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By Lan Li, Izaak Williamson

"The efficient separation and storage of CO2 from power plant flue gases can reduce the amount of CO2 released into the atmosphere and mitigate global warming. Potential candidates for industrial applications are solid sorbent materials. Crucial factors to control the efficiency of porous sorbent materials include the framework and pore structure, and the chemical and physical reactivity of CO2 within the pores. Computational modeling approaches, based on density functional theory (DFT) and van der Waals-DFT, have been applied to nanoporous solid – manganese dioxide a-MnO2. We found that the types and charges of cations as dopants in the a-MnO2 and the concentration of CO2 influence the structural features of a-MnO2, which control its CO2 selectivity performance within the flue gases.IntroductionCarbon capture and storage is a technique to separate large quantities of CO2 from power plant flue gases before being released into the atmosphere. Porous solids are a potential candidate as sorbents to “trap” CO2 through chemical or physical adsorption on their porous surfaces[1]. Such separation efficiency is determined by the size and shape of its pores and by the interaction between the porous surface and the gas adsorbates. The incorporation of cations into the pore can act as a means of structural support and alter the pore diameter to be comparable to the kinetic diameter of the gas adsorbate, such as CO2.A porous solid of particular interest for CCS is manganese dioxide a-MnO2, an octahedral molecular sieve (OMS) composed of edge-sharing MnO6 octahedra that are linked into a nanoporous framework[2]. The framework consists of (1×1) and (2×2) tunnels, referred to as OMS-2. Due to the larger tunnel size, cations and gas adsorbates prefer to reside along the (2×2) tunnel axis of the OMS-2. As seen in Figure 1, a potassium cation K+ is located in the (2×2) tunnel, known as cryptomelane-type MnO2. Its pore diameter of ~ 4.6 Å gives it a good CO2 selectivity performance, because the diameter is comparable to the kinetic diameter of 3.3 Å for CO2[3]. Alternatively, replacing potassium K+ with other cations, e.g. barium Ba2+, sodium Na+ or lithium Li+, in the OMS-2 tunnel is of great research interest, due to the effects of their concentrations, types and charges on the CO2 selectivity efficiency and sorption hysteresis phenomenon[2,4]."

Jan 1, 2014

By B. L. Chulu

In the carbothermic reduction of lead sulfate to produce lead, the inclusion of soda ash (Na,CO,) in the charge provides for the control of sulfur dioxide in the effluent gas. An important mechanism in the process appears to be the carbothermic reduction of the sodium carbonate whereby sodium gas and carbon monoxide are produced. These intermediates then participate in the reduction of the lead sulfate to produce lead metal and stable sulfur species in the molten slag phase. In addition, there is some evidence that the presence of lead metal in the charge may also serve to increase the lead recovery in the process. These aspects were investigated by conducting laboratory-scale smelting tests with small charges (;3g), at 1173°K(9000C). Recovery did not exceed 74w% and the role of incipient lead metal in the charge could not be clearly assessed.

Jan 1, 1993

By D. G. Mason

During the design of copper refinery tankhouses, there is a need to develop mass balance calculations for many process components, so that optimum physical plant configuration is achieved. Each mass balance is complex, possibly with over 120 interactive variables as basic input data. Recent developments in tankhouse design (e.g. permanent cathodes) have greatly increased the design options available for any project, multiplying even further the requirement for calculations. In the past these calculations were tedious and susceptible to human error. A comprehensive computer program can now simplify the task of the process metallurgist, enabling more sophisticated and sensitive plant designs to be produced. The paper describes the successful development of a flexible mass balance program that originallly was used in a feasibility study which had to be completed within a short time schedule. The program has been further developed and used for design and energy calculations; it can be usefully applied to existing plants to assess the impact of variations in operating parameters. The software takes account of staged liberation, electrolyte purification bleed and generates a reliable process inventory listing: it can also cope with stripper starting sheet options and disparate commercial circuits.

Jan 1, 1987

By Huyang Xie, Rishi Raj, Vera A. Versteeg

"A new method for MOCVD has been developed in which a precursor solution is directly injected into a reaction chamber. The vaporization of short pulses of liquid is facilitated by atomization with a piezoelectrically-operated nozzle. The system has been used successfully to grow oriented, thin Ti02 (rutile) films on sapphire substrates with the crystalline relationship (101)[010]R I (1120)[0001]s. A growth rate of approximately 2 monolayers per pulse was achieved at 650°C for a reactant impingement rate of about 800 monolayers per pulse. Also, epitaxial LiTaO3 thin films were grown on (0001) sapphire from a single source, bimetallic precursor, lithium tantalum hexa-t-butoxide as the precursor. X-ray diffraction shows that the LiTaOa c-axis is normal to the sapphire surface. The x-ray pole figure and crosssection TEM diffraction show that the films were also in-plane oriented, with sapphire [1010] parallel to lithium tantalate [1010]. These films are shown to have extremely low optical attenuation, and refractive index that compares well with bulk values.IntroductionMetalorganic chemical vapor deposition (MOCVD) techniques have come into increasing use in recent years, due to the growing versatility and availability of precursors and improved environmental advantages over the halogenated compounds used for conventional CVD. Most commonly, the films are deposited by dissolving the metalorganic reactant (typically a metal alkoxide) in a carrier gas, which is carried through heated lines to a heated substratel . The metal alkoxides decompose by pyrolysis, leaving the films on substrates. While this method has been used to produce excellent epitaxial and heterepitaxial films, it has the disadvantages of complexity: the precursor must be heated to fix its vapor pressure, the gas flow rate carefully controlled, and the carrier lines heated to prevent condensation before reaching the reactor. Additionally, this conventional method cannot be used with certain low-volatility precursors that decompose upon heating."

Jan 1, 1994

By Z. Zhang, Zongshu Zou, Nan Wang

"Thermodynamic calculation is applied to make an investigation on the equilibrium phase relations and liquids of CaO-SiO2-Al2O3-FeOx system for different temperatures. The calculated results with FactSage6.1 show that the effect of temperature on the the equilibrium phase relations and liquidus of CaO-SiO2-Al2O3-FeOx system and its sub-systems is appreciable. The liquid phase regions enlarge with increasing temperature from 1573K to 1873K, while the primary phase fields reduce distinctly.IntroductionThe main oxide components of vitrified bottom ash slag are CaO, Al2O3, SiO2, Fe2O3, MgO, and Na2O, accounting for more than 90% of the bottom ash by weight[1]. During slag processing, the knowledge of thermodynamic properties and liquidus temperature in the related slag systems is highly required [2, 3], which is not yet available. Through literature survey [4-6], it is clear that the systematic information on the concerned complex slag system is scarce. So far the engineers in the field have to make assumptions of the thermodynamic properties of the simplified oxide system, without taking into consideration the interactions of the different oxide components, which hinders the development of the slag valorization and utilization. In order to provide thermodynamic properties for the application of the vitrified bottom ash, the six-component oxide system (CaO-MgO-Al2O3-SiO2-FeOx-Na2O) is highly required. A preliminary phase diagram of the CaO-MgO-Al2O3-SiO2-FeOx-Na2O system can be obtained from extrapolation of the thermodynamic functions of constituent subsystems such as CaO-SiO2-FeOx-MgO, CaO-SiO2-FeOx-Al2O3, CaO-SiO2-Na2O-MgO and CaO-SiO2-Na2O-Al2O3. In this work, the equilibrium phase relation and liquidus of CaO-SiO2-FeOx-Al2O3 system, one subsystem of the concerned complex slag system, are calculated and the effect of temperature is also discussed."

Jan 1, 2012

By Edita Vircikova

The best demonstrated available technology (BOAT) for the removal of dissolved arsenic and some heavy metals as reported by USEPA (Contaminants and Remedial Options at Metal Sites, Draft Report, August 1993) (1) is still the chemical precipitation. Coprecipitation with the excess of iron is usually practised because of the availability of iron at low/no cost and also in order to meet the stringent regulatory discharge limits. The arsenic is usually removed with iron because of its common occurence in the mined orebodies and the excellent adsorptive property of the precipitated hydrous ferric oxide compounds. There has been controversy, however, over the long-term stability of the arsenic-bearing ferrihydrite which is produced.

Jan 1, 1995

By Toshihiro Kuzuya

A hydro metallurgical process has been developed for the recovery of metal values such as Co, Ni and rare earths from the electrode materials of spent nickel metal-hydride(Ni-MH) secondary battery. MmNis_xCo. (Mm : Misch metal) intermetallic compound could be separated from the electrode materials mixture by sedimentation. A typical chemical composition of MmN5-xCox was approximately, in mass%, 56.0%Ni, 13.4%Ce, 10.6%La and 7.9%Co. The time dependency of leaching intermetallic compound with sulfuric acid solution was examined with processing factors such as sulfuric acid concentration, temperature and agitation intensity, The leaching of rare earth metals proceeded very rapidly, reaching completion in less than 1.8ks. On the other hand, the slow leaching of nickel was observed. The percent of nickel leached at 328K could only reach about 70%.

Jan 1, 2003

By V. Vergara

Four copper composites were obtained by mechanical alloying, using as dispersed phases of four carbide powders; they were: boron carbide, chromium carbide, silicon carbide and zirconium carbide. The purpose of this work was to study some characteristics of these compounds and their feasibility for use as materials for electrical equipment. Raw materials used were copper powder finer than 150 mesh, and 2-4 vol % of powder carbides finer than 325 mesh. The alloying process was carried out using both a Spex 800-D mill with tungsten jars and balls and a hardened stainless steel jar and balls, the purpose of which was to measure the degree of contamination induced by the milling media. The changes in particle size, morphology and microstructure of copper alloys were studied with SEM and TEM for each alloyed powder. The degree of saturation of copper by the carbides was measured by X-ray diffraction. Sound samples were obtained by hot isostatic pressing at 1073°K. The best characteristics were obtained for the compound copper-chromium carbide, based on their hardness, tensile strength and electrical conductivity values. The other alloys failed due to their excessive brittleness after hot pressing.

Jan 1, 1999

By Marco Olper

The CX-EW technology, developed by B.U.S Engitec, is improved introducing besides the battery paste electrowinning, the direct electrorefining of metallic lead (grids and poles) obtained from CX breakers. This new concept of electrorefming the antimonial lead scrap is aimed to the production of 99.99 lead and of slimes with high antimony content, avoiding gaseous emissions in melting lead scrap, and expensive and pollutant thermic refining operations. In this way, practically all lead content in the battery is available as 99.99 lead, hence with a wider market for the lead recyclers. This paper will describe the tests performed on a pilot plant scale with special reference to the relatively low energy consumption of the process.

Jan 1, 1993

By Raymond F. Dalton

Despite the ready availability of numerous zinc sources, the process of solvent extraction- electrowinning (SX-EW) has as yet found little favour in the zinc industry. It is suggested that this is largely due to the previous lack of availability of suitable selective reagents having the particular features required to enable them to fit in to a solvent extraction-electrowinning based process for zinc, particularly with regard to strength and selectivity for zinc over iron. This paper describes work on the development of new selective extractants for the recovery of zinc from both sulfate and chloride aqueous solutions and suggests how they might be integrated into new zinc processes.

Jan 1, 1994

By Toshiyuki Nohira, Eiichi Takeuchi, Tetsuo Oishi, Hideki Ono, Hirokazu Konishi

The Dy-Nd-Pr-Ni alloy sample was prepared by cathodic potentiostatic electrolysis at 0.65 V (vs. Li+/Li) for 1 h using a Ni plate in a molten LiCl-KCl-DyCl3-NdCl3-PrCl3 system at 723 K. The highest mass ratio (Dy/Nd+Pr) in the alloy sample was observed to be 50 at 0.65 V. Anodic potentiostatic electrolysis at 2.20 V for 12 h was conducted using the Nd-Fe-B magnet electrode in a molten LiCl-KCl system. All elements were almost dissolved from the magnet, and the original form of the magnet disintegrated. After anodic potentiostatic electrolysis at 2.20 V, cathodic potentiostatic electrolysis was conducted at 1.00 V for 5 h using a Mo plate in order to remove the dissolved Fe from the bath. Finally, cathodic potentiostatic electrolysis was conducted at 0.65 V for 12 h using a Ni plate. The mass ratio of Dy/Nd in the alloy sample was determined to be about 18.

Jan 1, 2015

By Aiyuan Ma, Kun Yang, Weiheng Chen, Jinhui Peng, Shiwei Li, Feng Xie, Libo Zhang

In this thesis, a new process of recovering zinc sulfide ores was developed. The novel synthetic coordination leaching process mainly included two steps: microwave assisted phase reconstruction and compound coordination leaching. By applying various techniques, such as chemical composition analysis, X-ray diffractometry (XRD) and Raman spectroscopy, it could be concluded that sulfide phases would directly oxidized to zinc oxides under the 500 ºC microwave roasting and adding 30% Na2O2. What’s more, zinc leaching rate reached to 61.16% within 2 hours. Compared to the current technologies, this procedure had the advantage of avoiding SO2 emission, high leaching efficiency, simple process, manipulate easily, and low cost, which could be expected tremendous application potentials.

Jan 1, 2016

By Motoyasu Sato

Highly pure pig irons were produced in a multimode microwave reactor from powdered iron ores with carbon as a reducing agent in the nitrogen atmosphere. The grains in compacted powder absorb microwave energy selectively. Microwave-matter interaction creates thermal non-equilibrium state microscopically and enhances chemical reactions and the phase mixing at the grain boundaries very rapidly. The visible light spectroscopic techniques was used to monitor the progress of the reactions. Up to 650°C, the heated powders radiate the continuous spectrum of blackbody emission. The small non-equilibrium hot spots rise, move and finally burst in to brighter light emitting from all over the surface at 650°C. CN molecules and Fe (I) atoms were identified in the recorded spectrum. These bursts are similar to the ?ignition propagation? normally observed in chemical reactions. The line spectra originated from CO molecules have not been detected yet. The solid-solid reaction could be expected between the iron oxides and carbon to produce CO2 directly. A loss in the sample weight was accelerated during the excess-emission. These are the clear evidence that microwaves cause thermally non-equilibrium state and accelerate reduction process. The reduction of iron ore is completed at 1380°C and relatively very pure pig iron was produced. It should be noted that the impurity level of Mg, S, Si, P and Ti is only 5-10% of what is found in the pig irons produced by modern conventional blast furnaces in the steel industries. The necessary amount of carbon needed was 1/2 compared to conventional blast furnace to produce the unit weight of steel, if we applied renewable energy or nuclear power for the microwave excitations.

Jan 1, 2006

By Wiraseranee. Chompunoot, Kazuki Morita, Toru H. Okabe

"Aiming at the development of more effective recycling processes, dissolution behavior of rhodium into molten slag was investigated. Using a pure rhodium crucible and Na2O-SiO2 slag system, equilibration experiments were carried out for 18 h at 1423-1623 K under various oxygen partial pressures of 0.005-1 atm with varied slag basicity. Rhodium solubility increased with increasing oxygen potential, slag basicity, and temperature. Rhodium dissolved into slag as rhodate ion ([RhO2]-) by the endothermic reaction: Rh(s) + 3/4O2(g) + 1/2O2-(in slag) = [RhO2]-(in slag). In the dissolution reaction, the “rhodate capacity” of slag is newly-defined. The correlation between rhodate capacity and optical basicity is reported.IntroductionDue to its high chemical resistance and outstanding catalytic properties, rhodium (Rh), one of the platinum group metals (PGMs), is utilized in various applications such as catalysts, molten glass vessels and containers, and electronic devices. Owing to the rarity of Rh resources in nature, recycled Rh from scraps such as spent automobile catalytic converters is currently considered as an important source of Rh supply [1]. According to the recycling practices, Rh is currently mainly recovered from scraps along with other PGMs such as platinum (Pt) and palladium (Pd) by a dry process (e.g., smelting), a wet process (e.g., leaching and subsequent separation of PGMs from aqueous solution), or a combination of both processes [2]-[4]. Among these processes, smelting is commonly applied because PGMs can be effectively separated from a relatively large amount of various impurities coexisting in scraps. In the smelting process, Rh and other PGMs are collected in the collector metal (e.g., iron and copper), and impurities in scraps are removed into slag [4]-[6]. The process may be carried out at a temperature range of 1573-1973 K, in either an oxidizing or reducing atmosphere. Due to the high oxidation resistance at high temperatures, Rh is expected to be collected efficiently in the metal collector rather than being oxidized and forming RhOx in a molten slag. However, Rh loss into slag does occur in this process [7]."

Jan 1, 2011

By Dianyuan Dang, Guihong Han, Wenjuan Wang, Tao Jiang, Yanfang Huang

In this study reduction kinetics and swelling behaviors in "two-step process” were investigated by weight-loss technique and visualizing physical changes of pellet. Results showed that reduction degree (r) increased with increasing temperature and time. According to the dynamic calculation, when reduction temperature was lower than 1000°C the reduction process was controlled by chemical reaction with apparent activation energy of 72.27 kJ/mol. When reduction temperature was higher than 1000 , the equation of t/[1-(1-r)1/3] against [1+2(1-r)-3(1-r)2/3]/[1-(1-r)1/3] followed straight lines, demonstrating that reduction was mixed-controlled. Swelling experiments indicated that the maximum swelling index increased with the increase of reduction temperature and CO content.

Jan 1, 2016

By J. D. McCain

Magma's San Manuel smelter has adopted new operating techniques resulting in 21% increased productivity and 87% reduction in lost time accidents. Reverberatory furnaces were converted to coal firing from expensive natural gas and fuel oil. Slag and matte flow problems and safety were improved by implementing hydraulic slag stopping and matte tapping machines. Coordination of furnaces, converters and acid plant was improved by using a computer-aided converter controller/scheduler function. Manual mudding of converter lips after each collar pull was replaced with a gunning system for coating the mouth castings. One converter punch car was automated using robotic technology. An automatic anode take-off was installed with fewer moving parts and a mechanism for ear twisting one cell contact. Anode copper refining was improved by replacing propane/hydrogen mixtures with high pressure/velocity natural gas tuyeres. Improved converter scheduling increased acid plant production 43% with more autothermal operation time. Six dedicated computers/microprocessors are utilized for automation, data acquisition, process monitoring and on-line air quality information for the Supplementary Control System.

Jan 1, 1983

By Jin Yu, Fang-Qiu Zu, Yun Xi, Li-Na Mao

"According to the behaviors of resistivity-temperature of Cu-Sb70 melt, which suggests a partly reversible temperature-induced liquid structure transitions (LST) could occur in this alloy, in this paper, we investigated the dependence of solidification on the liquid state. Both resistivity and temperature were measured to track solidification process. The results show that the nucleating undercooling of the melt which experienced the LST increased and the solidified time decreased. Meanwhile, the solidified microstructures refined evidently, with the microscopic pattern of primary phase changes from disordered pillarlike dendrites into homotaxic ones. Moreover, it is verified that the microstructures would be different if the reversible part of the LST was restrained. The new phenomena and results reflected in this paper suggest that grasping the rules of melt structure change with temperature before material processing will give help for controlling the solidification more effectively and finally resulting in more ideal microstructures.IntroductionThe structure and quality of liquid alloys have a direct and important influence on the structure, performance and quality of the solidified ones. In recent years with in-depth study of liquid structure, researchers have found that some liquid structure transitions (LST) could occur on dependence of the temperature or pressure [1-5]. And the article [6] reported that a pressure-induced reversible LST was found in liquid triphenyl phosphite, which further confirmed the authenticity of the existence of the LST. Furthermore, in our earlier studies of Sn-based melts using resistivity method, some abnormal structure changes induced by temperature have been found at hundreds of degrees above liqiudus, and these LSTs are partly reversible[7]. This phenomenon has been discussed and it is suggested that the reversible LST in Sn-based melts are related to the short-range ordering (SRO) structures of Sn, which are tetrahedron structure with covalent bonding. However, does this reversible LST exist in other melts too?"

Jan 1, 2012

Thallium is a very minor element found in lead ores. It's behaviour during lead smelting has recently become of much greater interest due to the effects it had on the health of waste heat boiler maintenance contractors at a Canadian smelter. In this paper the behaviour of thallium in both traditional and direct lead smelting processes will be examined using computational thermodynamics techniques. Yazawa and his coworkers have made extensive use of computational thermodynamics to examine and illustrate pyrometallurgical processes. It has been shown that thallium behaviour during smelting is strongly influenced by the extent of oxidation of the lead concentrate and by the presence or absence of chlorine in the charge. The condensation behaviour of thallium species in the waste gas handling system was also modelled and it has been confirmed thallium-rich deposits can form at the high temperatures prevailing in waste heat boilers.

Jan 1, 2003

By J. R. Parga

A shortage of landfill space and growing environmental concerns in Mexico are renewing interest in the recyclability of scrap from automobiles. This work describes a pyroumetallurgical process for the recovery of metallic lead from waste lead paste. Argentopyrite concentrate is commingled with lead paste residue and smelted in a fuming process thereby transferring the precious metals into lead bullion. The process consists of smelting lead paste and argentopyrite, sodium carbonate, and metallic iron at smelting temperatures of about 1100 T. The reaction products are slag and molten lead bullion enriched with precious metals. A major feature of this process is the removal of precious metals from the bullion by means of zinc, whereby a silver-zinc intermetallic compound is formed and floats out of the lead. The recoveries of precious metals are about 98%.

Jan 1, 1996

By Shunsuke Yagi

A surface alloying technique was investigated using alternating pulsed electrolysis in an aqueous solution containing a single metal component for the formation of an Fe-Cr layer on an iron substrate. In the process, the iron substrate was dissolved during each anodic polarization of the pulsed electrolysis, providing iron ions in the vicinity of the substrate, while the Fe-Cr alloy was electrodeposited during subsequent cathodic polarizations. A bright, flat, and crack-free Fe-Cr layer with a composition gradient was obtained using a solution containing a trivalent chromium component and a complex forming agent together with some supporting or buffering salts.

Jan 1, 2006