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By P. N. Anyalebechi

"The effects of solidification rate, initial melt hydrogen concentration, and grain refining on porosity formation in aluminum alloy 2024 have been investigated with unidirectionally cooled laboratory-size ingots. The ingots were prepared from melts containing hydrogen concentration of 0.059-0.27 cm3/100 g and solidified at 0.2-37 °C/s. As expected, the amount of porosity, average pore size, and pore number density increased with increase in melt hydrogen concentration and decrease in solidification rate. However, the effect of solidification rate was greater at the very low melt hydrogen concentration (0.059 cm3/100 g). These results are consistent with reported effects of solidification rate and melt hydrogen content on porosity formation in other aluminum alloys. Interestingly, addition of grain refiner slightly increased the amount of porosity and the average pore size, especially at solidification rates above 1°C/s. IntroductionIn shaped castings and wrought products fabricated from ingots, billets, bars, or slabs of aluminum and its alloys porosity formation is a problem. This is because it compromises their tensile strength, fracture toughness, and fatigue properties [ 1-18]. The pores are usually the crack initiation and propagation sites [6,8,9] and the largest pores tend to dictate the fatigue life of the aluminum products [9,10,14]. Porous regions within an aluminum product probably yield first due to the reduced tensile load bearing capacity, causing the concentration of the strain near the voids which subsequently results in premature fracture. In aluminum alloy ingots, billets, bars and slabs porosity formation is particularly problematic because of its persistence through fabrication and potential for reappearance or exacerbation during subsequent thermal treatment processes before and/or after fabrication [19]. In fact, persistence of microporosity is a serious problem in large thick plates of wrought aluminum alloy products that must be rolled from correspondingly large direct-chill or electromagnetic cast ingots. Some of these thick plate products are machined into large aircraft components that are required in service to withstand multi-directional stresses and to possess high fatigue strength, fracture toughness, resistance to stress corrosion cracking, and strength in the short-transverse direction [1,20]."

Jan 1, 2011

By G. Roy Chaudhury

Adsorption techniques are comparatively low cost and effective for treatment of arsenic contaminated drinking water. Various adsorbents such as alumina, ferrihydrite and manganese ores have been used, but there has been little investigation of modifying the structure of ferrihydrite to improve its adsorptive efficiency of As(III) and As(V). In the present study the incorporation of manganese oxide into the ferrihydrite structure was carried out and the prepared materials used in arsenic adsorption experiments. The compounds were X-ray amorphous, but TGA/DTA and FTIR analysis showed some structural characteristics. Sorption studies reported in this paper indicate the excellent arsenic removal properties of the manganese/iron compounds with a loading capacity of 0.3 mmol/g. Adsorption follows first order kinetics and the results fitted to adsorption and mass transfer models. Arsenic levels in water containing 1 mg/L As(V) were reduced by 50% in 20 minutes and 90% in 60 minutes using 1 g/L manganic ferric oxyhydroxide.

Jan 1, 2003

By Isabela Leao Amaral da Silva, Felipe Perisse Duarte Lopes, Alice Barreto Bevitori, Sergio Neves Monteiro

"Jute fibers have in the past decades being investigated as possible reinforcement of polymer composites. However, information is still needed on the fiber interaction with a polymeric matrix for a complete evaluation of the capacity of load transference inside the composite. The present work investigated the interaction of jute fibers with polyester matrix by means of the critical length assessment through pullout tests. Tensile tests of polyester sockets embedded with different fiber lengths allowed the critical length to be determined and then the interface shear stress to be calculated. A relatively low interfacial strength was found, which indicates a weak adhesion between the ramie fiber and the polyester matrix. The SEM analysis of pulled out fibers corroborates this result.Introduction Natural fiber, mainly those lignocellulosic extracted from plants, have, in the past few decades, attracted the attention not only of scientists but also of industrial technologists of our society interested in their engineering applications. As it is well known, uses of natural fiber in clothes carpets, baskets, ropes and low cost construction roofing has existed from the beginning of our civilization. Today environmental and energy saving issues are motivating research works on new uses of lignocellulosic fibers in polymer composites [1-6]. Moreover, industrial application of lignocellulosic fiber composites are already in technological sectors such the automobile industry, packing and civil construction [7-9].In addition to environmental, economical and social benefits, some lignocellulosic fibers present specific properties that are comparable to those of other synthetic fiber used for polymer composite reinforcement. For instance, the specific strength (GPa.cm3/g) of curaua (1.31), sisal (0.92) and ramie (0.93) fibers, from results obtained with very thin diameters [10] are relatively closer to that of glass fiber E (1.33). Therefore, in principle, it would be technically justified to replace glass fiber, which is more expensive, toxic and represents a problem to the environment [ll], by a strong lignocellulosic fiber. However, serious drawbacks such non-uniform dimensions and heterogeneous properties [6] as well as the tendency to form aggregates during processing and incompatibility with a hydrophobic polymer matrix, reduce the potential of lignocellulosic fiber to be used as composite reinforcement [1-6]. In particular, a low interfacial strength causes a weak adhesion between the hydrophilic fiber and the polymer matrix."

Jan 1, 2011

By Alwin Frei, Aldo Steinfeld, Peter G. Loutzenhiser, Enrico Guglielmini

"Using concentrated solar radiation as the energy source of high-temperature process heat, the carbothermal reductions of Al2O3 to Al and SiO2 to Si were examined thermodynamically and demonstrated experimentally at vacuum pressures. Reducing the system pressure favors Al(g) and Si(g) formation, enabling their vacuum distillation and avoiding contamination by carbides and/or oxycarbides. Exploratory experimentation in a solar reactor was performed with mixtures of charcoal with alumina and silica in the ranges of 1300-2000 K and 1997–2263 K, respectively, at 10-3 bar by direct exposure to concentrated thermal radiation. Distilled samples contained up to 19 wt% of Al in Al-Al2O3 mixtures and 79 wt% of Si in Si-SiO2 mixtures. When the reducing agent is derived from a biomass source, the solar-driven carbothermal processes are CO2 neutral.IntroductionMetallurgical extractive processes for producing Al1-2 from Al2O3 and Si3-6 from SiO2 are characterized by their high specific energy consumption and concomitant emissions. Alternatively, concentrated solar energy can be used as a high-temperature heat source to drive the carbothermal reductions and, thus, avoid greenhouse gas emissions and other pollutants derived from fossil-fuel-based processes7-12. When the reducing agent is biomass charcoal, the solar-driven carbothermal reduction is CO2 neutral. The carbothermal reductions of Al2O3 and SiO2 are represented by the simplified overall stoichiometric reactions:"

Jan 1, 2011

By José Antonio, Silva Souza, Luis Alves Venancio, Emanuel Negrão Macedo, Antonio Ernandes M. Paiva

"The production of alumina from bauxite using the Bayer process generate 1.25 ton of the residue known by red mud and 460 kg of CO2 per ton of alumina.The direct use of exhaust gases from the alumina refineries to react and neutralize the bauxite residue may allow a double gain: open a wide range of new applications for bauxite residue reducing the reactivity of red mud and sequester approximately 15% or 67 kg of CO2 per ton of alumina.This paper shows the reaction of a suspension of bauxite residue-water with a simulation of the calcinator exhaust gases of the refinery. The influence of the temperature and the ratio water red mud is also analyzed.2 IntroductionThe production of millions of tons per year of alumina around the world generates around 1.25 tones of the residue known as red mud and 0.4 ton of CO2 per ton of alumina . The vast majority of the red mud is stored in large sealed lakes. Due to the high reactivity is considered dangerous and currently there is no operating process capable of reuse all the material at any refinery. These lakes after filled of solid material eventually have the surface revegetated. Otherwise will need monitoring for decades and remain as an environmental passive. The search of a industrial process that combine the reduction of the CO2 emission and the reduction the pH of the red mud opening the possibility of use in large scale in a economically viable way is the main objective of this work.The use of the exhaust gases of the refineries to neutralize the bauxite residue may allow a double gain: Open a large array of new applications for the residue with the reduction of its reactivity and sequester million of tones of CO2 plus other gases like SO2 [7] and NOx.This project main objective is to study the reaction of the CO2 with the Bayer process residue in order to obtain the basic parameters to design an equipment capable of process this reaction on a pilot scale. With this objective compositions of red mud on spray were processed with flow of gas containing CO2 at different temperatures and with concentration similar to the exhaust gases of the calcination process of the refineries. With the results, basic concepts of a pilot scale equipment were evaluated.A revision of the work already done on this type of residue were done [3, 9, 10]. Alternatives and potential barriers on chemistry and environmental fields were discussed. With the objective of industrial application the potential use of these materials were evaluated through the pH control, mass balance and x-ray diffraction."

Jan 1, 2010

By Bryce Clark

An outline of the current world's known sources and resources of cobalt, looking at both land and possible undersea deposits, is given as a prelude to an examination of current and historical actual world production on geographic/company basis. These production figures will be compared to apparent consumption by segments, both geopraghically and end-use based. Consumption of cobalt has been regarded as price sensitive and a historical look at prices against all other figures will be considered. Included in this scenario will be a brief overview of cobalt's uses and a comment on future trends. Tables will include: Resources, Production, Consumption, Prices, Markets.

Jan 1, 1993

By Adam J. Gesing

Eddy current separators are increasingly used by the auto shredder operators to produce higher grade of nonferrous metal concentrate for recycling. While this increases the unit price of the concentrate, metal losses through inefficient metal recovery quickly offset the price differential. We show how to optimize the eddy current separation system at the shredder to maximize mate- rial throughput, nonferrous metal recovery and grade of the nonferrous metal concentrate.

Jan 1, 1998

By Manuel Alvarado, David Nemir, Jan Beck

"Thermoelectric generation using special N-doped and P-doped semiconductors is well known as a means for direct heat energy to electrical energy conversion without the need for moving parts. The technology is used today in niche markets for low level electricity production and has been proposed as a scalable means for capturing large scale energy from waste heat streams. The choice of geometry of the thermoelements and conductors is critical to the successful implementation of a waste heat recovery system in order to manage losses due to Joule heating and diffusive heat flows. This paper describes a simulation study to define the performance impact of different aspect ratios for the active thermoelements and the electrical interconnect. The use of a finite element model that incorporates the intercoupled heat and electrical energy flows highlights some of the issues impacting scalability.IntroductionThermoelectric phenomena arise out of the intercoupled electrical and thermal currents in a material. A two-element thermoelectric generator is depicted in Figure 1. It is constructed by connecting an N-type thermoelement and a P-type thermoelement in electrical series, with both elements in thermal parallel between a heat source and a heat sink. The electrical series connection is made by attaching conductors as shown. Ideally, these series connection elements will be both good thermal conductors and good electrical conductors.The two element generator in Figure 1 is disposed between two thermal reservoirs: the heat source, which furnishes heat energy; and the heat sink, which absorbs heat energy. Heat energy flux Q, flows from the heat source to the heat sink, driven by the temperature difference between the source and the sink. As depicted in Figure 1, when a resistive load, R, is attached, electrical current, I, may be extracted from the thermoelectric generator and furnished to the load. The N-type and P-type thermoelements, are the active portions that do the actual conversion of heat energy to electrical energy. Although thermoelements may be built using conductors such as bismuth and antimony, higher efficiency thermoelectrics are built using heavily doped semiconductors. Thermoelectric devices are generally formed by connecting many pairs (couples) of N and P type thermoelements in electrical series and in thermal parallel. A commercially available module having 127 couples (254 elements) is shown in Figure 2."

Jan 1, 2011

By A. M. T. S. Bandara

The solubility of rare earth (RE) salts in aqueous solutions depends on many factors including the type of cations and anions in solution, their concentrations, temperature and the type of solid precipitated. Experiments were conducted using anhydrous La2(SO4)3 and Ce2(SO4)3⋅8H2O as solids and lanthanum(III) perchlorate prepared by dissolving La2O3 in HClO4 solutions as RE-sources. Solutions of H2SO4, H3PO4 and their mixtures in the presence or absence of Na+, Ca2+, Fe(III) or Al(III) as perchlorates served as test solutions. Saturated solutions and precipitated solids were assayed and characterized using standard techniques to show that the La(III) and Ce(III) ions precipitate as hydrated sulphates, phosphates or double salts with sodium, depending upon the solution composition. The change in solubility of RE-salts with solution composition and temperature is the result of the composite effect of changes in solubility products (pKSP) of salts, pKa of acids and other equilibrium constants for ion-association.

By J. A. Bakken

Thermal plasmas are interesting for a wide range of metallurgical and chemical processing applications. The 300 kW experimental reactor PRESS, which has been in use since 1987, is operated in the transferred arc mode with three or one plasma torches . Tests include remelting of silicon fines and production of ultrafine silica. Work on a novel three stage process for production of silicon metal is under way. A 1:1 model of the plasma reactor is used to measure the wall heat flux distribution calorimetrically. The cold walls of this model are divided into several water-cooled sections. The same plasma torches as in the real hot-wall reactor are used. In parallel to the experiments and calorimetric measurements theoretical work is done on numerical modelling of one and three transferred arcs. A modified version of the flow simulation program FLUENT from Creare Ltd. is used.

Jan 1, 1991

By Shan He, Qiang Wang, Xuling Chen, Min Gan, Lishun Yuan, Xiaohui Fan

"The sintering properties of vanadium-titanium magnetite concentrate(VTC) was studied in this paper. Through the optimizing the sintering process of VTC, the suitable granulation moisture and coke proportion were determined. The sintering velocity decreased from 23.05 mm/min to 18.22 mm/min. With the increase of VTC proportion from 0 to 46%, the specific productivity and tumbler index were respectively decreased from 1.55 t/(m2·h) to 1.21 t/(m2·h), and 62.93% to 57.73%. The temperature of liquid phase formations of mixtures increased, the amount of liquid lowered, and the content and sharp of sintering mineral gradually changed with the increase of VTC ,these lead that sinter quality became worse.IntroductionIn recent years, the steel industry of China is developing rapidly. And the steel production was 627 million tons in 2010. At present, the resources of vanadium-titanium magnetite concentrate(VTC) was about 14.4% of the total national iron reserves of China[1]. VTC has been used as sintering material by Magang, Chenggang and Pangang. The amount of VTC in Pangang is maximum. However, there exist many problems in VTC sintering, which involve in high specific productivity, bad sintering tumbler strength and high energy consumption[2~5]. That’s why the proportion of VTC is limited in sintering.The high quality of iron ore resources is worse in China. Therefore, it’s necessary to study the properties of VTC sintering, and to find out the reason how the VTC ratio affect the sinter performance. Purpose and significance of the research is to get high-quality sinter with the proportion of VTC greatly raised."

Jan 1, 2012

By Metehan Erdogan, Furkan Özdemir, Ishak Karakaya, Mustafa Elmadaglı

Tungsten is mainly produced by H2 reduction of WO3 which makes its production difficult and costly. A promising method was recently reported for direct electrochemical production of tungsten from CaWO4 (scheelite) which is estimated as the seventy percent of the all tungsten reserves of the world. This paper investigates the application of pulse current in the electrochemical reduction of CaWO4 pellets attached to a current collector. The electrolyte was composed of calcium chloride and sodium chloride salts at eutectic composition (48 pct mol NaCl at 873 K). The reduced samples were cleaned with dilute hydrochloric acid solutions and characterized by X-ray diffraction and scanning electron microscopy. Examination of the results revealed that metallic tungsten was obtained by pulse current reduction.

Jan 1, 2016

By Jack S. McPartland

The recent developments on the concentration and recovery of gold from leached gold thiosulfate solutions by solvent extraction, reduction-precipitation, and electrochemical deposition are reviewed in this paper. Alkyl phosphorus esters have been found to extract gold only in alkaline thiosulfate solutions, The recovery of gold increases with thiosulfate concentration in the aqueous phase and with alkyl phosphorus esters concentration in the organic phase with aliphatic hydrocarbon diluents. The addition of ammonia improves the extraction. The extraction of gold with amines in either aliphatic or aromatic diluent decreased in the following order: primary>secondary>tertiary amines. Increase in the extractant concentration at high pH increased the extraction of gold. At pH < 9, the primary amine, RR&apos;CHNH2 with 1&apos;9-23 carbon atoms is the main extractant with TBP as the synergistic reagent and at pH >9, the primary amine shows a synergistic effect on the extraction of gold&apos; with TBP. TheAu(I) ions in thiosulfate solution are reduced by sodium borohydride (SBH) to metallic gold, with particles in the sub micron range, At an SBH/ Au ratio of 6.25, pH = 6, and at room temperature, the I e ppm Au(I) in a solution of ] 0 gil thiosulfate was completely reduced to metallic gold in about 60 minutes.

Jan 1, 1999

By Michael A. Krstich

A soil washing pilot plant to treat soils at the U.S. Department of Energy (DOE) owned Fernald Environmental Management Project (FEMP), was designed based on extensive bench-scale testing. The system&apos;s design incorporated a combination of physical separation and&apos; chemical extraction processes and was tested on two soils. The textural composition of the two soils was approximately 20 percent sand, 60 percent silt, and 20 percent clay. Since this grain size distribution was not considered optimum for physical separation techniques, thesoil washing pilot plant had to be designed with selected equipment to provide specific soil size fractions during processing operations. A trommel, vibrating screen deck, centrifuge, and attrition scrubber were used in the system to selectively separate specific soil size fractions at 4.75, 2, 0.3, and 0.02 millimeters (mm). The trammel used high pressure water [1000 pounds per square inch (psi)] during the initial step of the process to reduce soil aggregates to single grain composition, separate out greater than 4.75 mm gravel, and dislodge chemical contaminants from the individual soil particles. The vibrating double-screen deck provided 2 - 4.75 and 0.3 - 2 mm soil fractions that, when combined, averaged greater than 75 percent solids for both soils. The centrifuge was designed to take the less than 0.3 mm soil slurry from the screen deck and produce a particle size of 0.02 mm. The centrifuge produced a high solids stream that averaged greater than 70 percent solids for both soils. These 0.02 to 0.3 mm soil solids from the centrifuge were combined with the 0.3 to 4.75 mm soil solids from the screen deck and processed through the attrition scrubber. The data collected from the pilot-plant operation was used to aid in the design of a full-scale system and was instrumental in formulating full-scale process operations and the selection of equipment.

Jan 1, 1995

By C. Damiani

The Chuquicamata smelter, operating since 1952, has gone through several developing stages which have been characterized by the addition of peak technology for copper concentrate smelting (Teniente converter and Outokumpu flash furnace) with an intensive use of technical oxygen, which has permit-ted to partially discontinue the reverberatory furnace utilization. This paper shows the main indicators and operational practices at present, as well as those concerning maintenance aspects. Finally, the most relevant topics related to the future development of the smelter are mentioned with special remarks on the Decontamination Plan, which allows US to keep the high level of production, reducing the emission of contaminants according to the legal requirements in force.

Jan 1, 1993

By Marcelo A. Martorano, Moyses L. Lima, João B. F. Neto

"Directional solidification is an essential refining step to obtain solar grade silicon from metallurgical silicon. This step can be carried out in a Bridgman furnace, where nearly constant temperature gradients and solidification velocities are imposed on the solid-liquid interface. In the present work, this directional solidification was conducted in a static furnace, in which large temperature gradients and low solidification velocities were enforced to increase macrosegregation. The resulting ingots were analyzed regarding their macrostructures, microstructures and chemical composition. Using measured cooling curves in the ingot as boundary conditions, a mathematical model based on the concept of a stagnant liquid layer at the solid-liquid interface was implemented to predict the macrosegregation profiles. The chemical analyses of the ingots show macrosegregation of several impurities to the ingots top. The mathematical model indicates that liquid convection plays an important role in stabilizing the planar solid-liquid interface, increasing the macrosegregation of impurities.IntroductionMost of silicon used for photovoltaic (PV) energy production is obtained by chemical processes, such as, Siemens and its derivations [1]. However, these chemical processes have drawbacks related to relatively high energy consumption and investment costs, and to safety and environmental problems. In order to overcome these difficulties and to fulfill the silicon demand for PV applications, several metallurgical routes are under development [2] to produce silicon of enough purity to PV applications (SoG-Si) from metallurgical grade silicon (MG-Si).Metallurgical routes involve different steps among which the directional solidification is pointed out as a fundamental one [1]. Directional solidification can cause macrosegregation of impurities to the last part of the ingot to solidify. The impurity segregation during solidification is related to the low solute partition coefficient (k0) between liquid and solid silicon. Most of the impurities in MG-Si have k0 << 1, except for boron, phosphorus and oxygen, which require specific steps of the metallurgical routes to be eliminated. The equilibrium partition coefficient and the solubility limits for the most important impurities in MG-Si are shown in table 1"

Jan 1, 2014

By Jose Hector Figueroa P.

Mexicana de Cananea, S.A de C.V. is a major copper producer mining a large deposit of the disseminated porphyry type considered one of the largest copper resources of the world with 2.7 billion tons of 0.60% copper for the mill plus 4.1 billion tons of averaging 0.26% copper for leaching. Mining of low grade sulfide leach ore, has been an important part of the overall production of the open pit mine which started in 1944. Before this time all the mining in Cananea was by underground methods. The leaching process in Cananea began on the 1920&apos;s with in situ operations in the underground mine and small dumps up to the 1950&apos;s. Large scale leaching operations began in 1960 and the copper solutions produced were treated in precipitation plants until 1,980 when the first SX/EW Plant was put in operation in Cananea. Leaching action is essentially ferric-bacterial, with no fiesh acid added to the leaching solutions. Traditionally, 5540% copper extraction is recovered fiom ROM, 70- 120 meter high leach dumps in 80 months of leaching. Cananea has successfully improved copper recoveries by implementing several actions that include: 1. Stripping of old dumps. 2. Leaching of old dumps through slotted casing. 3. Crushing conveying leach ore to minus 8 inch and stacking it in 30 meter lifts. As result of these actions, copper recovery has been increased&apos; to about 70% of total copper with actions 1 and 2 and up to 85% in half the time by crushing-conveying the leach ore, based on the same solubility index of the run-of-mine ore. This paper describes the above actions that were implemented to enhance the leaching recoveries from. sulfide leach dumps and the economics of such actions.

Jan 1, 1999

By T. Watanabe, T. Fujiwara, S-Wan Song, Y. Nakagawa, R. Teranishi, M. Yoshimura

"We have tried a new method to fabricate cobalt oxide films onto porous films directly by an electrodeposition method at low temperature. The porous substrate films (membrane-filters and paper) were placed between a LiOH solution and a CoSO4 solution and treated under electricalcurrents of ~1 mA/cm2 using carbon cathode and anode. Effects of temperatures, flow rates and electrical currents have been investigated. As a result, we found that the LiCoO2 films and Co3O4 films were successfully fabricated on paper and/or porous PTFE filters at 120 °C, while CoOOH films were deposited at 80 °C. Furthermore, LiCoO2 films did not cover whole the substrates, but was fabricated just over the anode. The chemical reactions of electrodeposition were also considered from these results.IntroductionRecent agreements on global environment require rapid progress of low energy and low waste processings for the fabrication of thin films that succeed to the mass production with the high consumption of the fossil fuels (such as physical vapor deposition°, chemical vapor deposition2), dip coating with firing3) etc.). The total energy consumption in aqueous systems should be the lowest among all these processing routes, because a much lager excess of energy is necessary to create melts, vapor, gas, or plasma than to form an aqueous solution at the same temperature4)The ""Soft Solution-Process"" (SSP) was one of the best concepts to realize the low energy and low waste fabrication of inorganic materials. 5) Generally speaking, SSP gives similar results to any other processing using fluids (such as vapor, gas plasma) and/or beam/vacuum processing. However, the total energy consumption of all these possessing routes should be the lowest in aqueous systems, because a much larger excess of energy is necessary to create melts, vapor, gas or plasma than to form an aqueous solution at the same temperature (Fig. 1). This idea can be easily demonstrated, using the simple example of BaTiO3. The energy diagram for the formation of BaTiO3 from various precursors is shown in reference 4. The driving forces (AG) for representative synthesis reaction of (1), (2), (3), (4) and(5) are 38, 727, 3685, 17 and —14kcal/mol, respectively at room temperature. 6' 7"

Jan 1, 2000

By I. Iwasaki

Platinum group elements (PGE) are often found in arsenide and sulfarsenide minerals as inclusions in copper-nickel bearing gabbroic rocks. Major losses of platinum in flotation have been attributed to the poor recoveries of the arsenic minerals. Flotation characteristics of a synthetic nickel arsenide and arsenopyrite were studied through rest potential and oxidation rate determinations, surface analyses, and micro-and batch-flotation tests. The use of nitrogen during grinding and flotation together with copper activation improved the PGE recoveries from Duluth Complex ores. The flotation behaviors of the sulfarsenide minerals are still unresolved. The role that electrochemical interactions play among arsenides, sulfarsenides, sulfides and grinding media on their f10atabilities is discussed.

Jan 1, 1988

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