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By Nagahiro Saito, Takahiro Ishizaki, Mituhito Hirota, Akio Fuwa

"Owing to their extremely high toxicity in the environment, the dioxins have been attracting social, technical and scientific attention in recent years. The authors theoretically had predicted the thermodynamic properties of all the dioxins via quantum chemistry and statistical thermodynamics and elucidated the generation-decomposition behavior of dioxins in the equilibrium calculation· of C-H-0-Cl system. In actual combustion processes, it is said that metallic compounds have much influences on the dioxins behavior. The aim of this study is to reveal the roles of metallic compounds the generation-decomposition behavior of dioxins is revealed from the viewpoints of quantum chemistry. Especially, the catalytic effect of copper has been investigated for the reaction, 2HCl(g)--H2(g}+Cl2(g) and for the etherification reaction from precursors, which is Phenol(g) here, to dioxins. The catalytic role of Cu is shown to have much influence on the generation -decomposition of dioxins.1. IntroductionIt is well known that dioxins are very harmful not only for our health but also for that of our children and grandchildren because they are very stable substance and their reaction rates of decomposition are considerably low. On the other hands, it is not well know how dioxins are generated and decomposed; the generation-decomposition conditions and paths as well as the catalysts to decompose them'1l. The authors believe that the thermodynamic and kinetic study of dioxins is useful to find a solution to these issuers. The authors have been investigating the following problems to reveal the generation-decomposition behavior of dioxins; (a) the prediction of the thermodynamic parameters of dioxins (2), (3), (b) the generation -decomposition behavior of non-chlorinated dioxins by the thermodynamic equilibrium calculations in C-H-O system(4) and (c) the generation-decomposition behavior of dioxins by the thermodynamic equilibrium calculations in C-H-O-CI system(5). Summaries of these thermodynamic researches are as follows.(I) The thermodynamic parameters for dioxins, which had been unknown and/or inaccurate'6 l, could be predicted and are available within the scientific accuracy."

Jan 1, 2000

By James O'Brien, Lyman Frost, Grant Hawkes, S. Elangovan, Manohar Sohal, J. S. Herring, Joseph Hartvigsen, Carl Stoots

"Pressing environmental and energy security concerns have brought much needed attention to economic production of hydrogen as the secondary energy carrier for non-electrical markets as well as to meet increasing demand for crude upgrading and desulfurization. While steam reforming of natural gas is currently the dominant method of hydrogen production, it is depleting a valuable fossil fuel while emitting green house gases. Thus, in the long run, efficient, environmentally friendly, and economic means of hydrogen production using nuclear and renewable energy needs to be developed. High temperature electrolysis using solid oxide electrolyte cells is an exceptionally efficient means of generation of high purity hydrogen. It is also capable of directly converting steam and CO2 into synthesis gas. This co-electrolysis process enables conversion of CO2 recovered from concentrated industrial sources into a feedstock for synthetic fuels production. Use of CO2 provides a means of storing hydrogen in a concentrated and convenient form – a hydrocarbon. This is also an effective storage medium for intermittent renewable energy sources such as wind and solar.Ceramatec, Inc and the Idaho National Laboratory are applying solid oxide fuel cell technology to the production of synthesis gas by high temperature co-electrolysis of steam and carbon dioxide. This technology utilizes solid oxide fuel cell stacks to electrochemically remove oxygen from steam and CO2, leaving a clean stream of hydrogen and carbon monoxide suitable for fuel synthesis. By varying the relative concentrations of carbon dioxide and steam, the hydrogen to carbon monoxide product ratio can be controlled as required by the desired type of synthetic fuel being produced from the syngas. The resultant synthesis gas has been used as the feedstock to produce synthetic methane and Fischer Tropsch liquid fuels.Alkaline and proton exchange membrane electrolysis cells typically operate below 100°C, while solid oxide electrolysis cells operates in the 750-850°C range. This higher temperature improves the efficiency significantly. Practically, it translates into a lower cell operating voltage, 1.1-1.4V for high temperature electrolysis vs. ~1.8V for water electrolysis. Hydrogen production is stoichiometric with current in all types of electrolyzers.Carbon dioxide is a valuable resource as a feedstock for energy storage as a hydrocarbon. There is a vast amount of renewable energy that cannot be effectively utilized as grid electricity, but which could be used to convert CO2 to hydrocarbons, offering a solution to the even more difficult (than supplying grid power) challenge of production of sustainable, domestic transportation fuels. Conventional electrolysis and chemical processes could be deployed to accomplish this conversion. However, high temperature co-electrolysis of CO2 and steam to produce synthesis gas using solid oxide fuel cell technology has the potential of improving the efficiency by nearly 50%. A domestic synfuel industry will enable a much larger reliance on intermittent renewable energy than can be accommodated by conventional electric demand profiles while increasing our energy security."

Jan 1, 2010

By Guy Deschênes

In spite of the wide use of lead compounds to enhance cyanidation of free milling sulphide-bearing gold ores, an industrial control method was only implemented four years ago. This study presents the results of the investigation that led to the development of the on-line control technology. Two free milling sulphide-bearing gold ores and high purity minerals were used to develop and test the concept. The first ore contains 2.8 g/t Au, 6.2% pyrrhotite, 2.1% pyrite 0.6 % arsenopyrite, 0.1% chalcopyrite and 0.1% organic carbon. The second ore contains 10.4 g/t Au, 3.2% pyrite, 0.8% pyrrhotite and 0.38% chalcopyrite. The first ore showed a much higher oxidation rate in the pre-leach than the second one and consumed seven times more cyanide. A relation between the formation of thiosulphate and thiocyanate and the additions of lead nitrate were quantified. The ?reducing power?, a titration with permanganate, predominantly determines the concentration of thiosulphate and thiocyanate in cyanide solution. The relation between the reducing power and the addition of lead nitrate at various concentrations of pyrrhotite and chalcopyrite in the ores was established, providing a monitor/control strategy for lead nitrate addition.

Jan 1, 2006

By Ennio Bonetti

The technological applications of MgH2 hydrides for hydrogen storage demand the overcoming of some critical issues: an improvement of the reaction kinetics and a reduction of the desorption temperature. The synthesis of nanocrystalline MgH2 by reactive milling and inert gas condensation and a proper metal catalyst addition, constitute recently employed strategies. In the investigation of the hydrogen short and long-range dynamics, sorption kinetics and nanostructure stability, the mechanical spectroscopy offers some specific advantages. In the present research this technique was employed with other experimental approaches (XRD DSC) to investigate relaxational and structural damping processes in nanocrystalline MgH2 with added catalysts (Fe). Time/temperature variation of the dynamic elasticity moduli and mechanical quality factor are correlated to hydrogen anelastic relaxation processes and concomitant structural transformation of MgH2 to Mg associated to long range H diffusion. Results are discussed with reference to microstructural modification strategies able to assist hydrogen release.

Jan 1, 2006

By Ravi Vancheeswaran

The consolidation of ceramic fiber reinforced metal matrix composites is a key process step in the synthesis of high performance composite systems. A simulation tool has recently been developed for predicting the evolution of the composites internal state microstructural variables (eg. relative density, fiber microbendinglfracture, and chemical reaction layer thickness at the fiber-matrix interface) during the consolidation processing of spray deposited composite mono-tapes. A Generalized Predictive Control (GPC) scheme is used in conjunction with the simula-tion tool to design near optimal process paths that minimize fiber damage and reaction product thickness while simultaneously maximizing the composites relative density. The microstruc-tural evolution depends nonlinearly on the process conditions and therefore the scheme uses a constantly updated linearization of the model to optimize the input process variable vector. A control simulation is presented to illustrate the performance of the design scheme and to assess the feasibility of its use for the achievement of goal state microstructures at the completion of consolidation cycles.

Jan 1, 1996

By Ibrahim Yusufoglu, Cem Kahruman, Mert Zoraga

In this study, a strontium sulfate mineral (celestite) was converted to strontium oxalate in solutions containing ammonium oxalate as a reactant. The experiments were carried out under isothermal conditions. The effects of stirring speed, ammonium oxalate concentration, particle size and temperature on the conversion rate were investigated. During the conversion process, definite volumes of solutions were taken from the reactor after different reaction times for the determination of sulfate ions using ICPOES. Fractional conversions of strontium sulfate were determined at different times and fractional conversion vs time diagrams were generated. It was found that the conversion of strontium sulfate was increased by increasing the ammonium oxalate concentration and temperature in addition to decreasing the particle size. The effect of stirring speed was negligible on the reaction rate. It was observed that above 328 K, a protective layer of strontium oxalate was formed on the strontium sulfate particles. X-ray Powder Diffraction technique was used for characterization of solid substances.

Jan 1, 2014

By Filipe de Menezes Torres, Augusto Pereira de Sa, Itavahn Alves da Silva, Eliana Ferreira Rodrigues, Carlos Antonio da Silva, Varadarajan Seshadri

Top slag eye opening which happens as a result of gas injection is a function of the gas flow rate in addition to other factors such as ladle geometry, porous plug location as well as slag properties. Slag eye opening leads to entrapment of atmospheric nitrogen, oxygen by the steel melt affecting adversely the steel quality. In this work aspects of mixing and eye formation in steel making ladles with inert gas injection have been analyzed through physical and mathematical modeling techniques. Influence of ladle, gas flow rate and distribution and slag properties has been assessed. A correlation for estimating eye opening has been developed. Results from PIV measurements and images of eye opening obtained using a camera have been utilized to validate results from CFD simulation.

Jan 1, 2015

By S. Suzuki, Y. Maeda, N. Wakamatsu

"A new pyrometallugical technology, named KLS process, has been developed by Dowa Mining at its Kosaka Smelter to smelt various kinds of lead raw materials.The process consists of clearly separated two reaction steps, smelting and reduction. For this purpose, respective stationary furnaces are installed which are connected by a slag launder.Dry raw materials, together with pulverized coal and oxygen-enriched air, are injected through a lance pipe into the molten slag in the first furnace. It is kept under a high oxygen potential to remove sulfur completely. Resultant PbO rich slag overflows to the second furnace where pulverized coal and insufficient air are also injected through a lance pipe to reduce PbO to lead bullion and to compensate for thermal deficit. The entire operation is carried out continuously. The process development started back in 1981. In late 1986, a pilot plant with a capacity of 3.5t/H was constructed.Already nearly 20,000 tons of raw materials, mostly lead sulfate mixtures have been smelted successfully.IntroductionFor a long time, main raw materials for lead smelting at Kosaka smelter have been such secondary incombustibles as lead sulfate and lead-barium sulfate. The former is leach residue of the copper smelter flue dust and the latter originates from Iijima zinc refinery. While the most of lead concentrates produced locally has been smelted by an ISF of Hachinohe smelter in which Dowa Mining has a share.The surplus lead concentrates were processed at Kosaka by a hydrometallurgical method to convert PbS to PbSO 4 as pretreatment, and followed by simultaneous smelting together with the above secondary materials (1). Approximate output has been 1,5000 /M of lead bullion and slightly more than 2,000t/M of refined lead by adding lead bullion returned back from Hachinohe smelter (2)."

Jan 1, 1988

By Michael J. Marinigh

"Increased safety requirements, higher operational costs, greater environmental restrictions, and new competitive processing techniques are the challenges smelter operators must confront in order to remain economically viable.In converting furnaces which have tuyères such as the Noranda Reactor and the Teniente, Peirce- Smith and Hoboken converters, efficient tuyère line management is critical to optimizing blowing rates, increasing refractory life, and improving safety.This paper will describe recent improvements made to equipment used for tuyère punching, tuyère silencing, tuyère pyrometry and refractory drilling of tuyères and how the proper application of the equipment can lead to operational and safety improvements."

Jan 1, 2009

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 Kirsi M. Riihilahti

The oxidation characteristics of solid copper matte particles under simulated Kennecott-Outokumpu Flash Converting conditions are presented. The effects of feed matte grade, matte particle size, oxygen-to-matte mass ratio, oxygen content of the process gas and temperature on the particle oxidation rate, quality of conversion, particle size change and particle morphology were determined. The converting quality was highest (~68) with the 58% copper matte at 1100°C. At similar conditions, the 72% copper matte was more likely to produce copper oxides and leave unoxidized particles rather than directly produce sulfur dioxide at 1100°C, resulting in an average converting quality of 55. The quality of conversion was poorest for the 72% matte at 920°C (~45); the sulfur removal was extremely low even with a relatively high degree of oxidation. Fragmentation of the particles was significant in all cases with the 72% matte. A higher O2/matte .ratio and higher temperature, in general, resulted in increased fragmentation while oxygen enrichment had no significant effect. With the 58% matte, particle size was found to increase for the finest fractions rather than to decrease due to particle expansion.

Jan 1, 1998

By Alex I. Kociubczyk, Wilky Desrosin, Lucía Mabel Boycho, Alicia E. Ares, Carlos E. Schvezov

In the present research, commercially pure Sn and Zn, and Sn-Zn alloys (Sn-1wt.%Zn, Sn- 2wt.%Zn, Sn-4wt.%Zn, Sn-8wt.%Zn and Sn-8.9wt.%Zn, weight percent) were obtained by a horizontal directional solidification process with two opposite senses and heat extraction. The solidification process was realized using a horizontal furnace with two heat extraction systems at both ends. The temperature was measured using eight K-type thermocouples and an electronic recorder of temperature data. The resulting structures were analyzed using optical microscopy. From the solidification process the thermal and metallographic parameters were determined in all samples. The presence of defects in the solidified pieces was observed. Internal defects pretended to be dependent not only on the composition of the alloys under consideration but also on the size of the structures formed, also, on the velocities and accelerations of interphases, and on the variation of thermal gradients. A model of the phenomenon from the first principles is presented.

Jan 1, 2015

By Walter E. Dean

Twenty six samples of carbonaceous gold ores and associated rocks from outcrop and mine localities in northcentral Nevada were analyzed for concentrations of major. minor, and trace elements, total sulfur, and organic carbon. Q-mode factor analysis was used to define six distinctive carbonate, organic, and detrital associations of elements, and to group samples based on these associations. The trace metals that have clearly enriched the organic-carbon-rich samples are V, Zn, Ni, Cu, Cr, and Mo, although few of the samples could be considered "metal-rich" when compared to other organic-carbon-rich black shales. Rock-Eval pyrolysis was used to evaluate thermal maturity and hydrocarbon yield of the samples. Unfortunately, most samples were too thermally altered to be suitable for routine organic geochemical characterization of organic matter. The 813C values of organic carbon in rocks from different deposits have a trimodal distribution, but there is no clear distinction between the three groups of deposits that can be related to age, thermal history, or depositional environment.

Jan 1, 1987

By Z. Smieszek, J. Botor, Z. Miczkowski, S. Sobierajski

"From 1978, the direct process for the smelting of chalcocite concentrates in a flash furnace by the Outokumpu method has been applied at the Glogów II copper smelter. The chemical composition of these concentrates make it necessary to control the process very strictly. In this paper, the method for controlling and measuring the main technological parameters of the copper production by flash smelting is being presented. It includes the determination of the chemical composition of the concentrate, its grain structure, the temperature of liquid products of the process, oxygen content in process gases, as well as lead concentration in copper and copper concentration in slag.The main process parameters are determined from the mass and energy balances. The relations between parameters, such as an effect of grain structure of a concentrate on oxygen and oil consumption, and dependence of chemical composition of a concentrate on capacity and products quality are discussed. 1. IntroductionThe Polish copper concentrates, as most concentrates occurring worldwide, contain from 18% to 30% Cu, and less sulphur (7-11%) and iron (2-5%). The main copper-bearing mineral contained in the concentrates is chalcocite, while bornite and chalcopyrite are present in smaller quantities. Moreover, the organic carbon (5-7.5%), arsenic (0.05-0.3%) and lead (1.2-3.0%) are also contained in the concentrates. The gangue consists mainly of silica, aluminosilicates, calcium carbonate and magnesium carbonate. Their proportions make the addition of slag-forming agents unnecessary.The composition of Polish concentrates, especially their low iron content, allows their application in the direct flash smelting process for blister copper production. Low sulphur content is the factor which determines the necessity of oxygen application in this process."

Jan 1, 1989

By Yushiro Hirai

Saganoseki smelter & refinery had operated two flash smelting furnaces from 1973, attaining 330,000 mtpy of copper production in 1989. In 1996, however, it carried out a "integration of two flash furnaces". That is, it doubled the feeding capacity to one flash furnace to shut down another furnace while maintaining the same production. Single flash furnace operation has successfully started in March 1996 accomplishing a great reduction of the total production cost. The production had reached to 350,000 mtpy in 1997, and further increased to 450,000 mtpy by executing the expansion program with single flash furnace in 1998. This paper introduces results of the single flash furnace operation and describes about an outline of the expansion.

Jan 1, 1999

By Desmond Cook, Cynthia P. Dogan, Dale Govier, Gary Korth, James C. Rawers

"The microstructural and mechanical properties of iron powders processed in an attrition mill are highly dependent upon the processing environment. Extended high-energy ball milling in argon resulted in nanocrystalline bcc-Fe microstructure, while processing in nitrogen or alloying with carbon resulted in both nanocrystalline bcc-Fe and bct-Fe microstructures. In this U.S. Bureau of Mines study, both X-ray diffraction and Mössbauer analysis were used to show that the infused carbon and nitrogen concentrations were predominantly on the grain boundaries. Explosive consolidation resulted in a fully dense product with microstructure similar to the microstructure of the mechanically processed powder. Hardness values of the compacts correlated highly with grain size, independent of the processing conditions.IntroductionNanocrystalline materials have been theorized and shown to have unique properties that make them interesting for material scientists and promising for material engineering applications. Several conferences have been devoted solely to the techniques of preparing nanostructured materials have been held(l,2,3.). To date, most techniques used to generate nanocrystalline materials produce only a few grams of particles(1). High-energy ball-milling, however, is an efficient and effective technique that can produce substantial quantities of nanocrystalline materials with homogenous chemical composition that cannot be produced by conventional processing techniques(3).Applications and material evaluations of nanocrystalline materials require several grams of solid samples. Because nanocrystalline microstructures' are thermodynamically unstable, producing consolidated macro structures of nanocrystalline material has proved to be very difficult(2,3). In particular, retention of the nanocrystalline microstructure during consolidation of nanocrystalline particles has proven to be a problem. In contrast to many consolidation techniques that require elevated temperatures, explosive compaction uses a shock wave for consolidation( 4,5)."

Jan 1, 1994

By A. G. Raraz

Reactive metal electrorefining presents a number of problems that pose obstacles to commercial operation. Cerium has been chosen as the surrogate for certain reactive metals because of its thermodynamic and electrochemical characteristics. A comparative review of the properties for cerium and plutonium has been presented to justify the choice of cerium as the surrogate metal for studying electrorefining. This review has addressed the electrochemical, thermodynamic, and kinetic parameters of molten salt electrorefining of cerium metal to provide an insight to this extremely important process. The cell components and configuration, current efficiency of the process, purity of the cathodically deposited metal and the power requirement of the system are evaluated for a molten CaCl2-MgCl2 salt electrolyte using a molten, stirred impure anode. Crucible designs, salt electrolyte, cell temperature and electrode materials are also evaluated. Selection of the salt electrolyte and the cell temperature have been suggested from this study.

Jan 1, 1992

By Jillian Spindura

This work investigates the carbothermic reduction of the complex sulphide mineral, pentlandite, in the presence of lime. The effects of change in temperature and the use of different carbon sources are studied and the role of these variables on the reducibility of pentlandite mineral is discussed. The microstructures of the heat-treated pellets are examined using X-ray diffraction and scanning electron microscopic techniques. The latter analytical method also allows any variation in the morphology and composition of the metallic phases formed, with temperature, to be considered. The kinetics of the reduction process is studied and the magnitude of the overall activation energy is determined from the plots of percentage reduction versus time.

Jan 1, 1996

By Yunhua Gan, Xiaowen Chen, Yang Tong

Experimental studies of electro-spraying were carried out using ethanol as fuel in a microcombustor under combined electric field. And the effects of different electro-spraying modes on the combustion efficiency were analyzed. Results showed that when ring electrode potential was invariant, there were four different electro-spraying modes with the variations of nozzle potentials, which were varying with the flow of ethanol. The cone-jet mode was the stablest one during the whole experimental process. The atomized ethanol was ignited and combusted stably near the steel mesh, the combustion efficiency increased firstly and then decreased along with the increasing of the equivalent ratios, reached the maximum values when the equivalent ratio equal to 1.0. And the maximum values were the highest at the cone-jet mode, and the lowest at the pulsed-jet mode.

Jan 1, 2016

By D. P. Briand

Falconbridge Limited operates a smelter in Sudbury, consisting of fluid bed roasters, acid plant, electric furnaces and Peirce-Smith converters, to treat local concentrate and other custom materials. The products are a low iron, nickel- copper-cobalt matte and sulphuric acid. This paper describes the operation and highlights some of the recent efforts to improve human resource effectiveness, to reduce sulphur dioxide emissions and ground level concentration excursions, to develop and expand the custom feed business, to improve productivity and performance in safety and hygiene, and to improve furnace integrity and process control.

Jan 1, 1993