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By Richard B. Diver, Mark D. Allendorf, Daniel E. Dedrick, James E. Miller, Roy E. Hogan, Andrea Ambrosini, Eric N. Coker, Anthony H. McDaniel, Nathan P. Siegel, Gary L. Kellogg

"Converting carbon dioxide and water to hydrocarbons is an attractive option for storing solar energy and, coupled with appropriate CO2 capture technology, for recycling carbon and impacting atmospheric CO2 concentrations. For any process, high solar-to-fuel efficiency is necessary for large scale viability and favorable economics. Thermochemical approaches for solar-to-fuel conversion are potentially highly efficient as they avoid the inherent limitations of photosynthesis and also sidestep the solar-to-electric conversion necessary to drive electrolytic reactions. Solar-driven two-step metal-oxide-based thermochemical cycles for producing the components of syngas, CO and H2, from CO2 and H2O are the basis of the “Sunshine to Petrol” project. Multi-cycle production of both H2 and CO has been demonstrated over several iron- and cerium-based compositions fabricated into monolithic pieces both in the laboratory and at the National Solar Thermal Test Facility. These compositions are being developed for deployment in a unique and continuous solar-driven reactor prototype, the counter-rotating-ring receiver reactor recuperator or CR5.IntroductionThe interconnected challenges posed by increasing global competition for petroleum and the increasing concentration of atmospheric carbon dioxide are now widely recognized. Meeting these challenges requires recognition that although hydrocarbon fuels are ideal energy carriers, they can no longer be thought of as primary energy sources. It is necessary to take the realistic view that our conventional fossil fuels are in fact “stored sunlight” in the form of “sequestered carbon.” This view leads to a search for options to use and store sunlight more directly.Sunshine to PetrolIn combusting hydrocarbons we unlock the energy for utilization, but we also release the carbon to the atmosphere. However, nature teaches us that with an appropriate persistent energy source, e.g. solar irradiation, it is possible to effectively reverse the combustion process and “reenergize” CO2 and H2O back into hydrocarbon form."

Jan 1, 2010

By R. Cavanagh

Studies relating to the fixation of sulfur by reaction of 4 to 8 mm diameter cylinders of calcined limestone or dolomite with high strength sulfur dioxide in the temperature range 880°C to 1020°C were undertaken. Dolomites are far superior in sulfate capacity and reactivity than dense limestones even at high strength SO2. The sulfation reaction was first order with respect to SO2 concentration below 100 percent. Zero reaction rate at 100 percent SO2 concentration indicates that sulfate was the exclusive reaction product and that sulfite had no role in the reaction. At relatively low SO2 concentrations gaseous diffusion through the reaction product layer has a marked effect on the rate. As SO2 concentrations were increased up to 100 percent more complex rate controlling mechanisms unfold. By sectioning partially reacted dolomitic limestone pellets a moving interface was observed. Reaction ceased because of pore plugging for dense non-porous limestones at 30% conversion. With dolomitic material virtually complete sulfation of the calcium was observed. S.E.M. analysis showed that the average atom ratio Ca:S was 1.01, thus supporting the argument that little if any of the magnesium was sulfated.

Jan 1, 1996

By Miroslav Raudensky, Kallol Bera, Jaroslav Horsky, Jee G. Chang, Ampere A. Tseng

"A combined experimental and finite element approach to study the local heat transfer coefficient is presented in this paper. The heat transfer coefficients at different cooling regimes in a roll are quantified by an inverse heat conduction technique; the heat transfer phenomena involved are then discussed. A discussion of the application of the heat transfer information found in the present study for better design of a roll cooling system is also included. Finally, an identification of areas where further work is needed is presented.IntroductionIn metal rolling processes, the roll is used as a tool to deform the workpiece at very high speeds. As shown in Fig. 1, the heat transfer phenomena involved in the process are complicated by the interaction between the roll and the strip, mainly including 1) the heat transferred from the workpiece to rolls in the contact regions, 2) the heat created in the interface due to the deformation of the workpiece and the friction between the workpiece and roll, and 3) the heat removed by watercooling as well as the ambient air. All of these transport phenomena occur at extremely high pressure, high speed, and high heat flux; these make the control of the roll temperatures an extremely challenging problem.In hot rolling, proper cooling of rolls can lead not only to improve the roll shape quality by controlling the thermal crown of the roll, but also to extend the roll life by minimizing the thermally induced stresses [1,2]. Also, knowledge of roll temperatures can contribute to insights about the roll/workpiece interfacellubricant behavior, and lead to the desired surface condition of the workpiece. Therefore, adequate roll cooling or control of roll temperatures is of critical concern to mill designers and process engineers. In order to have proper operation of the process, a good understanding of the influence of cooling practices on the roll is essential [3]."

Jan 1, 1994

By F. Tailoka

Microporous membranes have been used to create a very fine dispersion of bubbles which greatly enhances the mass transfer of electroactive species to the electrode. Using this system, it has been shown that it is possible to electrowin copper as a coherent planar deposit, at high current densities, from copper chloride solutions.

Jan 1, 1990

By Hiroyuki Sano, Chikabumi Yamauchi, Mitsuru Tanahashi, Toshiharu Fujisawa, Shin-ya Iwahori

"Pyrometallurgical process using Cu2O-based slag was proposed as a recycling process for copper scrap. However, it is difficult to remove nickel from copper by oxidative refining. Therefore, it is necessary to reduce the concentration of nickel in copper before the oxidative refining. In the present work, the copper enrichment stage in this recycling process, where copper scrap melt is separated into the Fe-C-Cu melt and the molten copper, was taken up and the compositions of both melts were measured. Based on the above results, the distribution ratios of nickel between the Fe-C-Cu melt and the molten copper were calculated. Furthermore, the optimum condition of copper enrichment stage was discussed from the viewpoint of nickel removal and copper recovery. The possibility of recovering 4N-purity copper by using this recycling process was confirmed.IntroductionRecycling is well known as a method for saving resources and reducing environmental damage. More than 99% of copper is used in metallic form - as metal or copper alloys[l]. High-grade copper scrap is directly re-melted and reused, while low-grade copper scrap is transported to copper smelters to be pyrorefined and electrorefined. Nevertheless, a great amount of copper is being stockpiled in the cities and should be recycled in the near future. At that time, the current recycling process will face new problems due to the increases in the recycling rate to the smelters. This includes insufficient combustion heat to melt copper scrap and ·almost no benefit in electrorefining because the scrap does not contain gold and silver. Thus, an alternative pyrometallurgical method for copper scrap refining will be required."

Jan 1, 2000

By George P. Demopoulos

n this study we have sought to highlight the critical linkage between individual reaction kinetic parameters (usually determined in small bench scale experiments) and large continuous reactor performance by focusing on the industrially significant zinc pressure leach process. To this end a comprehensive mathematical model previously developed for the description of this process was employed. In this paper we have examined in particular how small variations in key kinetic parameters impact on the autoclave&apos;s performance, i.e. attainment of autogenous steady-state temperature, zinc conversion and solution chemistry. The reaction parameters studied were: (i) stoichiometry of the marmatite leaching reaction; (ii) the activation energy of the same reaction, E,; (iii) the rate constant of the ferrous to ferric oxidation reaction, k,; and (iv) the apparent equilibrium constant for ferric precipitation, K,. This parameter sensitivity analysis was done under no oxygen mass transfer control limitations. Model predictions were found to be more sensitive to the kinetic parameters under certain conditions than others. The most dramatic finding was the one related to the small amount of sulfate produced during marmatite leaching. In connection to this it was found that the small percentage (< 5 %) of sulfate produced enhances the autothermal operational stability of the autoclave. The need for accurate kinetic parameter determination under conditions similar to those encountered in industrial zinc pressure leaching was demonstrated.

Jan 1, 1999

By Godwin J. Igwe

For soil remediation technology to be effective, a thorough understanding of the interactions between a targeted contaminant and the soil matrix is crucial. Proper selection of remediation technology, based on understanding the bonding/binding characteristics of the soil and contaminant, can often result in significant remediation cost savings. Contaminated soil cleanup is complicated by both the physical nature of the soil formation and the behavior of contaminants introduced into the formation. Contaminants can exist in the subsurface in different phase attached to the soil surfaces, dissolved in the ground water, or occupying pore spaces as a separate gaseous or liquid phase. Contaminants properties and how they exist in the subsurface influence their toxicity, mobility and treatability with different remediation technologies A soil characterization study was performed to provide information for remediation technology selection for an inorganic lead contaminated soil. The soil pH, TCLP analysis, thermogravimetric analysis, the soluble anions and cations present, equilibrium leaching tests, analysis by x-ray fluorescence, sequential extractions and speciation analysis using scanning electron microscopy, were all used. Results provided many insights into contaminant behavior in the soil, indicating ultimately whether soil washing or solidification/ stabilization remediation technologies were applicable.

Jan 1, 1994

By Nicholas E. Vanderborgh

Projections show that domestic coal will serve for the majority of energy supplies during the next decades. Thorough chemical cleaning of this coal can be accomplished in long-residence time, slurry-transport systems to produce high-quality fuel product. Concurrently, mineral recovery from coals will supplement existing ores. This paper describes this concept and gives preliminary engineering considerations for mineral recovery during transport operations.

Jan 1, 1982

By Ali S. Al-Watban

"In this paper, the room temperature friction and deformation properties of various polycrystalline diamonds; i.e. aggregates of diamond crystals with a ""binder"" phase of cobalt and a polycrystalline coating produced by a chemical vapour deposition processes (CVD) were studied when softer metallic and ceramic sliders were used. The experiments were conducted· at relatively low sliding speeds (10 mm/min), in a vacuum of 10-5 mbr after having cleaned the specimen surfaces by out-gassing them for about 30 min at 800 °C. As a result of increasing the number of traversals significant wear of the coated diamond by softer metallic sliders (aluminium and mild steel) was observed. With ceramic sliders, it is shown that the multiple traversals result in the formation of wear groove. With diamond silicon carbide, high friction and adhesion lead to significant metal transfer which then pre-empts cumulative deformation of the harder materials. With the diamond-cobalt composite, the friction is surprisingly low, there accumulation of wear debris on the tip of the slider but no permanent transfer of metal and the harder specimen is not damaged even after 5000 traversal.IntroductionPolycrystalline diamond is mainly produced as tool materials for the machining of hard metals and composites. Thus, the sliding friction and wear resistance are amongst the most important properties relevant to those applications.During cutting by PCD the wear mechanism is mostly influenced by the chemical affinity between the tool material and the workpiece. For example, diamond based materials are not recommended for machining ferrous materials because carbon is highly solubie in iron: This leads to the graphitisation of diamond particles and hence a high rate of diffusion wear is observed (Brookes and Lambert, 1982)."

Jan 1, 2000

By Matthew C. Binsfield

The simultaneous electro winning of zinc and manganese from waste water treatment plant sludge was studied as a part of the overall research program, which was conducted to develop the methods for removal of environmentally hazardous metals from the Bunker Hill Superfund Site. This paper discusses the electrolytic method for recovery of zinc and manganese from the solution produced by leaching of sludge with S02 + H2S04. After three stage purification of the leaching solution, zinc and manganese were electro won simultaneously in an undivided electrolytic cell. Zinc was deposited on an aluminum cathode, while manganese was simultaneously produced (as Mn02) on a lead silver anode. The electrowinning parameters studied were the effects of: temperature, current density, electrode material, spacing of electrodes, composition of electrolyte, and electrolyte additives. Anodic and cathodic efficiencies were 30 and 91%, respectively. In light of the process design parameters discussed in the paper, which are affecting the electrowinning, these efficiencies were found as acceptable with regard to the quality and marketability of the products.

Jan 1, 1996

By John W. Graydon

Incineration is an attractive alternative to the disposal of MSW in landfill sites. However, the process of incineration generates fly ash which contains significant levels of leachable heavy metals - particularly cadmium, lead, and zinc - and it is essential to manage this fly ash in an environmentally sound manner. The compositions, phases, textures, morphologies and size of fly ash particles have been studied by light microscopy, scanning electron microscopy, X-ray microanalysis, and X-ray diffraction. The detailed spatial relationships and speciation of the environmentally significant constituents have received particular emphasis. The information obtained is useful in understanding how fly ash is formed during incineration, in understanding the leaching behavior of untreated fly ash if it is disposed of in a landfill and, most importantly, in guiding the development of the best treatment strategies for fly asti to mitigate its environmental impact.

Jan 1, 1992

By Cesimiro Fabian

The crystallite size of copper electrodeposits was determined by X-Ray powder diffraction analysis using a General Area Detector Diffraction Solution (GADDS) diffractometer. Crystallite size was calculated for copper thin films which were deposited on a 316 stainless steel rotating cylinder electrode (RCE) in the presence and absence of additive ?A?. The crystallite size was calculated from a corrected full width at half maximum (FWHM) of the [110] peak profile using the Scherrer equation. The test of significant difference on crystallite size was derived using Kruskal-Wallis method. It was found that in the absence of the additive the median crystallite size was 426, which decreased to 364 in the presence of the additive. As the additive degraded, the crystallite size increased to a size similar to that observed in the absence of additive.

Jan 1, 2003

By B. Mishra, W. A. Averill

"The application of various hydrometallurgical, pyrometallurgical and electrochemical processes in the extraction, purification and production of radioactive metals as well as the use of various materials, ego metals and alloys, ceramics, polymers, etc. in the process, construction and handling equipment in the nuclear industry has generated a large stockpile of radioactively contaminated waste material and scrap metal which can not be directly discarded, recycled or considered for long-term storage due to its volume and potential hazards, without the separation of radionuclides. This paper reviews the emerging methods that have been investigated and suggested for dealing with some of these wastes and scrap material.The separation technologies studied for the recovery of radioactive components from the pyrometallurgical and electrochemical processing wastes have been discussed in details with results from some of the recent theoretical and physical modeling work as well as the data obtained from the actual waste treatment. Specific processes shall be described in terms of its advantages and limitations. These emerging separation technologies are being considered by the US Department of Energy as alternatives for dealing with the issues of environmental management [EM] and decontamination and decommissioning [D&D].IntroductionThe high temperature carbothermic or metallothermic smelting reduction methods for metal production are associated with the generation of significant quantity of waste as slags, flue dusts, sludges, residues, effluent salts etc. Certain hydrometallurgical processes also generate lots of aqueous waste due to the inherent nature of the technique. Also, the gas-based reduction processes are not applicable to many stable metal compounds, such as alumina, titania, beryllia, lanthanide and actinide oxides, etc. due to thermodynamic considerations. All these methods cause substantial environmental hazard. There is a need to develop alternative processes which have low waste or ideally a ""zero-waste"" generation.Pyrochemical processes using molten salts provide a unique opportunity for the extraction and refining of many reactive and valuable metals either directly from the beneficiated ore (aluminum, beryllium, neodymium, plutonium, uranium, etc.) or from other process effluent that contain reactive metal compounds. The processes reduce metal compounds electrolytically (A12O 3 and BeCI2) on a carbon anode or by calciothermic reduction (Po, Nd). The by-product, in the latter case, is a calcium oxide saturated halide salt. The waste-treatment to recycle the halide has to be done as a separate step or stored as a contaminated waste. A successful separation technology can provide a new insight to the waste minimization strategy for the nuclear industry."

Jan 1, 1996

By Willy Persson

A common feature of the kinds and amounts of impurities present most pyrometallurgical, processes is injection of oxygen to, remove various in the feed. The degree of success of a specific process step relies critically on control of the instantaneous oxygen potential/oxidation stage, throughout the step as well as upon termination of the step. This will, for instance, determine the distribution of impurities between metal and slag. As long as the operation is perturbation free -detailed analysis of all additions and application of advanced models often yield satisfactory control means However, a pyrometallurgical process is seldom free from disturbances, which reduces the accuracy of the static models and leads to inconsistencies in scheduled route might be uncontrollable changes in quality and quantity of feed, operator interventions and shift changes, timing of cranes, lining wear and accretions etc. The implementation of dynamic, control to correct for disturbances and, more generally for process optimization, requires continuous on-line information on, the actual status of the process. The implementation of sensors for continuous process monitoring, e.g., as regards the instantaneously prevailing oxygen potential or oxidation stage, has been hampered by the highly aggressive environment in smelters; This is. where remote-sensing techniques based on optics and spectroscopy, have proven to form invaluable, tools towards the realization of dynamic production control. Since about 15 years Semtch has developed and industrialized a remote-sensing technology, based on ,optics and spectroscopy, for continuous on-line process monitoring and production control of various pyrometallurgical processes. The presentation will discuss applicability aspects with examples and experiences from installations and tests in ferrous and non-ferrous industry. Keywords: Applied spectroscopy, Metallurgy, Process monitoring, Production. Control

Jan 1, 2003

By C. J. McKee

A gold-silver-lead-zinc deposit at Montana Tunnels, Jefferson County, Montana is located in a diatreme of middle Eocene age (45 to 50 m.y.). Sulfide minerals within the diatreme occur as disseminations, veinlets, and locally as breccia matrix. Principal sulfide minerals are pyrite, sphalerite, and galena. The diatreme is a matrix-rich quartz latitic breccia with a fine grained rather soft matrix and heterolithic clasts. The ore deposit contains approximately 50 million tons of ore at a grade of 0.025 oz/ton Au, 0.5 oz/ton Ag, 0.25 % Pb, and 0.65 % Zn. Mining is by open pit methods. The original process flowsheet included flotation and cyanide leaching. Problems with the leaching circuit led to a change to the straight flotation process which is presently in use. To maintain a reason-ably uniform feed material, blending of ore is required for grades of four metals as well as for ore hardness and oxidation.

Jan 1, 1988

By Fumito Tanaka

The Mitsubishi process is the sole pyrometallurgical process for the continuous production of blister copper from Copper concentrates and has been successfully operated around the world. The development of calcium ferrite slag (CaO-FeOx-Cu10), the so-called "C-slag", has enabled continuous converting from matte to blister copper in the commercial scale operations. Commercial interests in the slag led to many papers over the CaO-FeOx slag. However, Cu2O bearing slag has not been studied well due to experimental difficulties. The authors have quantified the thermodynamic properties of the CaO-FeOX-Cu2O system. The results have been utilized to analyze various issues related to the converting furnace, such as the magnetite precipitation from the slag or from blister copper and to develop better controlling criteria for the continuous converting operation. -

Jan 1, 2003

Reduction of titania and ilmenite ores by Cf4-H2-Ar gas mixture was investigated in a laboratory fixed bed reactor. Titania was reduced to titanium oxycarbide in the temperature range of 12OO-1500°C. At 1400-15000C, the extent of reduction of titania to titanium oxycarbide achieved more than 85% in 90 min. Optimum conditions for titanium oxycarbide synthesis by reduction of titania include temperature in the range of 1300-1450°C, methane content 8 vol% and hydrogen content above 35 vol%. Ilmenite ore was reduced by Cf4-HrAr gas mixture to metallic iron and titanium oxycarbide. Metallic iron catalyzed methane cracking and solid carbon deposition. Titanium oxycarbide formed at temperatures as low as 950°C. The optimum temperature for reduction of ilmenite is 1200°C and the optimum methane content is 8 vol%. Increase in hydrogen content increased both rate and extent of reduction. With 5 vol% CH4-75 vol% Hr20 vol% Ar gas mixture, the reduction of ilmenite completed in 60 min. Reduction of titanium oxides to oxycarbide with following chlorination may be an efficient alternative technology for processing of titanium minerals.

Jan 1, 2001

By M. S. Moats

The treatment of oxidized residues of zinc with high iron content continues to present a technical challenge in both the steel and zinc industries. Two main problems are commonly identified and include high treatment costs and environmental concerns about contaminated, iron-bearing residuals. A new approach to this problem is described in which selective separation of the iron and zinc into salable products may be potentially feasible. The waste material is first leached to give a solution having an approximate concentration of 110 g/l Zn, 15 g/1 Fe and 40 g/1 H2SO4 and other impurities such as Pb, Cd, Cu and Sb. A suitable organic, such as D2EHPA, is used to load the majority of the iron. The aqueous phase is then acceptable for zinc electrowinning after standard solution purification. The novel step in the flow sheet is the efficient recovery of the ferric iron from the organic solvent using a solid metal to reduce the iron to the ferrous state. The Fe+2 is easily stripped into an aqueous phase in a relatively pure form, suitable for use in water treatment. Process parameters and possible flow sheet designs are described and discussed.

Jan 1, 1995

By Sergey Shabala

Green leaf tissues convert solar energy into the energy of chemical bonds of sugar molecules during the process of photosynthesis. The efficiency of this conversion can be much higher than efficiency of any of the currently known silicon-based solar panels. Importantly, vast amounts of CO2 are assimilated during this process. The efficiency of photosynthesis is critically dependent on the availability of a large number of nutrients, among which metal cations such as K, Ca, Mg, Cu, Zn, Fe, Mn, and Ni play a key role. In this paper I summarize basic requirements and major functions for each of these essential nutrients in plant photosynthesis, both at the whole-plant and molecular level. I will talk about how these requirements may be affected by the global climate trends and discuss the prospects of creating artificial photosynthetic “bioreactors” for efficient energy conversion and CO2 assimilation.

Jan 1, 2009

By S. E. James

EAF dust has been listed as a "hazardous waste" due to the presence of lead and cadmium, and at times chromium. The 550,00 tpy production of . .EA]&apos; dust, estimated for the United States alone, contains more than 10,000 tpy of lead and about 250 tpy of cadmium in addition to nearly 1&apos;00,000 tpy zinc. Even though the listing of .EAF dust as a hazardous material stimulated extractive metallurgical work worldwide, process development efforts have focused only on the recycle of the potentially-valuable zinc units. However, the recycle of the lead and cadmium, while not lucrative, is the more critical effort. Horsehead Resource Development Company, Inc. (HRD), in conjunction with its sister company, Zinc Corporation of America (ZCA), has taken a unique approach to total recycle of the toxic heavy metals found in the EAF dust. Impure oxide, produced by either a Waelz kiln or FLAME REACTOR Process and containing the lead and cadmium, is calcined in a rotary kiln at Palmerton, Pennsylvania, to produce a refined zinc-rich intermediate for ZCA&apos;s electrothermic zinc plant at Monaca, Pennsylvania. During the calcining operation, lead and cadmium are concentrated in a fume product and shipped to ZCA&apos;s electrolytic plant at Bartlesville, Oklahoma. At Bartlesville, a new hydrometallurgical circuit has been constructed and the existing cadmium plant expanded. The combined facilities permit the total recovery of cadmium to refined metal and the lead to .a silver-rich intermediate, which is sold to lead smelters. In this paper the Waelzing, calcining and new leaching facilities will be described.

Jan 1, 1990