ ceramic composite materials are being produced via a collaboration between Fireline TCON, Inc. and Rex Materials Group. These materials were found to be extremely resistant to erosion and corrosion by molten aluminum alloys during an evaluation funded by the U.S. Department of Energy and it was concluded that they positively impact the performance of refractory systems. These findings were subsequently verified by field tests. Data will be presented on how TCON shapes are used to significantly improve the thermal management of molten aluminum contact applications and extend the performance of such refractory systems.IntroductionThe production of molten aluminum creates aggressive environments for processing equipment, thereby requiring refractory materials to contain the aluminum during melting, transfer, treatment, and casting operations. Degradation of these refractories not only causes issues with reduced product quality and production yields, but also increases heat losses as the insulative properties of the refractories are compromised. Furthermore, in addition to disrupting production output, refractory failures lead to further impacts upon energy efficiency as large amounts of energy are lost during the cooling and subsequent reheating of the equipment as the refractory linings are repaired or replaced.The need for improved refractory materials is recognized throughout the industry. A joint U.S. Department of Energy and industrial workshop held in 2000 on applications for advanced ceramics in aluminum production [1] noted that refractory materials used in melt processing equipment have many limitations. The workshop report noted that these issues may be addressed by using advanced ceramics, but new materials must be cost effective when compared to current refractory materials. Also, in 2005 the Canadian aluminum industry produced a technology roadmap [2] having the goal of identifying and bridging gaps between current technological resources in the industry and future requirements. One of the areas identified as being crucial to the future of the industry was the need for improved molten aluminum-resistant materials."

Jan 1, 2009

By Zhang Yongzhu

In hydrometallurgical processes of PGMs separation and refining, differences between 1-PGMs (Ru;Rh;Pd) and h-PGMs(Os;Ir;Pt) in thermodynamics and kinetics have been observed. The successful practice in the separation and refining of PGMs in China, is mainly based on the following two kinetically extraction sequences of: (1) for the extraction of PGMs complexes in different configurations with coordination mechanism (AuCI,) -> (MCl6)2-> (MCl4 )2-> (MCI6) 3- , and the substitution rate for h-PGMs complexes with higher effective nuclear charge Z' is much more slow than that of I-PGMs. and (2) for the extraction of PGMs in different configurations with oxonium (or ion -exchange) mechanism (AuCl4)-> (MCl4)2--> (MCl6)2-> (MCl6)3- and the extraction of h-PGMs complexes with low surface charge density is more fast than that of I-PGMs complexes. In view of atomic structure theory, the similarity of atomic radii and chemical properties and difficult separation of PGMs resulted from the Lanthanide Contruction between 5th period (1-PGMs) and 6th period (h-PGMs). The differences between h-PGMs and 1-PGMs are due to the loss shielding of 4f subshells on 5d electrons for h-PGMs with higher nuclear number, which makes h-PGMs have a higher Z' (effective nuclear charge) and strong attraction for outer space electrons. As a result, h-PGMs metals and complexes are thermodynamically more stable and kinetically more inert than the corresponding 1-PGMs. The differences between h-PGMs and 1 -PGMs in aspects of elements properties, complexes, hydration, substitution and redox reactions , are discussed.

Jan 1, 1993

By Adam Powell, Soobhankar Pati

"Solid Oxide Membrane (SOM) Electrolysis is a new energy-efficient zero-emissions process for producing high-purity magnesium and high-purity oxygen directly from industrial-grade MgO. SOM Recycling combines SOM electrolysis with electrorefining, continuously and efficiently producing high-purity magnesium from low-purity partially oxidized scrap. In both processes, electrolysis and/or electrorefining take place in the crucible, where raw material is continuously fed into the molten salt electrolyte, producing magnesium vapor at the cathode and oxygen at the inert anode inside the SOM. This paper describes a three-dimensional multi-physics finite-element model of ionic current, fluid flow driven by argon bubbling and thermal buoyancy, and heat and mass transport in the crucible. The model predicts the effects of stirring on the anode boundary layer and its time scale of formation, and the effect of natural convection at the outer wall. MOxST has developed this model as a tool for scale-up design of these closely-related processes.IntroductionSolid Oxide Membrane (SOM) Electrolysis is a variation on the Hall-Héroult process for molten salt electrolysis of oxides which promises to solve many of the problems of its predecessors. Magnesium in particular is both soluble in molten salts and highly reactive, such that it migrates to the anode and reacts with the oxygen or C02 anode product, reducing current efficiency to as low as 10-20%. But a zirconia solid electrolyte between the molten salt and anode blocks this reaction, boosting current efficiency to at least 90%. Separating the anode from the molten salt also opens up anode material selection to liquid metals and SOFC cathode materials such as Lai.xSrxMn03 (LSM) and YCr03. And zirconia's selectivity makes the oxygen by-product very pure."

Jan 1, 2012

By Ana Bohé

Nowadays, Gas-solid processes are widely used in the industry. The chloration and carbochlorination of metallic compounds are some of this kind of non catalitic heterogeneous reactions. In particular those related with extractive metallurgy of refractory elements (Zr, Ti, Nb, Ta, RE, etc). The development of materials to be used in reactors at elevated temperatures and with high corrosion performance, enhance the application of this kind of processes. Although they are currently carried out in the production of many comodities, the mechanism of most of them are yet not well understood. The present work is a deep discussion on the most important aspects to take into account for determining the mechanism of gas- solid reaction, and those criteria fulfil in this analysis were applied to chlorination and carbochlorination examples. The microstructural characteristic of solids, the mass and heat transfer phenomenon, the adsorption and desorption of gaseous species on active surface, surface diffusion processes and chemical elementary steps, which are the mainly contributions to the mechanism of these reactions were analysed. Furthermore, the effect of them on the reactivity of solids and the control step of the reactions were determined. The application of catalitic mathematical models to this kind of reaction and the modification for the better interpretation of experimental results is also undertaken. The most appropriate experimental procedures for following these reactions and the microstructural characterization techniques needed to be use in each case, there limits and applicability are also indicated.

Jan 1, 2006

The paper describes the propensity of tin to form intermetallic compounds with microalloying elements such as Nb, Ti and aluminium, which are commonly used as additions to achieve particular combination of strength and toughness. Two series of alloys were prepared by arc melting under an argon atmosphere. Each series was based on Fe, Sn and A1 with either Nb or Ti additions. The microstructures were studied using scanning electron microscopy, transmission electron microscopy, energy dispersive X-ray spectroscopy and microprobe analysis. It was found that the level of Nb addition has an effect on the formation of Sn-rich compounds. For small Nb additions, no Sn containing compounds were found, whereas in higher Nb alloy, a Laves phase (FezNb, hexagonal, a = 0.4830 nm and c = 0.7879 nm) containing about 1 at % Sn was found. A FezNb3 phase (cubic, a = 1.1261 nm) associated with the formation of alumina was also found but did not contain tin. No Sn containing compounds were found with Ti additions. The experimental observations have been compared with thermodynamic calculations performed using MTDATA.

Jan 1, 1999

By Jiao Li, WenhuiMa, KuixianWei, YongnianDai, Cong Zhang

The paper studied the diffusion process of nitrogen and characteristic distribution of iron impurities in the bottom of cast crystalline silicon ingot along the direction of crystal growth. According to the dynamics analysis of the decomposition of Si3N4 coating, the diffusion process of nitrogen into multicrystalline silicon ingot during casting process should be divided into three steps. The diffusion length of nitrogen in multicrystalline silicon ingot is 700 μm. The results of EDS analysis indicate that the distribution characteristic of iron in multicrystalline silicon ingot is concerned with the diffusion process of nitrogen in this length. Based on the above research results, the distribution model of iron in casting multicrystalline silicon ingot was established and verified by the experimental results.

Jan 1, 2015

By Theodore Ineich

The “BIOMOre” project aims to prove the technical feasibility of indirect in situ bioleaching of sulfide minerals contained in a deep underground deposit, by bringing together the disciplines required to make a success. The underground location in Poland was provided by project partner KGHM inside an operating copper mine. Key components of this project were the design and construction of a pilot plant, and its operation in an underground environment. This project also included a ∼250 t (100 m3) fragmented rock reactor hydraulically connected to the pilot plant. The pilot plant consisted of several tanks and pumps, a fluidised bed ferric iron generating bioreactor containing immobilised acidophilic iron oxidation biomass, and all the required instrumentation and utilities. Before the bioleaching phase could start, the rock reactor had to be flushed continuously firstly with water to remove chloride salts that are corrosive and also harmful for the bacteria used in the bioreactor, and secondly, with sulfuric acid solution to react with the carbonates present in the ore matrix. This paper summarizes the design, construction, commissioning, and operation of the pilot plant.

By R. A. Spitz, R. Leiby, M. Bricker

Electrochemistry plays a significant role in minimizing wastes at East Penn's secondary lead smelter. East Penn has been recovering spent battery acid for reuse in new batteries since 1992. East Penn also produces a fertilizer feedstock from sulfur dioxide in the smelter stack gases. The success of these processes is, in large part, due to the installation of electrochemical cells. The cells in the acid recovery plant allow the waste from this process to be concentrated into less that 10% of the original spent acid. The cells in the fertilizer plant treat the solution to remove dissolved metals prior to sale to fertilizer manufacturers.

Jan 1, 2000