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By M. Cassir

"The unique properties of molten carbonates offer a large scope of applications in the field of energy. In effect, these molten salts are in the center of chemical and electrochemical reactions involving carbon and carbonaceous species, carbon dioxide and carbon monoxide, significant for energy generation or even for the production of fuels. Moreover, such media have also an oxidative character; they dissolve molecular oxygen and oxygen reduced species, O 2-, O22- and hypothetically o-, which may have an important role in waste treatments, homogeneous catalysis and synthesis of oxides. In this presentation, an overview will be given on the principal physicochemical properties of molten carbonates, before focusing on their main known application, the molten carbonate fuel cell (MCFC). Progress in other new fuel cells applications will also be analyzed, such as direct carbon fuel cell (DCFC), hybrid carbon fuel cell (HDCFC) and composite high-temperature fuel cells combining the features of MCFC and solid oxide fuel cell (SOFC). Afterwards, membranes for the separation and capture of C02 will be reviewed. Finally, other topics, as the oxidative coupling of methane in molten carbonates, will be briefly mentioned.IntroductionIn the thirty past years, the molten carbonate science and advances have been mainly dedicated to the understanding and optimization of the molten carbonate fuel cell (MCFC), which is still a major issue in the heart of a new vision of energy development. More recently, new topics related to other kinds of fuel cells (DCFC, composite SOFC/MCFC systems) and C02 capture have emerged and are concentrating important research and technological efforts. Moreover, new fields of implementation, related to molten carbonates, are also present: geology, glasses, production of nanocarbon particles etc. Considering other areas where this molten phase plays a major role, such as catalysis, waste destruction, surface treatment, it can be confirmed that the field of molten carbonates is very rich and offers many opportunities for fundamental science and competitive applications. Whatever their specific application, molten carbonates activity is associated to more efficient energy systems with low production of C02 and, in a prospective sense, to non-polluting energy using the value of C02. A recent event, the International Workshop on Molten Carbonates & Related Topics, IWMC201 I, held in Paris in 2011 , have put in evidence the importance to improve and exploit this investigation and technological domain."

Jan 1, 2012

By Riyad N. Ahmad-Bita, Shadia J. Ikhmayies

"SnO2:F/CdS:In structures were prepared by the spray pyrolysis technique on glass substrates at a substrate temperature Ts = 450°C. NH4F and HF were both tried as the sources of fluorine in the precursor solution of SnO2:F. A comparison between the properties of structures obtained by using the two doping compounds was performed. X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmittance measurements were used to characterize the films. The structures prepared by using HF as a fluorine source were found to have more ordered crystal growth, larger grain size and sharper absorption edge. From the inspection of the first derivative of the absorbance it is expected that more interdiffusion on the SnO2:F/CdS:In interface takes place in the structures made by using HF. These results confirm that these films are better as forecontacts for CdS/CdTe solar cells.IntroductionThin film CdS/CdTe solar cells built in the superstrate geometry rely on transparent conducting oxides (TCOs) to make the front contact The investigation of combined CdS-TCO films has recently been developed owing to the great interest of better understanding the effect of these bilayers on the absorbers [1]. Usually SnO2 is utilized as a front contact for these solar cells. Optimizing the properties of the SnO2/CdS structures is an important step on the way to get high performance CdS/CdTe solar cells.There are different methods to prepare SnOz thin films, such as reactive sputtering [2], evaporation [3], chemical vapour deposition [3, 4], dip coating [5] and spray pyrolysis [6-9]. At the same time CdS thin films can be prepared by different techniques such as chemical bath deposition [10], thermal evaporation [11], screen printing [12] and spray pyrolysis [7, 13]. However, the spray pyrolysis technique is a very low cost and simple technique that enables intentional doping and getting large area and uniform thin films [14]. For these reasons it is choused to prepare SnOz and CdS thin films in this work. To improve the properties of these compound semiconductors, SnOz was doped with fluorine and CdS was doped with indium where such doping is well known for these compounds."

Jan 1, 2012

By Zhigang Liang

Effects of the configuration parameters of submerged entry nozzle on the flow field in slab mold were investigated through a water modeling. The experimental results showed, when the original submerged entry nozzle was applied, there was an appreciable level fluctuation in the mold with obviously naked surface and entrapment of mold flux at higher casting speed. By increasing the outlet area of submerged entry nozzle, without any change of other configuration parameters and submergence depth, a proper fluid field with active surface and good covering of mold flux can be obtained, which is proper to meet the requirement for increasing the casting speed and improving the slab quality simultaneously.

Jan 1, 2009

By S. Saptharishi

Selenium, which is a 6A group element of the periodic table, constitutes about 7x10-5 % of the earth?s crust. Even though selenium is a dispersed element with respect to its commercial exploitation, it is capable of forming number of minerals and nearly forty selenium minerals have been identified, out of which the copper ores are the richest sources of selenium. Electronics industries and glass industries are the major consumers of selenium, while pharma grade selenium used as micronutrient for humans and animals. Various methods have been developed to recover selenium as a by-product from copper anode slime during copper refining. Selenium being amphoteric in nature, it is soluble in both acid and alkali. While acid roast process is widely used, considerable work has been carried out in Russia for recovering selenium through alkali route. This paper enlightens the process developed at Central Research and Development Laboratory, for recovering selenium from decopperised slime through alkali pressure leaching. The decopperised slime is pressure leached with alkali under oxidizing conditions by which almost all the selenium present is converted to alkali selenate, which is easily separable from the rest of the decopperised slime. The solution so obtained is neutralized, during which, most of the impurities are precipitated out. Then selenium is precipitated in its elemental form upon purging sulphur-di-oxide under warm acidic medium. The purity of the selenium obtained by this process is higher than that of the selenium from acid roast process. Moreover selenium can be crystallized as sodium selenate and it can be marketed. The acidic content of the effluent is recovered and it is recycled back to the process. The sodium content of the effluent is converted into high purity sodium sulphate, which is marketable. The hazardous waste containing arsenic is precipitated as its sulphide and can be disposed off as landfill.

Jan 1, 2006

The reported values of the standard reduction potentials of the Au(NH3)2+/Au(0) and Au(S2O3)23-/Au(0) couples are reviewed to emphasise the experimental difficulties associated with the measurement of reliable values for these quantities. The standard reduction potential for Ag(I)/Ag(0) in ammonia and thiosulphate solutions measured at ionic strength 0.1 and 25oCis used to predict the following relevant stability constants () for gold complexes based on the linear free energy correlations: Au(NH3)2+2 = 1013, Au(S2O3)23-2 = 1024 and Au(NH3)43+4 = 1033. The equilibrium constant ( 10-11) for the reaction Au(S2O3)23- + 2NH3 = Au(NH3)2+ + 2S2O32- based on these stability constants is in reasonable agreement with the measured value (10-9) based on potentiometric and spectroscopic data when excess ammonia was added to a solution of Na3Au(S2O3)2. This also indicates that the stability constant of Au(NH3)2+ is 9 to11 orders of magnitude less than that of Au(S2O3)23-. Relevant species distribution and Eh-pH diagrams based on the revised data are presented.

Jan 1, 2003

By P. Chris Pistorius

"Use of coke in blast furnace ironmaking is the main origin of carbon dioxide emissions from integrated steelmaking. Use of pre-reduced iron feedstocks would reduce the coke rate and, if pre-reduction were carried out with natural gas, would decrease the overall carbon intensity of ironmaking. Blast furnace productivity would also increase, because the blast volume per unit of hot metal would decrease. This paper shows that these trends can be predicted quantitatively, by using a conceptually simple Rist-style blast furnace mass and energy balance, assuming furnace productivity to be limited by the tuyere gas flow rate. Such predictions would assist in optimizing the choice of the degree of reduction and relative amount of pre-reduced blast furnace feed.IntroductionSteelmaking is responsible for some 5% of world CO2 emissions, at a rate of approximately 1.9 tonnes of CO2 per tonne of cast steel [1]. In integrated steelmaking, the ultimate source of most of the CO2 emissions is coke, the indispensible (and expensive) fuel and reductant for blast furnaces. There are several research programs underway worldwide which seek to lower the carbon intensity of ironmaking; one of the largest is the European ULCOS program [2], in which the main proposed change to blast furnace ironmaking is to scrub CO2 from the furnace off-gas (for possible sequestration), recycling the remaining gas to the furnace. To limit the recycling nitrogen load, oxygen rather than air is used to combust coke.A conceptually simpler approach is to charge prereduced feed (direct-reduced iron) to the blast furnace. This approach has been used for some two decades at the AK Steel Middletown plant, where some 200 kg of direct-reduced iron (DRI) is charged per tonne of hot metal [3]. The Middletown blast furnace has exceptionally high productivity (rate of iron production relative to the furnace hearth area), simply because less coke is required per ton of hot metal if part of the feed is already metallic. Midrex [4] has provided some quantitative predictions of the implications of DRI use in the blast furnace, stating that for every 10% of Fe in the feedstock that is in metallic form, the fuel requirement decreases by 7% and the productivity increases by 8%."

Jan 1, 2012

By D. Valic

In 1997, 9.2 million tonnes of mined, recoverable copper was produced, of which, 1.8 million tonnes or 19.4% was produced by leaching, solvent extraction and electrowinning. The amount of copper produced by this method grew faster than those attained from concentrate smelting, signifying the growing importance of this low-cost production method. Statistical experimental design, unlike traditional approaches, allows for proper distribution of experiments within the boundaries of factors being studied such that the number of experiments required to develop a sound relationship between the factors and a response is minimized. In the past, very little use has been made of statistical experimental design in copper electrowinning studies. Traditional one- variable-at-a-time approaches are widely employed for this purpose. The present study employs a factorial experimental design to relate current efficiency with current density (180 and 300 A/m2), copper concentration (25 and 65 gL), and temperature (40 and 60 °C). Pure synthetic electrolyte with a constant acid concentration of 180 g/L was used throughout the study. The designed study produced a linear relationship where the independent variables of current density, copper concentration, and temperature, and their interactions, were found statistically significant. It was shown that current efficiency could not solely be used as a predictor of copper cathode quality. The quality of the deposit is difficult to be incorporated into a model or relation. It was determined that other measures, such as cathode morphology and crystal structure should be considered. This was done through XRD and SEM analysis.

Jan 1, 1999

By Naiyang Ma

High zinc concentration in basic oxygen furnace (BOF) steelmaking offgas (OG) cleaning system solid wastes is one of the main barriers for recycling of the solid wastes in sintering – blast furnace ironmaking process. One of the possible solutions is to utilize zinc-free scrap in BOF steelmaking so that the BOF OG solid wastes will not be contaminated with zinc and can be recycled through sintering – blast furnace ironmaking. This paper describes a model for helping to decide whether to use zinc-free scrap in a BOF process. A model computing marginal price increment of zinc-free scrap is developed. The marginal price increment is proportional to value change of the BOF OG solid wastes after and before using zinc-free scrap, to ratio of BOF solid waste rate to purchased galvanized scrap rate, and to price of galvanized scrap. Due to the variations of consumption rate of purchased galvanized scrap and home galvanized scrap, iron ore price, landfill cost, and price of purchased galvanized scrap, using zinc-free scrap in a BOF process might be economically feasible for some ironmaking and steelmaking plants or in some particular market circumstances.

Jan 1, 2015

By Steven Wright

The extent and the rate of reduction of slags produced from the smelting of recycled lead batteries were investigated under laboratory conditions using graphite as reductant. Simultaneous reduction of PbO, Fe2O3, Sb2O3 and As2O3 occurred at temperatures of 1180 and 1200°C, with Sb and As reporting to the metal phase while the PbO content of the slag was above 2 wt%. Fuming of As from the metal occurred at lower concentrations of lead in the slag. Discard slags with low levels of As, Pb and Sb were produced. Arsenic levels were reduced to less than accurately measurable by ICP analysis, and Sb levels in the final slags were in the range of 0.1 to 0.2 wt%. The kinetic data obtained were analysed and compared with other measurements on lead oxide containing slags. The results showing a dependence of the reduction rate on the oxidation state and the basicity are consistent with other studies on well characterised industrial and. synthetic lead slags. These results indicate that when carbonaceous reductants are used, the rate of interfacial reactions play an important role in enabling the production of environmentally acceptable discard slags.

Jan 1, 1994

By Corby G. Anderson

Laboratory testing, interpretation and application of metallurgical technologies can be tedious, time consuming and costly. This paper outlines the use of proven statistical design of experimentation software for rapid optimization of laboratory testing and operating plants with limited representative sample utilization. This results in less costly required testing, a more thorough understanding of results and the ability to simultaneously optimize several variables and outcomes at once. At the Center for Advanced Mineral and Metallurgical Processing, this testing methodology has been used successfully in many metallurgical development and plant optimization projects thereby confirming its real world utility and application. Accordingly, several applied examples in flotation and hydrometallurgy will be outlined in this paper. This will include flotation testing of a copper gold ore, flotation testing of a copper, cobalt and gold ore, optimization of an industrial hydrometallurgical jarosite circuit and optimization of industrial nitrogen species catalyzed pressure leaching of a copper enargite concentrate.

Jan 1, 2006

By Pinakin C. Chaubal

Today?s steel industry is in a vibrant and resurgent mode. This transformation has been in the making for some time now. Over the last few decades, the industry was steadily transforming itself into becoming a high tech industry. New technology was adopted, efficiencies were enhanced, lean manufacturing concepts were brought in and a strong customer focus was developed. Today?s mills employ sophisticated instrumentation, computerized monitoring, on-line smart systems etc. driving processes that are producing at rates of many tons/minute. All this is not possible without judiciously using the latest available technologies in various fields and developing a more sophisticated work force. Prof. Sohn has been a pioneer in driving the concept of process engineering in process metallurgy. In this paper the focus is on some aspects of process engineering ? primarily process modeling - as applied to iron and steelmaking processes. Examples are shown to demonstrate how problems have been addressed. Some thoughts on future directions are presented.

Jan 1, 2006

By Clodualdo C. Conde

In order for Philippines Associated Smelting and Refining Corporation (PASAR) Corporation to remain a leader in the copper smelting and refining industry, continuous improvements in plant technology are required. Reliable performance of plant equipment is essential for a competitive smelting operation. PASAR is constantly searching for the best equipment and technology to allow us to manufacture products more efficiently. When the Smelter was commissioned in 1993, the Flash Furnace off-gas treatment system was a constant source of problems. There were frequent shut-downs of the electrostatic precipitator due to material buildups on the discharge electrodes and collecting plates. In 1998, the precipitator was successfully upgraded to eliminate the buildup problems and to increase the collection efficiency. The upgrade greatly reduced down time and maintenance, and the enhanced collection efficiency also eliminated pluggage problems and material losses in the Acid Plant. This extensive precipitator upgrade was accomplished during a 30-day Smelter turnaround.

Jan 1, 1999

By Michael G. King

The primary non-ferrous metals industry is the principal supplier of the minor metals selenium, tellurium and bismuth. It is also a major supplier of antimony. These minor elements are recovered from by-products of base metals production. To ensure that these elements remain available, the cost of production must be compatible with four other factors - method of production, available supply, technological niches, and product stewardship. This paper first describes the relationship between the copper industry and the production of tellurium and selenium. The more complex relationship between the lead industry and bismuth production is then discussed, followed by comments on antimony availability. Product stewardship programs are essential to the growth or certain specialized markets for these metals. Smelters and refineries of non- ferrous metals will play a major role in the recycling of scraps and wastes from these markets. Examples on how such materials can be recycled are given in the paper.

Jan 1, 1995

By S. J. Kohut

Until recently SX-EW technology has only been used to produce conventional cathode for the cyclical commodity marketplace. Unlike electrorefining, SX-EW lends itself to the integration with the downstream manufacturing technologies for direct mine site production of value added products. The integration of SX-EW and downstream manufacturing results in the elimination of redundant process steps, the cost savings, and the access to value added product markets which can buffer the producer from swings in the cathode market. SX-EW production of copper powder and powder-based products has been demonstrated at the pilot plant level. The SX-EW process has been successfully redesigned to meet the more specific demands of engineered products. Challenges include the solution purity, the cell ventilation, the high current density operation and the product handling. Successful demonstration of mine site production of value added SX- EW products opens up new non-commodity marketplaces to the mining industry.

Jan 1, 1999

By L. Z. Villanueva

An investigation and evaluation has been performed to determine the potential utilization of electron beam irradiation technology for sulfur oxides removal from reduced-S02-strength metallurgical gases from copper smelters. These off-gases, though too weak to be converted to usable, concentrated: sulfuric acid by conventional means, are characterized by SO2 content higher than 2,000 ppm and a complex chemical composition, including high oxygen content and its generation occurring in a cyclical, fluctuating pattern. This work was based on information supplied by principal smelter companies in Chile. A laboratory facility with flow rate of 20 Nm3/h and equipped with an electron accelerator of beam energy 8.00 keV, has been used for testing. Influence on SO2 removal efficiency of operational parameters such as gas temperature, water vapor content, ammonia feed ratio and irradiation dose was established. The main conclusion of this work, from experimental laboratory tests as well as engineering studies, is that the Electron Beam Process (EBDS) is a cost-effective, simple and appropriate chemical process means for emission abatement. EBDS can, on a site-specific basis, adequately augment SO2 removal to upgrade overall abatement as required and in an optimal manner.

Jan 1, 1999

By V. G. Papangelakis

The implementation of a flow-through yttria-stabilized zirconia (YSZ) sensor for pH measurements in high temperature and concentrated electrolyte systems relevant to hydrometallurgical processing of nickeliferous laterites is discussed. Instrumentation involved the use of a custom made flow-through titanium electrochemical cell. Accuracy and validity of the pH measurements at temperatures up to 250C were assessed using concentrated sulphate process solutions ranging from synthetic binary sulphuric acid ? water solutions to progressively multicomponent metal ? sulphate solutions simulating laterite Pressure Acid Leach conditions. The measurements were also compared with theoretical models using recently obtained thermodynamic data. A difference of ±0.25 pH units was observed between measured and calculated pH values at temperatures. This is an acceptable difference given that these are the first direct high temperature pH measurements ever on the concentrated acidic sulphate solutions. This result is encouraging more research for the development of industrial electrochemical systems for direct pH measurements in autoclaves.

Jan 1, 2003

By J. L. Bill

The capacity of the Mount Isa Mimes Limited Copper Smelter was expanded in 1998 from 180,000 tomes per year of anode copper to 265,000 tpy. It is based on the innovative Copper ISASMELT technology, which currently treats concentrate at up to 184 tph. Increasing lance-air oxygen enrichment increased the ISASMELT furnace feed rate from 102 to 184 tph. The increased feed rate was achieved without any modifications to the ISASMELT furnace. The first refractory campaign following the upgrade lasted for two years. Future campaign lives of four years or more--without water cooling-are possible. Other Copper ISASMELT furnaces are operating in the U.S.A., Belgium, and India, with additional smelters under construction in China and Germany. In addition, Lead ISASMELT furnaces are operating in the U.K. and Malaysia. The paper discusses the performance of the MIM Copper ISASMELT furnace and the Copper Smelter since the expansion, including operating data and refractory performance.

Jan 1, 2002

Over the years, numerous hydrometallurgical processes have been proposed as an alternative or complement to smelters for the treatment of copper concentrates. Most of these initiatives met with limited success. Bioleaching is applied commercially for secondary copper minerals heaps and dumps, and bacterial leaching processes are being developed for copper concentrates, although industrial application is still years away. More recently developed processes usually include pressure leaching and/or ultrafine grinding. This paper proposes a new leach process to treat copper sulphide ores or concentrates: the process operates under atmospheric pressure and uses limited concentrations of ferric sulphate as oxidant; the key to the process is the regeneration of the ferric ion, which can be effected in-situ (direct process) or ex-situ (indirect process) using SO2/O2. Examples are presented for the treatment of copper concentrates by agitation leach and of copper ores by heap leaching. Application of the process to copper gold ores and chalcopyrite concentrates is also discussed.

Jan 1, 1999

By M. J. Perpich

Electrochemical and chemical leaching tests were carried out on chalcocite, covellite and chalcopyrite in acidified iron sulfate solutions sparged with a mixture of O2 - SO2. The gas mixture catalyzed the ferrous to ferric oxidation reaction in situ and, therefore, increased the redox potential and oxidizing strength of the solution. Anodic polarization curves in dilute sulfuric acid on copper sulfide electrodes showed that chalcopyrite passivates and dissolves at current densities orders of magnitude less than chalcocite and covellite. The addition of a depassivating agent (Ag+) increased the passive current density of chalcopyrite and caused breakdown near 0.625 V (SCE). The depassivating effect was also observed during the leaching of chalcopyrite particulate samples as small amounts of Ag+ added to acidified iron sulfate solutions in the presence of O2 - SO2 mixtures greatly increased the leaching rate and the total amount of Cu oxidized (> 90%). Passivation was prevented in the absence of Ag+ by decreasing the initial oxidizing power of the solution and by pretreating the sample in a reductive leach. Both of these methods resulted in transformation of the chalcopyrite surface from its characteristic greenish-gold into deep black. Increased concentrations of Fe+++ due to 02 - S02 sparging were then able to oxidize the transformation product.

Jan 1, 1999

By Robert S. Sokolowski

The future of Materials Processing in Space (MPS) in the Space Station Era is being assured today by a strong coordinated science program which looks to solve these problems, the answers to which serve to underpin the technical foundation upon which future metallurgical and materials processes will be built. The critical link between the product and process development activities that accompany this science endeavor is the "nuts and bolts" hardware that will ultimately operate in the space environment. Ground-based facilities including drop facilities and aircraft provide excellent product development and process concept study tools. Shuttle flights with Spacelab and commercially developed space facilities represent the evolutionary path to Space Station processing facilities. Today the most promising areas of MPS are crystal growth, containerless, and quasicontainerless processing. The unique features of these processes will be highlighted. Finally a more visionary perspective of MPS will be presented that incorporates the limits of today's knowledge with the economic "necessity" of tomorrow.

Jan 1, 1988