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By Melinda Channel, Alan W. Weimer, Jonathan R. Scheffe

"There is a need to develop cost effective renewable energy processes for the production of clean fuels that can simultaneously mitigate the U.S. energy/global environmental security issue. If H2 can be obtained cost effectively via the splitting of water using concentrated sunlight, then it’s possible to operate a fuel cell using renewable H2 or to synthesize other fuels based on renewable H2 for generating electricity or for running internal combustion engines. For example, H2 can be reacted with sequestered carbon dioxide (CO2) to produce syngas (H2/CO) via reverse water gas shift (RWGS), i.e. H2 + CO2 ? CO + H2O. The syngas can be catalytically methanated to form synthetic natural gas (SNG) or it can be catalytically reformed to produce liquid fuels such as “green” gasoline via the MTG process (syngas? methanol ? gasoline). The desert SW United States is home to world class sunlight. Fundamental ferrite thermodynamics will be reviewed, an example of the beneficial effect of ferrite surface area on reaction kinetics will shown, and process economics will be investigated for a 100,000 kg/day facility to produce H2.Introduction and Background ThermodynamicsSpinel ferrites of the form MxFe3-xO4, where M generally represents Ni, Zn, Co, Mn, or other transition metals, have been shown to be capable of splitting water according to the two step cycle shown below:MxFe3-xO4 + solar thermal energy ? xMO + (3-x)FeO + 0.5 O2 (1)xMO + (3-x)FeO + H2O ? MxFe3-xO4 + 2H2 (2)This is an inherently clean and sustainable process, as the only net inputs are solar energy and water, and the net outputs are hydrogen and oxygen. Ferrite water splitting cycles are advantages compared to other high temperature water splitting cycles, such as the ZnO/Zn and Mn2O3/MnO cycles, because thermal reduction has been demonstrated at significantly lower temperatures[1, 2]. As a result, overall efficiency may be increased due to the fact that radiation losses increase as the fourth power of temperature, and material considerations for reactor design should be more flexible. Additionally, cycle repeatability has been demonstrated with relative ease as compared to other thermochemical cycles [3-6]. However, the amount of hydrogen per mole that is generated is significantly less than for other high temperature thermochemical cycles due to the fact that only Fe3+ is capable of being reduced at the temperatures of interest[6]. In addition, water oxidation kinetics appear to be very slow, likely due to diffusion or surface area limitations created by near surface oxidation [6, 7]."

Jan 1, 2010

By D. H. Rubisov

The neural networks modelling approach is one of the most elegant black-box type methods to model industrial processes. In this paper, this approach is applied to model the performance of the CEZ zinc electrowinning plant. The model that was built was found to exhibit an excellent predictive ability for voltage and current density. The model was also used to investigate the sensitivity of the process to various key variables such as temperature, current density, zinc and sulphuric acid concentration, etc. Optimal regimes for zinc production were identified from the power consumption standpoint.

Jan 1, 1996

By D. Van Dooren

The final goal of the research project is to develop a 3D FEM model that is able to predict the kinetics and micro-structural evolution during the bainitic transformation. The input parameters consist of thermodynamic and atomic mobility data obtained from the ThermoCalc and mCTRA databases combined with structural mechanics data extracted from the stress-strain curves of the fcc and bee phases. In this paper the general principles of the model are outlined and some interesting preliminary results are shown and commented. The full implementation of the model has presently not been achieved yet. In the model the bainitic transformation is considered as a sequence of martensitic (re)nucleation and growth of a ferritic subunit followed by the carbon rejection into the surrounding austenite. The (re)nucleation of the subunits will be described through a non-classical martensitic nucleation criterion. Once a nucleus has been activated at a specific location in the material, a full-sized subunit is instantaneously formed through a displacive mechanism. The stress state in the system that arises due to the transformation strain can be calculated by a 3D FEM programming code. Immediately after the formation of the subunit, another 3D FEM programming code calculates the carbon diffusion from the supersaturated ferrite into the surrounding austenite. The resulting stress state and carbon profiles will be used to determine where and when a new subunit will nucleate based on a renucleation criterion. Keywords: Bainitic Transformation, Modeling, Eshelby, Carbon Diffusion

Jan 1, 2003

By I. D. Reznik

Results of thermodynamic computations have been presented for reactions occurring in the process of segregation roasting of oxide nickel ores to describe more accurately the mechanism of the process. Under conditions of laboratory-scale roasting in combination with close-circuit flotation flow-sheets and magnetic separation, a recovery of 80-82% of nickel into 8 to 10% Ni concentrate and a recovery of up to 66% of cobalt was achieved. Process conditions have been selected for processing of both high-iron and high-magnesium ores. The feasibility of conversion of 94-98% of nickel and cobalt into solution by oxidizing pressure leaching with sulfuric acid has been demonstrated. It has been substantiated that it is reasonable to introduce double-stage segregation roasting.

Jan 1, 2003

By Norman Schapiro

Future ore bodies will, most likely, be more costly to find, mine and process than those now in production because most of them will be of lower grade or found deeper. To evaluate an ore deposit for extraction of metal values it is important to select the optimum economic process from among the many available options. The physical and chemical behavior of the minerals present should govern the process selection. Process mineralogy which combines mineralogy and petrography with process development engineering generates the data on mineralogy, composition and texture of gangue and valuable minerals from which the optimum process steps can be selected in the commercial design of the ore processing plant. These insights also help in solving operating problems caused by changes in the ore body

Jan 1, 1981

The standard procedure of fire refining consists of sulphur removal via air injected through tuyeres, arsenic slagging via soda-lime flux and oxygen reduction by air or oxygen deficient air or a steam fuel mixtures. The use of porous plugs to stir with an inert gas has been mainly considered as a surface renewing agent that increases the product quality and shorten the refining cycle. In the present study the effect of the bottom stirring by nitrogen gas injection through porous plugs for the treatment of the crude copper in the range of 400-150 ppm sulphur, 3,000-2,000 ppm arsenic and 14,000-7,000 ppm oxygen content was investigated. The combined effect stirring-reducing, by the use of air or a steam fuel mixtures through tuyeres for oxygen removal, follows a kinetics of first order where the constant, K, can be represented by the following polynomial expression: K = A * R2 + B * R + C Where A, Band C are constants that depend on the nitrogen flow rate and R is the air-fuel ratio or the steam-fuel used in the reducing step. Depending on the optimization of the flow of nitrogen and the air-fuel or steam-fuel mixture and only if just the oxidation, complexing and reducing steps are considered, the process cycle might be shortened by 45%.

Jan 1, 2003

By Xinghui Meng

The leaching behavior of platinum powder in .iodide solutions under oxygen pressure in an autoclave was investigated. Ammonium salts were added to the leaching solution at neutral pH as a key lixiviant for platinum. The effect of temperature, partial pressure of oxygen, concentration of iodide and of arttmonium salts on the dissolution rate of platinum was examined. Under experimental conditions, the leaching behavior of platinum powder exhibited a complex reaction mechanism. A precipitate was found during the leaching process and was identified to be platinum ammine iodide, Pt(NH3hI4. The dissolution rate was controlled by a series of chemical reactions, the equilibrium concentration of the platinum ammine iodide being responsible for the ultimate limit to the recovery.

Jan 1, 1996

By Jorge Alberto Soares Tenório, Denise Crocce Romano Espinosa, Solange Kazue Utimura, Amilton Barbosa Botelho, Carlos Gonzalo Alvarez Rosario

In this study, the recycling of waste materials is interesting in the environmental aspect to reduce the amount of waste in land fill and attenuate the pollution of groundwater, air and soil due to the liberation of dangerous elements. Recycling materials is an important issue once it represents a potential source of valuable metals. Waste printed wired boards (PWBs) as a principal part of Waste Electrical and Electronic Equipment (WEEE) and it is a fast growing stream with complex composition. The composite materials from PWBs are ceramic, polymers and metals. Biohydrometallurgical route may offer possibilities to recycle PWBs from discarded computers with the order to recover copper. The extraction of copper from PWBs by bioleaching processeswas studied using a mixed culture of acidophilic bacteria fromacid mine drainage (AMD) and the bacteria Acidithiobacillus ferrooxidans (A. ferrooxidans). The bioleaching experiments were performed in shaker flasks at temperature 30 °C and 170 rpmwith 10% (v/v) inoculum and pulp density of 35 g/L. Themetals concentration was determined by energy dispersiveX-ray Fluorescence (XRF). The results showed that the maximum copper recovery from PWBs using A. ferrooxidans was approximately 89% and with a mixed culture of bacteria from AMD the copper recovery was 92%.

Mar 1, 2017

By C. Acuna

The standard procedure of fire refining consists of sulphur removal via air injected through tuyeres, arsenic slagging via soda-lime flux and oxygen reduction by air or oxygen deficient air or a steam fuel mixtures. The use of porous plugs to stir with an inert gas has been mainly considered as a surface renewing agent that increases the product quality and shorten the refining cycle. In the present study the effect of the bottom stirring by nitrogen gas injection through porous plugs for the treatment of the crude copper in the range of 400-150 ppm sulphur, 3,000?2,000 ppm arsenic and 14,000-7,000 ppm oxygen content was investigated. The combined effect stirring-reducing, by the use of air or a steam fuel mixtures through tuyeres for oxygen removal, follows a kinetics of first order where the constant, K, can be represented by the following polynomial expression: K = A .* R2 + B * R + C Where A, Band C are constants that depend on the nitrogen flow rate and R is the air-fuel ratio or the steam-fuel used in the reducing step. Depending on the optimization of the flow of nitrogen and the air-fuel or steam-fuel mixture and only if just the oxidation, complexing and reducing steps are considered, the process cycle might be shortened by 45%.

Jan 1, 2003

By Gerald M. Ellis

Exploration for gold .deposits on Hispaniola has taken place sporadically over the years but has expanded in the past decade. There are veintype, disseminated, alluvial and elluvial deposits. Investigations were previously undertaken in Haiti by combined Haitian, Bureau of Mines, and UN geological teams at Grand Bois Limbe(Milot) and Cap Coq areas. Later studies were conducted at the Miches and Moncion districts. Gold occurrences were reported in quartz, silicic-barite veins and gossans. An important deposit ?at Pueblo Viejo is? a disseminated type where extraction is taking place in the oxidized zone. Exploration by Japanese and West German firms with local geologists are described in this paper together with Pueblo Viejo, Miches, Restauracion, Milot, and Meme ?areas where occurrences are known. Copper deposits with associated gold va1ues are also described. These include vein deposits in Central Cordillera and disseminated deposits at Terrier Rouge and Blondin.

Jan 1, 1989

By Ray Y. Lin, Randall A. Blue

"Joining of silicon carbide with infrared using a mixture of Si-30wt.%C as the brazing material has been investigated. Joining was performed at a temperature of 1500 °C in a flowing argon atmosphere for processing times ranging from 5 to 60 seconds. The joining filler materials include thin film silicon obtained by thinning down silicon wafers to about 70 /!m and graphite powder of a 15 /!m average particle size. Joint strengths were determined with a specially designed shear-in-compression jig for testing shear strengths of brittle materials. Cross section examinations of the joined specimens with optical microscopy, scanning electron microscopy and transmission electron microscopy have shown that all joints are essentially void free with excellent wetting between the base SiC and the brazing material. Silicon carbide in the B form has been identified as the reaction product in the joining zone with a transmission electron microscope (TEM) and selected area diffiaction (SAD) analysis. At 1500 °C with a joining time of 60 seconds, the joint has consisted of primarily SiC. With such a high SiC content in the joint, the joint strength is comparable to those by other joining techniques, such as diffusion bonding, as reported in the literature. A kinetic model for the formation of SiC from liquid silicon and carbon is proposed to explain the observed joint microstructural evolution.IntroductionSilicon carbide is of great interest for high temperature structural applications because of its excellent high temperature strength, wear resistance and anticorrosive characteristics [1]. Even though the interest in SiC is high, the use of the material has been limited by the high cost and difficulties involved in forming components of complicated shapes [2]. It is these limitations that necessitate the development of effective joining techniques that are cost effective and able to provide strong joints."

Jan 1, 1996

By Geoffrey A. Brooks, M Akbar Rhamdhani, Md Saiful Islam

A novel electrically-enhanced metal purification using slag has been developed. This was achieved by applying DC potential between liquid metal and slag phases. The concept was demonstrated through small-scale experiments at temperatures of 1500-1600oC for the removal of boron from Si-B melt using CaO-SiO2-16wt%Al2O3. Silicon (containing B) and slag were reacted in an alumina crucible in a resistance tube furnace. A circuit was produced by immersing graphite rods into the silicon bath and the slag layer. Electrical potential differences of up to 3.5 V were applied during the reactions. The reaction rates, the opencircuit voltages and short-circuit currents (in the case when the potential was applied) were then measured and determined for various slag to silicon ratio. It has been shown from this study that both the apparent rate and the boron partition ratio were increased by a factor of approximately 1.6.

Jan 1, 2014

By Jing Zhan, Tian-zu Yang, Wei-feng Li, Li-Hua Jiang, Shi-yan Xu, Jian-yang Huang, Chuan-fu Zhang, Yan-qing Fan

The amount and activity of coal, reduction temperature and other parameters of the process of bottom-blown reduction of liquid high lead slag were investigated in laboratory. Methods to strengthen the bottom-blown reduction process were studied by industrial production. The results were in the follows: the reduction temperature was 1150℃; reduction time was 1.5h; the reductant was anthracite; lead content in slag was controlled to 2%; the rate of coal was 7% and gasification loss of coal in high temperature was severe; liquid lead slag reduction rate was faster with coal; prolonging the reaction size had little effect on reducing lead in slag; the size of the reactor can be further reduced.

Jan 1, 2015

By Emil B. Milosavljevic

The photochemical reactions of cyanide ion induced by light were investigated in the presence or absence of a titanium(IV) oxide semiconductor photocatalyst. The light sources employed were the sun and arrays of either mercury or fluorescent (cool white) lamps. The results obtained verify that cyanide decomposes much faster when TiO2 is present in the solution and that it is first oxidized to cyanate. However, contrary to the previous studies, it is established that cyanide is subsequently further oxidized via nitrite all the way to nitrate irrespective of the light source. As expected, the rates of the oxidation processes decrease with the illumination source utilized in the following order: Hg-lamps > sunlight > fluorescent lamps. As nitrate is a significantly less hazardous contaminant than cyanide, complete photocatalytic oxidation of cyanide to nitrate may be a viable method for decontamination of cyanide wastes. Contrary to previous claims, we find that cyanide is slowly photochemically decomposed even in the absence of TiO2. For example, with the mercury lamps as the light source, in two hours, cyanide concentration decreases to essentially zero; up to 7% was converted to cyanate and the remainder to unidentified products.

Jan 1, 1992

By Tianming Sun, Gabriella Tranell, Ragnhild E. Aune, Mark William Kennedy

Rare Earth Elements (REEs) are critical for the production of many advanced materials and products. Mining and primary production of REEs are generally associated with significant environmental impacts. By recovery of REEs from secondary sources, through recycling or as a byproduct, the adverse environmental impacts may be partly avoided. In the present study apatite concentrate originating from iron ore beneficiation done by LKAB in Kiruna, Sweden, is explored as a possible source for REEs. The composition and distribution of the REEs within the concentrates are studied using ICP-MS, XRD and SEM-EDS/EPMA, as well as the melting point and heat of fusion using DTA-TGA-MS. The behavior of the material during melting has also been studied through wetting and slag saturation experiments. The overall aim of the study is to evaluate the implications for future smelting experiments aimed at concentration and recovery of the REEs.

Jan 1, 2015

By Adam Powell

A Cahn-Hilliard phase field model is formulated to describe transport-limited electrochemical reactions coupled with fluid flow in a metal reduction cell. When the reaction is limited by mass transfer of metal ions from the electrolyte to the cathode, the metal-electrolyte interface at the cathode exhibits a Mullins-Sekerka instability, leading to the growth of dendrite-like "streamers" of liquid metal into the electrolyte, which in turn significantly enhance the apparent mass transfer coefficient there. Model results for iron reduction from ferrous oxide in slag show formation of these streamers. Although the double-layer is not included in this model, the related phenomenon of electrocapillarity can be represented by a gradient penalty term which includes the electric potential gradient, such that interfacial energy is a function of the electric field normal to the interface.

Jan 1, 2003

By Dale W. Collins

The disposal of arsenic from copper operations possess various health, environmental and processing problems. There are basically two areas of concern. The first being the disposal or treatment of smelter flue dusts and the second the removal of arsenic from refinery electrolytes. A number of treatment options have been proposed including the addition of soluble arsenic wastes to copper heap and dump leaching solutions. This approach will allow arsenic to be reintroduced to the ore via Solvent Extraction (SX) raffinate associated with hydrometallurgical operations. Knowledge of the attenuation behavior and mechanism during leaching is important in determining the long term stability of arsenic and the success of this approach. Parameters, such as uptake capacity, pH, particle size and solution chemistry have been investigated. Arsenic attenuation has been examined using column leaching with experiments employing both continuous flow and pulsed additions of As(V). In the initial stages of leaching, the attenuation of arsenic appears to depend on the pH and iron concentration in the effluent. Arsenic stability in the copper oxide ore has been examined with rinses of progressively lower pH.

Jan 1, 1994

By D. Doungdeethaveeratana

The extraction kinetics in a novel solvent extraction process have been investigated. In this process, the liquid-liquid emulsion is generated by bottom gas injection into countercurrently flowing aqueous and organic phases. This process has a number of advantages over the mixer-settler unit or the spray column in terms of simple equipment configuration, without any mechanical moving parts, and the ease of cleaning and process control, while providing a sufficiently large interfacial area for rapid mass transfer. The overall rate increased with increasing gas injection rate and height of the aqueous phase but decreased with increasing injector diameter at the same gas injection rate. The variation of the overall rate constant was correlated against a set of dimensionless numbers, representing the operating conditions. Extraction rates and efficiencies comparable to those in a mechanically generated emulsion were attained in this new process.

Jan 1, 1998

By A. V. Tarasov

The proposed process is based on creating a controlled frothed layer of molten slag, in which fine particles of carbonaceous reductant and raw material to be processed are mixed with emulsified iron. Frothing of the slag layer without external blowing occurs as a result of intensive evolution of gaseous reduction products. The froth reaction process is maintained due to the heat of an electric arc in the slag layer. When the metal bath is heated by the arc to 1400- 1 500°C, the low temperature of the slag surface of about 1200-1 300°C is maintained due to low thermal conductivity of slag froth preventing heat loss. In order to maintain the required slag froth level and control the process temperature, air tuyeres are installed above the slag bath; blowing air serves also for oxidation of zinc in fumes and for its transportation. High adsorption and thermal insulating properties of slag froth ensure virtually complete elimination of dust and mist entrainment along with low heat losses. The main macrokinetic regularities of the carbon thermal reduction of zinc-containing slag melts have been studied under frothing conditions. The mechanism of formation of gas-slag emulsion has been identified under the conditions of reaction [C]+[O]=CO occurring locally at the slag-metal interface. It has been demonstrated that under the froth reduction conditions the zinc removal rate from the melt increases on the average by 3 to 5 times. Based on the physical and chemical data obtained, basic principles of the dezincing technology have been developed for different intermediate oxide iron-containing products produced in the process of ferrous and non-ferrous metals production.

Jan 1, 2002

By D. Mukerjee, Ramen Datta, Sanak Mishra, R. Veeraraghavan, K. L. Rohira

"Recent efforts at Steel Authority of India Limited (SAIL) has led to the successful development of atmospheric and marine corrosion resistant high tensile Thermo Mechanically Treated (TMT) bars with minimum specified yield strength of 50 kg.mm-2. These rebars are increasingly being used for a wide range of end-applications, namely, concrete reinforcement structures, bridges, flyovers, dams etc. Welding is an important processing tool for each of the above applications. In view of the importance of welding, a comprehensive evaluation of the weldability properties has been carried for the two grades of steels using Submerged Metal Arc Welding (SMAW) process; the most popularly used technique of welding of reinforcement bars (re bars).Implant tests were conducted to assess the cold cracking susceptibility of the steels. The static fatigue limit (SFL) value, determined for the atmospheric corrosion resistant (Cu-TMT) rebars under no preheat and no rebalcing conditions was found to be 63.8 kg mm-2, which was significantly higher than the Minimum Specified Yield Strength (MSYS) (50 kg.mm-2). This indicates adequate resistance to hydrogen induced cracking (HIC). On the other hand, the SFL value obtained for the marine corrosion resistant rebars (Cu-Cr TMT) under no preheat, no rebaking conditions was found to be inconsistent. Repeat of the test with fully rebaked electrodes (350°C-2h) resulted in a high SFL value (60.3 kg mm-2)_The rigidity of the structure or restraint influences the susceptibility of the weld joint to cracking. The cracking tendency increases with restraint intensity (K) of an assembly. The critical restraint intensities determined for the two steels were found to be· in excess of 1680 kg/mm.mm, indicating good welding behaviour with the following welding conditions : for Cu-TMT rebars with no preheat and no rebaking and for Cu-Cr TMT rebars with no preheat and fully baked electrodes; that is under low hydrogen levels."

Jan 1, 1998