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By M. Neises, M. Roeb, C. Sattler, S. Stenger

"A two-step thermo-chemical cycle process has been developed and investigated. It is based on metal oxide redox pair systems, which can split carbon dioxide as well as water molecules by extracting oxygen atoms and reversibly incorporating them into their lattice. If concentrated solar radiation is used as the heat source, a promising method exists to produce synthesis gas from water and CO2. An easy way of operation is gained by the combination of a ceramic substrate as the absorber structure, which can be heated to high temperatures with concentrated solar radiation, and of a metal oxide coating which is capable to carry out the redox reactions. The performance and kinetics of a ferrite based redox material coated on ceramic substrates were investigated in a laboratory set-up. CO2 could be reduced with significant conversions. In addition, several side reactions were observed like the formation of carbon and like the Boudouard reaction.IntroductionThe search for alternative energy carriers and for processes able to reuse carbon dioxide stimulates the research for sustainable routes of alternative fuel production. In the scope of this search thermo-chemical processes combined with sources of concentrated solar energy have become more and more attractive. Ideally, the only raw materials for such processes are water (H2O) and carbon dioxide (CO2) enabling not only a process free of emissions, but also allow to reduce emissions of other processes by reusing CO2 to provide synthesis gas, which itself can be applied to produce chemical commodities or even better synthetic fuels like methanol or petrol.In contrast to the direct splitting of those raw materials, thermochemical cycles split water and CO2 in several steps and enable hydrogen (H2) and carbon monoxide (CO) generation at temperatures controllable by today’s technical equipment. One of the most interesting thermochemical cycles is a two-step process using metal oxide based redox systems. During the first step of this cycle (the regeneration step) the metal oxide is reduced setting some of its lattice oxygen free according to reaction (1). In the next step (the splitting) the reduced and activated material is oxidised by withdrawing oxygen from water and CO2 and at the same time hydrogen and CO is set free according to reactions (2a) and (2b) respectively."

Jan 1, 2011

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 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 Ximeng Zhu

The electrochemical behavior of mineral and coal pyrites in stirred and quiescent alkaline boratelsulfate solutions @H 7.9-10.5) have been investigated using cyclic voltammetry. Significant differences in the electrochemical response of these pyrites were observed. At the mineral pyrite surface, three anodic peaks at about -0.8 V, -0.1 V and +0.5 V (SCE) have been detected along with their corresponding reduction peaks. The first two peaks correspond to FeIFeOI) and FeOI)lFe(III) oxidation. The third peak is present for quiescent conditions but disappears as a distinct peak when the electrolyte is stirred. In the upper voltage region +0.30V (SCE), the current increases markedly during stirring and the reactions correspond to the oxidation of pyrite with the formation FeOII) oxides plus elemental sulfur. Also there is evidence that Fe oxy-ions form. Coal pyrites, under rapid sweep conditions display only the first two anodic peaks, the associated reduction peaks and an additional reduction peak corresponding to one or more of the high voltage oxidation products. After prolonged exposure to high potentials, coal pyrite displays reactions similar to those of mineral pyrite but at much higher current densities demonstrating the much higher reactivity of the coal pyrite. The reactivity sequence was Upper Freeport coal pyrite > Pittsburgh coal pyrite > mineral pyrite.

Jan 1, 1991

By Ronald Erdmann

Today the BOF filter dusts and sludges are mainly dumped due to their zinc contents. By typically ranging from 2 to 5 % they prevent the filter dusts and sludges from beeing recycled via the blast furnace route. Based on the different discharge kinetics of Iron and zinc during the main blowing period In a bottom stirred BOF a simple and efficient system for recovery allow zinc fractions has been developed. The obtained material Is suitable for recycling without nsc of shell formation In the blast furnace. Different subsequent development steps have been performed. By starling with a very simple lime dependent model the sludge from the BOF off gas cleaning system was collected in two different sludge channel systems. This model based an the fact that most of the scrap based zinc Is discharged from the melt within the first eight to ten minutes of the BOF process. To Improve the system a spectroscope zinc sensor was Installed at the hot section of the off gas cleaning system to get more reliable informations on the actual zinc concentation of the BOF dust. By use of the system up to 50 % of the BOF sludge can be recycled.

Jan 1, 1995

By Samson Adeosun, Sanmbo Balogun, David Esezobor

"Iron and steel making processes give rise to large amounts of usable and unusable materials, the latter generally being termed wastes. It is sometimes difficult to distinguish between re-usable by-products and wastes which cannot be sold or land-filled. Much depends on circumstances such as the local market for the material. This can itself vary from time to time with by-products which cannot be used or sold becoming wastes and vice versa. This paper defines the concept of “waste-free technology”, discusses its development in the steel industry and highlights the benefits of the technology to the manufacturing sector and the environment. The paper also articulates how the “waste-free” technology could be applied in the proposed Ajaokuta integrated steel plant in Nigeria.IntroductionIn the past, nature was considered an inexhaustible store. Its resources were consequently exploited and waste products therefrom were discarded. Today, attitudes have not changed appreciably even as raw materials cost rise by the year to pose a series of socio-economic problems, which, among others, may include the rational and optimum utilization of resources, environmental protection and reduction of waste formation. Consequently, industrialists now face unexpected regulatory pressure in areas of pollution prevention, waste minimization and hazardous waste disposal.Iron and steel making processes give rise to significant amounts of usable and un-usable materials, the latter generally being termed waste. It is sometimes difficult to distinguish between re-usable by-products and wastes which cannot be sold or land-filled. Much depends on circumstances such as the local market for the material. This can itself vary from time to time with by-products which cannot be used or sold becoming wastes and vice versa. In this paper, the term waste refers to those materials that are either irrationally utilized or, land-filled and part of the byproducts that are not utilized. It includes that part of used materials which is not incorporated into the products manufactured during a process stage and which in contrast to reuseable materials, is considered not suitable for any further use, owing to technical or economic factors. In general, these materials are inorganic and parts of them are either utilized or passed to the other processes; the other part should be disposed of using well-established waste disposal practices to avoid any environmental threat.Thus, creative methods must be developed to modify the manufacturing processes to reduce emissions and process wastes by fully utilizing all resources. One method of eliminating the negative effect of waste formation is the use of purification and cleaning structures (pollution control system, PCS). These are, however, quite expensive."

Jan 1, 2008

By I. M. Richardson, M. Janssen, W. Geerstma, I. J. Bennett, V. A. Popovich

Avoiding wafer breakage is a big challenge in the photovoltaic silicon industry, limiting production yield and further price reduction. Special fracture strength tests suitable for thin silicon solar wafers and solar cells, to be used in combination with Weibull statistics, finiteelement (FE) modelling and digital image correlation have been developed in order to study the mechanical stability of solar wafers. The results show that removal of the saw damage significantly increases the strength of crystalline silicon wafers. Furthermore, it was found that silicon crystallinity and the location where the wafer is extracted from the cast Si ingot have a significant effect on the strength, namely samples taken from the bottom of the ingot are 30% stronger than those taken from the top. The study also showed that there is a decrease in fracture strength when an anti-reflective SiNx coating is applied, which is caused by high thermal stresses.

Jan 1, 2015

By Timothy W. Ellis

"This paper presents the basic theory of operation, physical chemistry and phase equilibria which allow the development of liquid-liquid extraction circuits based on metallic solvents. The incorporation of reduction and reduction/diffusion processes into the process scheme is discussed and a detailed description of several liquid-liquid extraction schemes are developed. A synopsis of experimental results obtained using this method to separate rare earth and other metal based materials will be given.IntroductionConcerns over the effects of waste materials in the environment has been one of the significant social hallmarks of the late 20th century. Essentially every industrialized country has had to incorporate the cost of waste material into the equation of production. Legislative initiatives have led to the passing of very tough laws, by historical standards, which govern the environmental impact of materials processing.Liquid-Liquid extraction is a very common unit operation normally using aqueous and/or organic based solvents. Early work at the Ames Laboratory focused on the use of this technique for the reprocessing of spent fuel from liquid metal breeder reactors by the use of metallic solvents. Recently, we have revisited this area as a means to recycle/reprocess several emerging rare earth based materials, although this method has a much wider range of application. The reinvestigation of this technology is particularly timely as hydrometallurgical based processes are coming under increasing scrutiny in the U.S.A. by the Environmental Protection Agency (EPA). Although technology currently exists to remove contaminants from aqueous based waste streams, often the application of such methods is expensive. With proper design and judicious selection of reagents liquid metal extraction can achieve a high recovery along with a benign waste stream.This process has several possible advantages over other technologies. First is the elimination of aqueous solvents. Therefore, problems associated with disposal or reprocessing of the aqueous carrier are eliminated. Second, with proper system design, very high separation coefficients can be obtained thus limiting the number of stages required. Third, metals are extracted from metals with a metallic product, thereby eliminating the need to re-reduce metal for oxides or other compounds which are the common output for aqueous based extraction procedures."

Jan 1, 1996

By Dian Adisty, Leiv Kolbeinsen, Eli Ringdalen

In Si and FeSi production, the main Si source is SiO2, in the form of quartz. Reactions with SiO2 generate SiO-gas that further reacts with SiC to Si. During heating, quartz will transform to other SiO2 modifications with cristobalite as the stable high temperature phase. Transformation to cristobalite has been investigated and shown to be a slow process where the rate varies between the investigated quartz types. The effect of quartz versus cristobalite as SiO2 source has been studied for reaction (1) 2SiO2 + SiC = 3SiO + CO, by heating of pellets with SiO2 + SiC in Ar-gas. The reaction was faster with cristobalite than with quartz. Initial experiments indicates that this is the case only in Ar and not in CO-atmosphere The higher specific surface area of cristobalite is believed to contribute to the higher rate. The industrial consequences of the observed difference between quartz types are discussed.

Jan 1, 2014

By R. Hurman Eric

The flow of molten slag and matte and the estimation of the mass of settled matte in electric furnaces is discussed and the action of the electric furnace as a settler is considered. Particle size of the concentrate and its grade are major contributors to settler dimensions. Discussion on the production capacity of the electric furnace with reference to operating current, power input, furnace dimensions such as width and length and electrode diameter are given. These discussions are based on considerations derived mainly from experimentally determined properties of the slag such as its resistivity, viscosity and liquidus temperature. Extension of the design and operating considerations to circular furnace symmetry is also discussed.

Jan 1, 1995

By Andreas Siegmund

During the decade of the nineties the conventional method of primary lead smelting (sinter machine/blast furnace) was successfully challenged by the introduction of novel direct and continuous smelting processes. In combination with a significant shift in market structure, as well as more stringent government regulations these modem technological innovations like the QSL, Kivcet, and Isa/Ausmelt processes became more than major competitors. They have proven to be economically and environmentally viable. The intensification of the metallurgical reaction by applying oxygen enriched or pure oxygen bath or flash smelting principles resulted in cost savings and a higher flexibility with respect to raw materials and additives usage. By synchronizing individual auxiliary plant sections with the smelting process a virtually waste-free production and low-emission mode of operation with nearly optimum energy exploitation is achieved. The primary lead industry will gradually substitute the sinter -blast furnace operation with novel high-energy efficient technologies in the new millennium.

Jan 1, 2003

By F. E. Wagner, L. J. Cabri, Y. G. Safonov, N. S. Bortnikov, A. D. Genkin, J. Friedl, G. N. Gamyanin

"A multidisciplinary investigation (including INAA, SIMS, EPMA, and Mossbauer Spectroscopy) was used to characterize gold in four of the largest Siberian mesothermal sulfide gold deposits. These are the Olympiada (""'750 metric tons gold) and Veduga (estimated at 75-100 metric tons gold) deposits in the Enisei Mountain Range and the Nezhdaninskoye (z500 metric tons gold) and Sentachan deposits in the Verchoyansk-Kolyma area. It was found that some of the mineralization is refractory in all four deposits, largely due to the occurrence of ""invisible"" gold in arsenopyrite as well as within pyrite, but with a lesser concentration. The gold concentration and its distribution varies considerably both within and between arsenopyrite grains, with implications for processing options such as heap leaching. The ore most likely to be amenable to heap leaching is the oxidized ore of the #4 orebody of the Olympiada deposit, but further quantitative mineralogical investigations are recommended for this orebody's sulfide ore and for the ores of the Nezhdaninskoye deposit. Following a full mineralogical characterization, it is possible that economic viability will depend on a combination of pre-concentration with or without pre-treatment, followed by heap leaching of some tailings products.Acknowledgements· The Russian authors performed this study under an ""Eco res"" Project which was financially supported by the Ministry of Science and New Technology of the Russian Federation. C.J. Stanley wishes to thank John Spratt and Terry Williams for help with EPMA. F.E. Wagner acknowledges the Deutsche Forschungsgemeinschaft for a grant supporting the Mossbauer studies. L.J. Cabri is grateful to the following: M. Beaulne, D. Carson and J.H.G. Laflamme for technical support, K.E. Haque for technical comments, and D.M. Hausen and W. Petruk for editorial suggestions."

Jan 1, 1997

By Akira Yazawa

Experimental results for the distribution ratios of various elements between the slag, matte and/or copper in the silica-saturated copper smelting system were summarized. The experiments were carried out under an oxidative smelting condition with S02 gas flow, and also a reductive smelting condition equilibrating with metallic copper or iron. To evaluate the results thermodynamically, the availability of one atom cation base expression for the constituent compounds is emphasized from both of theoretical and practical standpoints. Both of oxidic and sulfidic dissolutions in slag are postulated for some elements such as copper, nickel and lead., and the experimental results are reasonably explained thermo-dynamically. The results for the mutual solubility between matte and ferrite slag and the distribution of minor elements between liquid copper and ferrite slag are also discussed.

Jan 1, 1983

By Brian Balmforth

Solvent extraction has been applied successfully to the recovery of a range of metals from a variety of process streams. Particular benefits are derived from the use of new highly selective extractants. These will be exemplified by case studies including the recovery of zinc from sulfate and chloride media using ZENECA's new extractants which show a very high selectivity over iron and the recovery of antimony and bismuth from copper refinery electrolytes using ZENECA's strong and selective extractant DS5834. The conclusions are drawn that solvent extraction is a cost effective technology for metal recovery and recycling, even when used to treat relatively small volume/low concentration process streams, and that it can provide the essential enabling components of a larger system for waste minimisation programmes.

Jan 1, 1996

By Yosry Attia

Recent emphasis on environmental effects and costs of conventional mining processing, plus success in accelerating bacterial action, suggest that biotechnology be explored for gold ore processing. In our paper, the past experience with organisms in processing gold is reviewed. The use of microorganisms for liberation of gold from sulfide ores as a substitute for fine grinding is discussed. The possibility of accumulation of gold from solutions, such as cyanide solutions, is explored as a potential replacement for such processes, such as carbon-in-pulp or ion exchange. The improvement in engineering technology and kinetics needed to scale-up from laboratory experiments to production scale are outlined.

Jan 1, 1985

By LuisW. Pommier

The industrial wastes generated by the plating industry, the circuit board manufacturing industries and other related industries normally contain high concentrations of metals, which make them hazardous. The extraction of the contained metals and their separation may be achieved by both pyro and hydro metallurgical processes. Some of the industrial wastes, those rich in some metals like nickel for instance, are being treated like mine ore concentrates and are being fed to smelting furnaces. The slags from these smelter operations are hazardous. They have, however, special environmental dispensations issued by the regulatory authorities. Hydro-metallurflcal processes have been reported. They also generate a residue which is hazardous because not all the valuable metals are leached out and also, because "non valuable" components, like chromium, are less readily leached. Residues from the plating industry, containing nickel, copper. zinc, iron and chromium as the major constituents and also sodium and calcium, together with cadmium, cobalt, lead. manganese, magnesium, molybdenum, and potassium, have been processed for the extraction of the valuable components. The generation of electrolytic nickel, copper and zinc and also of ferric chloride and chromium oxide is reported. The operation is achieved by a caustic leach for the extraction of zinc, followed by a sulfuric acid leach for the extraction of nickel and copper. This acid leach also extracts the iron and some chromium. The nickel copper and zinc are rendered pure by electrolysis, the iron is oxidized for the production of ferric chloride and the chromium is recovered as an oxide. The leaching operation is performed in two stages, first at a pH of 2.5 to generate an electrolyte for the partial recovery of the metals and then at a pH of 0.5 for the complete extraction of the metals. This leaching operation generates a residue, which although small in volume compared to the initial feed, still contains traces of the valuable metals and a portion of the chromium which makes it hazardous. Additional leaching with hydrochloric acid or nitric acid is required for its complete dissolution. The other minor constituents mentioned are present in concentrations each of less than 0.1% and are handled as impurities in the process. The metals which are soluble at a pH 0.5 and precipitate between 0.5 and 2.0 are bled off. Other impurities will concentrate on the raffinate from the solvent extraction operations from whence they are bled off. These bleeding streams are hazardous and the "impurity metals" are now present in concentrations which would make them valuable, however, the size of these streams is so small that they do not warrant their processing, however they could be marketed to specialized smelters. The extraction of the valuable metals, of the hazardous constituents, the generation of a marketable mixture of minor constituents and the production of a non-hazardous residue for declassification is profitably achieved.

Jan 1, 1998

By S. Abe

Various copper anodes to be electrorefined were subjected to a heat treatment comprising annealing at a temperature in the range of 700 °c to 1,000 °c followed by a slow cooling preferably on the order of about 150 °c, and using these heat treated anodes , a series of dissolution experiments were conducted under conventional electrorefining conditions. The results obtained have indicated that the above annealing/slow cooling process dramatically improves the dissolution activity regardless of the type of anodes. As an example, passivation times of l to 3 minutes in a standard test have been increased to more than 80 minutes by this innovated heat treatment. Other advantages sterning from the improved anodic activity include reduced electrical short circuiting which results in substantial labor effort in the tankhouse, reduced energy requirement, and reduced cost of processing anode slimes because the amount of anode slimes is reduced. In addition, this process gives rise to a dramatic change in the nature of anode slime layer formed in such a way that a comparable final cathode copper product can be achieved even from high-impurity copper starting material.

Jan 1, 1987

By G. G. Richards

The zinc slag fuming process is used to recover zinc from molten iron-calcium silicate slags by treatment with pulverized coal and air. The rate of zinc fuming is controlled by the complex interaction of several kinetic factors including the rate of entrainment of coal in the slag, the extent of the coal-slag reaction and the rate of ferrous oxide oxidation to ferric oxide. This paper briefly outlines the mechanism of fuming and, on this basis, optimization of process parameters is discussed. Modelling analysis and recent industrial trials at Cominco show that coal entrainment in the slag, bath temperature, and bath depth are critical variables affecting process rate and efficiency. The first step in process optimization is to assess coal bypass of the bath. In general, changes which promote operation at a higher temperature, greater coal entrainment in the slag and extended residence time of the coal in the bath increase fuming performance. Coal entrainment is controlled by injection conditions whereas bath temperature is a function of coal combustion and ferrous oxide oxidation. Residence time of the coal is largely a function of bath depth. The implication of model predictions for continuous fuming is shown.

Jan 1, 1994

By Zhang Duomo

A novel homogenous precipitation method, including microwave heating, solution conductivity controlling and freeze drying, was developed for the preparation of US nanoparticles. The effects of the precipitation conditions on the structure and morphology of CdS particles were discussed individually. It was found that under the experimental conditions the particle sizes were controllable in the range of 14nm to 100nm. Blend-type CdS was obtained from nitrate or sulphate solution and the more stable wurtzite-type US was obtained from chloride solution, which was ascribed to the coordination of C1 and Cd2+ altering the supersaturation of the solution as well as the different growth units and their connecting patterns, In the precipitation process the surface of US nanoparticles were surface modified with CH3CHSCOOH. The results demonstrate that the bifunctional thiols of thioglycolic acid modified the surface through Cd-S coordination bonding and the induced counter ion AOT-SO3 as the balance charge further increased the stability and dispersity of US nanoparticles. This surface-modified US nanoparticles had been used to prepare nonlinear optics and self-assemble catalysts.

Jan 1, 2003

By Donna Guillen, Matthew Lehar, Sebastian Freund, Jennifer Jackson, Helge Klockow

"Research and development is currently underway to design an Organic Rankine Cycle (ORC) system with the evaporator placed directly in the hot exhaust stream produced by a gas turbine (GT). ORCs can be used to generate electricity from heat that would otherwise be wasted, thus producing carbon-free energy. In conventional ORC configurations, an intermediate oil loop is used to separate the hot gas from the flammable working fluid. The goal of this research effort is to improve cycle efficiency and cost by eliminating the pumps, heat exchangers and all other added cost and complexity of the additional heat transfer loop by developing an evaporator that resides in the waste heat stream. Direct evaporation – although simpler and less expensive to implement than indirect evaporation of the working fluid – has historically been avoided due to a number of technical challenges imposed by the limitations of the working fluid. The high temperature of the hot exhaust gas may cause decomposition of the organic working fluid and safety is a major concern due to the high flammability of some of these working fluids. The research team has addressed these challenges and developed a new direct evaporator design that can reduce the ORC system cost by up to 15%, enabling the rapid adoption of ORCs for waste heat recovery. The ORC system is intended to integrate with the GT either as a retrofit or to be marketed as a single package, thus maintaining the manufacturer’s warranty.IntroductionWaste heat from turbines and engines used in industrial applications along with waste heat from industrial processes are exceptionally abundant sources of energy. If even a fraction of this waste heat could be economically converted to useful electricity, it would have a tangible and very positive impact on the economic health, energy consumption, and carbon emissions in the U.S. manufacturing sector. Land-based gas turbines are used in a broad range of applications to produce both shaft and electrical power. Most commonly known for generating electricity either as peaking units or as base load units, they are also used to directly drive pumps, compressors or other machinery requiring shaft power. Simple cycle gas turbines have the advantage of a short startup time relative to coal-fired and nuclear units, however, they incur a significant penalty on their efficiency. Large frame gas turbines usually are combined with bottoming steam-based Rankine cycles to increase the overall efficiency of the system and thereby improve their cost performance. Small-frame gas turbines with exhaust temperatures around 500°C could in principle benefit from steam bottoming cycles, but rarely use them in practice because of the high capital cost of the steam system. Particularly for base load small frame gas turbines, akin to those used in pipeline applications, an increase in efficiency is highly desirable."

Jan 1, 2011