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By Marco Antônio Siqueira Rodrigues

The possibilities for treating rinse waters fiom chromating bath by electrodialysis are discussed together with the possibilities of optimizing the treatment process for waste reduction and reuse of water and chemical products. An industrial effluent with 4600 ppm of Cr(VI), besides other metallic contamination, was used as work solution. This solution has been recirculated on an electrodialysis cell of three compartments, using exchange membranes Selemiom AMT and CMT. A migration of dichromate ions into the anodic compartment was obtained, so that an extraction of circa 99.9 % of Cr(VI) present on the solution was observed, resulting in water with a Cr(V[) concentration of 4 rnd. These results show that electrodialysis can be used to treat these effluents, and this water could be reused as rinse water. The solution of the anodic compartment, consisting at the beginning of the experiment of H2S04, 0.1 N, reached 7200 mg/l of Cr(VI). This concentrate could be reused on the chromating bath itself.

Jan 1, 1999

By B. Zilbergleyt

Current understanding of chemical equilibrium is based exclusively on the probabilistic considerations that are correct for isolated systems with only one chemical reaction to take place. For the systems with multiple chemical interactions, current paradigm of chemical thermodynamics promotes the idea of openness, artificially flavored with coefficients of thermodynamic activity. Recently introduced thermodynamics of chemical systems and the Method of Chemical Dynamics (MCD) offer explicit accounting for the multiple chemical interactions within the system. In the new theory, thermodynamic equilibrium of the j-subsystem obeys the logistic equation derived exclusively from the currently recognized concepts of thermodynamics. Having the only one new parameter -the subsystem's reduced chaotic temperature 'tj to describe external interactions, and reaction extent Ilj as independent variable, this equation covers the whole domain of the system's possible states from true thermodynamic equilibrium through the open equilibrium to bifurcations and chaos depending on the 'tj value. The MCD brings new opportunities to thermodynamic simulation of complex metallurgical and chemical systems, allowing for the analysis of their domains of states and the area limits, and for more accurate calculation of the equilibrium compositions. Its usage is exemplified in this paper by several applications. Keywords: chemical thermodynamics, open systems. complex systems, chemical dynamics.

Jan 1, 2003

By Yan Zeng

Lithium metal silicates (Li2MSiO4, M = Fe or Mn) composed of abundant and non-toxic elements are important cathode materials for Li-ion batteries (LIB). In contrast to solid-state or sol-gel methods, hydrothermal synthesis conducted in pressure reactors is a favorable processing route as it provides the potential for scalable production and is environmentally benign. However, the key is to control the precipitation reaction to obtain powders with desired properties to meet battery specifications. Through a systematic study, we have found that Li2MSiO4 with tunable size from 300 nm to 1.5 μm can be produced by adjusting precursor concentrations, temperature, and reaction time. Under optimum conditions, high purity Li2MSiO4 with minimum defects were successfully produced and examined as an LIB cathode. The use of complexing agents promoted the formation of unique hollow particles via the self-assembling of elongated crystals. A four-step formation mechanism is proposed based on extensive characterizations with XRD, HR-TEM, SEM, and Mössbauer spectroscopy.

By Cledwyn Mangunda

Mining operations generate Acid Mine Drainage (AMD) that poses a significant threat to the natural environment. AMD treatment using Ca(OH)2 leads to the precipitation of a sludge dominated by a mixture of ferri-oxyhydroxides. This sludge has poor dewatering tendencies and is deposited in landfills with potential for metal remobilization. This study investigated the dewatering behaviour of a precipitate formed during elevated temperature treatment of a primary, pre-settled sludge from the neutralisation of aqueous acidic Fe2(SO4)3 and Ca(OH)2 solutions in an MSMPR reactor. The resulting treated precipitates were analysed for micro-properties, with results showing that an increase in the secondary reactor temperature from 25 °C up to 50 °C led to an increase in mean particle size, a decrease in the number of particles and improved dewatering behaviour at a ferric concentration of 300 mg/L. This was ascribed to the attainment of a circum-neutral surface charge that favoured agglomeration and a change in micro and nano-structure that allowed for better water passage.

By P. Tim Johnson

Relentless increases in demand for nickel and vanadium for uses such as steelmaking, catalysts and battery materials, plus the growing financial and environmental costs of their primary extraction, have led to much interest in potential secondary sources of these metals. The presence of such metals in heavy fuel oils, bitumen and related materials offers both opportunities and challenges for potential extraction methods, especially with the growing production and importance of metal-rich fossil fuels around the world. For several decades, Tetronics’ DC plasma smelting technology has been used for the recovery of metals such as nickel and chromium from stainless steel melt dusts and other wastes in compact, environmentally-friendly and efficient plants. This paper explores the suitability of DC plasma smelting as part of a wider flowsheet with feed preparation and aluminothermic reduction techniques for smaller-scale extraction operations based on this important niche secondary source of these key metals.

By D. J. Droppert

This paper describes the precipitation-production of crystalline scorodite (FeAs04.2H20) from arsenic-rich sulphate-based metallurgical solutions at ambient pressure (95°C). Arsenic is precipitated by means of a controlled precipitation technique in which the supersaturation of the solution is carefully controlled. By controlling the supersaturation in the presence of seed material. the formation of amorphous ferric arsenate is prevented. Scorodite is known to be the most stable As(V) compound and is therefore preferred as host mineral for arsenic immobilization. The effect of the following parameters on the preCipitation behaviour and kinetics of scorodite are discussed: Type of base seed concentration initial [As]. sulphate concentration. neutralization rate. seed recycling and method of Fe(ll!) addition to Fe-deficient arsenic solutions.

Jan 1, 1996

By Andrew Case

The Port Nickel facility in Braithwaite, Louisiana, is known for pioneering hydrometallurgical processes for the 'separation and recovery of nickel, cobalt and copper. Ten years ago, in 1985, a new CRI-MET process for the recovery of molybdenum, vanadium, nickel, cobalt and alumina from spent catalysts was developed and implemented. Spent- catalysts from the petroleum industry consietute the majority of feed. These are not only a valuable-source of metals, but due to EPA regulations are frequently classified as hazardous under RCRA. Molybdenum and vanadium are selectively leached in an oxidative hydrothermal step. Alumina is then extracted in a caustic digestive leach. The unique technology produces four primary commercial products l molybdenum trioxide, vanadium oxide, aluminum trihydrate and nickel-cobalt concentrate. This paper discusses the process, modifications. during ten years of operation, and the relationship of these modifications to the future of the catalyst recycling business.

Jan 1, 1995

By F. J. Tavera

The column flotation technology, at first developed for application in mineral dressing, has received special attention in processing of non-mineral dispersions as a result of its low cost, high efficiency and relatively simple operation. This paper presents the results from the operation of a laboratory flotation column for the separation of vegetable oil and soap from aqueous industrial effluents, The flotation system was operated under continuous countercurrent conditions without and with additions of a cationic collector. The experiments show that it is possible to separate about 80% of the organic phase in a rougher flotation stage. These results suggest that the recovery of the organic phase is highly dependant on the dispersion characteristics (i.e. bubble size, gas holdup and bubble surface area flux) and the existing an optimum bubble size from which either smaller or larger, the recovery of the organic decreases.

Jan 1, 2003

By W. K. Connor, O&apos

Thermal Treatment Technology Division Albany Research Center, U.S. Dept. of Energy Oregon. This evaluation included a characterization study and direct smelting tests conducted in a bench-scale electric arc furnace (EAF). In contrast to other thermal treatment technologies considered for these wastes (i.e., fluidized bed combustion), direct smelting in the EAF can process 100% of the wastes without prior beneficiation, and utilizes solid oxidant additions (in this case iron ore) rather than air to oxidize the carbon. This solid oxidant addition is advantageous because it results in the production of several value-added furnace products. These products include cast iron resulting from the reduction of the iron oxides, baghouse dust containing virtually all of the zinc from the residues, and a clean (nonhazardous) slag product suitable for recycle as concrete aggregate or construction fill. Offgas from the smelting furnace also holds potential as fuel gas for cogeneration. The direct smelting tests conducted thus far were successful at producing the desired furnace products, exhibiting the potential for complete recycle of the waste pile. A cast iron product of comparable quality to conventional cast irons was produced, at nearly 80% iron recovery to the metal. The slag product was determined to be nonhazardous, based on the EPA TCLP. Lead and zinc partitioning to the dust product was greater than 99%. The material balance over the furnace indicates that for every ton of feed processed, 540 lb. of cast iron, 600 lb. of slag, and 150 lb. of dust would be produced. Energy consumption was roughly 1.10 kWxh/lb of feed material. Prior experience suggests that these figures measured in the bench-scale furnace would translate to 0040 to 0.50 kWxh/lb at the industrial-scale.

Jan 1, 2000

By Gopalakrishna B. Prabhu, David L. Bourell

"Three mol% Yttria-Stabilized Tetragonal Zirconia (YSTZ) was prepared by a sol-gel synthesis technique using zirconium tetrachloride and hydrated yttrium chloride precursors. After drying and annealing at 823K, the particle size was in the range 10 to 20 nm. The zirconia powder was sintered using a uniaxial hot press at an applied stress of 20 to 40 MPa. One hour, isothermal sintering was performed in air after initial heating at 50K/min. Theoretical density was obtained at densification temperatures above 1498K. After sintering, grain coarsening characteristics were studied using constant heating rate anneals followed by quenching, based on a model for grain coarsening in a linear heating rate cycle. The microstructural change was studied using SEM and TEM and the phases were determined using x-ray diffraction.IntroductionThe ability to sinter nanocrystalline materials to full density several hundred degrees below the normal sintering temperatures is one reason for their current interest. [1-5] Yttria Stabilized Tetragonal Zirconia (YSTZ) of grain size of about 300 nm has exhibited superplasticity, with elongations as large as 800%.[6-7] Fine grain size is critical for superplasticity. Retention of the fine grain size during sintering of nanocrystalline powder is important if a material is to exhibit superplasticity or to exhibit physical or mechanical properties associated with the ultra fine structure. This paper investigates the sintering behavior and the grain coarsening characteristics ofnanocrystalline YSTZ.Techniques for synthesizing nanocrystalline materials have been studied in great detail earlier. [8-12] The techniques used to synthesize nanocrystalline zirconia include alkoxide synthesis [9], the chloride method [11], the peroxide method [13] and the acetone-toluene method. [13] In this paper the method used in the synthesis of zirconia is the chloride technique. With this precipitation technique, either zirconium chloride or oxychloride and a corresponding yttrium salt or even pure yttria are used."

Jan 1, 1994

By Artur R. P. Junior Sergio, Pedro A. Netto, N. Monteiro, Foluke S. de Assis, Frederico M. Margem

Synthetic fibers are being replaced gradually by natural materials such as lignocellulosic fibers. Compared to synthetic fibers, natural fibers have shown advantages in technical aspects such as environmental and economic. So there is a growing international interest in the use of those fibers. The banana fiber presents significant properties to be studied, but until now few thermal properties on banana fiber as reinforcement of polyester matrix were performed. The present work had as its objective to investigate, by photoacoustic spectroscopy and photothermal techniques the thermal properties of diffusivity, specific heat capacity and conductivity for polyester composites reinforced with banana fibers. In the polyester matrix will be added up to 30% in volume of continuous and aligned banana fibers. These values show that the incorporation of banana fibers in the polyester matrix changes its thermal properties.

Jan 1, 2015

By Teuku A. R. Putra, Patrick R. Taylor

Various pyrometallurgical methods for treating copper concentrates that contain appreciable arsenic are reviewed. Various aspects of the engineering of these treatment methods are discussed. The methods discussed include: complete oxidation with arsenic fixation; selective volatilization of arsenic; acid baking, soda ash roasting, and others methods. Methods for the ultimate disposal, or marketing, of the arsenic are discussed.

Jan 1, 2014

By Denise Crocce Romano Espinosa, Andrea Moura Bemardes, Jorge Alberto Soares Tenorio, Daniella Cardoso Buzzi, Tatiana Scarazzato

"In copper plating processes, a fraction of raw materials are incorporated to the final products, while other portions are discarded as effluents. In this study, the application of electrodialysis (a membrane treatment process) was studied for treatment of wastewaters from cyanide-free strike baths, in order to reuse the components of this bath: copper and HEDP. The synthetic solutions studied consider 1 % of ion concentration of the bath used in this process, simulating the rinsing waters to be discarded. The electrodialysis allowed a percentage extraction up to 73% of copper ions and 72% of HEDP from the effluent. Complexes formation between the acid and copper indicates the possibility of recovery of components in the same compartment, obtaining a concentrated solution of these substances that can be reinserted in the process, for compensating drag-out losses. A diluted solution is also obtained, that can be reused as water in rinsing tanks.IntroductionIn metal finishing industries, contaminants in wastewater and the type of treatment required are determined according to the type of operation [l]. Generally, electroplating industries employ conventional wastewater treatments, e.g. oxidation of cyanide and chemical precipitation. This stage promotes reactions with soluble compounds to produce an insoluble precipitate, removed by physical separation. The sludge is dried by press-type filters [2].In this manufacturing sector, part of the raw materials are discarded as hazardous waste. The cost of discarded compounds and the treatment and disposal of waste may compromise profit margins. In addition, water consumption per unit of production stimulates the development of methods able to recover and reuse the largest possible amount of water [3].In some plating processes, cyanide-based substances are used as complexing agents and as raw materials in form of metal salts [4]. However, the toxicity associated with cyanide has been promoting research for the development of new raw materials in plating processes.A study conducted in Brazil [4] evaluated the modification of a commercial cyanide-free bath for processes of copper coating on Zamak. In the performed study, a new alkaline copper bath was formulated using l,hydroxyethane-1,1-diphosphonic acid (HEDP), an organic compound known for forming stable complexes with metal ions.As results of the study, the operational conditions and the formulation of a bath to obtain adherent, uniform and bright layers were established (Table I) [4]."

Jan 1, 2014

By A. Onozaki

The Iijima Refinery was put into operation in 1972 and today has an annual production capacity of 156,000 tons of SHG electrolytic zinc. At the Iijima Refinery, the recoveries of gold and silver are 98.0% and 98.2%, respectively. Gold contained originally in the zinc concentrates reports in the Cu-Pb-Ag residue produced in the residue treatment process. Silver contained in the concentrates is distributed between the Cu-Pb~Ag residue and the copper cake produced in the purification process. The Cu-Pb-Ag residue, which contains gold and silver, is sent to the Oyachi flotatfon plant of the Kosaka Smelter; about 82% of the gold and about 85% of the silver are recovered in the copper flotation concentrate.. In this paper, the distribution of gold and silver in the Iijima. Refinery is discussed and operational results of the Oyachi flotation plant are presented.

Jan 1, 1990

By Carvalho A. Felipe de

The search for environmentally friendly and cost-effective methods for gold extraction has been undertaken in order to provide alternatives to the use of cyanide leaching in the gold industry. Among such alternative reagents is the combination of chloride and hypochlorite ions due to their oxidation of metallic gold and its complexation. Therefore, the current work aims at investigating gold leaching from an oxidized material by means of a solution comprising calcium hypochlorite and sodium chlorite. The sample used in the current research contained 66.1% Fe2O3, 20.4%SiO2, and 35.7 g/t of Au. In addition, XRD and SEM-EDS analysis revealed iron oxide, quartz and muscovite as the main crystalline phases in the sample. For comparison purposes, cyanidation of the oxidized material resulted in 90% gold extraction in 24 h. The reference conditions for the leaching tests with the chlorite-hypochlorite system were: particle size −37 μm, solid/liquid ratio of 10% (w/v), 10 g/L NaCl, 10 g/L Ca (OCl)2, pH 5–6, 3 h of leaching. The effects of the: (i) Ca(OCl)2 concentration, (ii) NaCl concentration, (iii) pHrange and (iv) the effect of pulp density in the extraction of gold were assessed. In addition, the stability of the hypochlorite solutions (OCl−) was investigated. The ideal concentrations of Ca(OCl)2 and NaCl were determined as 25 g/L and 15 g/L, respectively, whereas the optimal pH range was 4–6. Under these conditions, the final gold extraction reached approximately 84%. By varying the solids content of the pulp (10%, 20% and 30%), it was observed that the lower solids value resulted in greater gold extraction (84%). The degradation of the hypochlorite solution and the possible catalytic effect of the presence of the solid were evidenced. To sumup, in the experiment, high gold extractions were achieved in shorter periods of time (3 h), as compared to the cyanidation of the same sample. On the other hand, itwas necessary to use significant amounts of the reagent due to hypochlorite instability at the pH conditions recommended for high gold extractions.

By Youn-Bae Kang

Evaporation mechanism of S from liquid Fe–C–S alloys at 1873 K was proposed by analyzing available experimental data. It has been known that increasing C content in liquid alloy increases activity coefficient of S ðfSÞ, and it could raise driving force for the evaporation reaction S = S(g). However, experimental data of the evaporation of S in the Fe–C–S alloys could not be accounted for only by considering the increases of fS. In the present study, formation of carbosulfides, CS(g) and CS2(g), was additionally taken into account in order to explain role of C for the accelerated S evaporation. Surface adsorption of S was also taken into account, which retards the evaporation rate of S. An evaporation model equation was formulated. It can be applied to calculate the evaporation rate of S over wider C content (from zero to its saturation to liquid alloy).

By A. R. Udupa

The reduction roasting behavior of chalcopyrite has been investigated using various combinations of a desulfurizing agent, i.e., CaO or Na2CO3, and a reductant, i.e., CO, H2 or C. Using these, combinations the sulfur is removed from the mineral as CaS or Na2S rather than SO2 as is the case with conventional copper smelting and converting. The laboratory reduction ex¬periments were conducted using thermogravimetric analysis (TGA) and boat tests of mixed combinations of fine particulate reactants subjected to a continuous gas stream. The degrees of metallization were determined by both weight loss and chemical analysis methods and the products examined using optical and scanning electron microscopy and electron probe microanalysis. The percent reduction after one hour at 900°C ranged from 60% to 94%. From these data It was possible to provide postulations as to the controlling reduction mechanisms.

Jan 1, 1983

By Katsuya Kase, Kaname Takeya, Keaji Ohmori, Yoshiyuki Asakawa

"The reduction-diffusion process (the R-D process) using Ca as a reducing agent has been practiced in industry in the production of the SmCos type, the Nd-Fe-B type and the 1b-Fe-Co type magnetic materials. The advantages of the R-D process are the generally high yield of rare earth metals and the single-stage conversion of a mixture of oxides and metal powders into a product of rare earth alloy powders. On the other hand, one of its disadvantages is the slightly high contents of oxygen and calcium. This disadvantage is remarkable in the Nd-Fe-B type. Singe-phase Nd2Fe14B alloy powders with low content of 0 and Ca, is obtained by choosing appropriate raw materials and performing the R-D process in a controlled way. These alloy powders are very suitable for the production of Nd-Fe-B sintered magnets and expected higher magnetic properties by adopting advanced magnet production method.IntroductionThe hard magnetic rare earth transition metal intermetallics, especially, have attained considerable technical importance. Examples are the alloys based on the intermetallics SmCo5[1], SmC017[2], NchFet4B[3], or the recently developed alloy SnuFe11Nx[4]. The reduction-diffusion process using Ca as a reducing agent has been well known as an economical method of producing rare earth based magnet materials[5]. The reduction-diffusion process has been practiced in industry in the production of the SmCos type, the Nd-Fe-B type and the 1b-Fe-Co type magnetic materials. The advantages of the reduction-diffusion process are the generally high yield of rare earth metals, the single-stage conversion of a mixture of oxides and metal powders into a product of rare earth alloy powders, the elimination of the crushing process of the alloy ingot, the inessentiality to special equipment, etc. On the other hand, one of its disadvantages is the slightly high content of oxygen and calcium. This disadvantage is remarkable in the Nd-Fe-B type. An outline of basic studies of the reduction-diffusion process was reviewed from the particular viewpoint of the production of magnet materials by Ogawa [6]."

Jan 1, 1998

By A. V. Reddy, C. Beckermann

"The DC continuous casting of a grain refined AI-4.5%Cu round ingot with realistic boundary conditions is numerically simulated. Of particular interest are the effects of the transport of free solid in the form of equiaxed grains on the macro segregation patterns and the final grain size distribution. The study uses a previously developed two-phase model that incorporates descriptions of heat transfer, solute redistribution, melt convection, and solid transport on the system scale with microscopic models of solutal undercooling, microsegregation and grain impingement. The numerical results indicate that grain transport inhibits the formation of inverse segregation in the ingot shell and promotes negative centerline segregation. This is explained by the reduction in the solid coherency next to the mold and the advection of solute-lean grains towards the centerline. Comparisons with the experiments of Finn et al. [5] illustrate the need for considerable improvements in the model. IntroductionMacrosegregation continues to be one of the concerns in DC continuous casting of aluminum ingots. The variation in composition over the ingot cross section results in the need to adjust alloy composition in order to meet mechanical property specifications in finished products. The extent of macrosegregation is greatly affected by the casting conditions, such as casting speed, superheat, cooling rate, mold size, alloy composition, and grain refining practices. Thus, it is of great interest to develop a comprehensive mathematical model to simulate the casting process, enabling the selection of conditions that minimize macrosegregation while maintaining a high productivity."

Jan 1, 1994

Based on experimental and computer simulation results from our group, we report a systematic, atomic level analysis of carbon dissolution from carbonaceous materials in molten iron. Experimental results on graphite / Fe-C-S system were obtained using carbon dissolution studies, XRD and FESEM investigations and were supplemented with Monte Carlo simulations. Three basic mechanisms, namely carbon atom dissociation rate, interfacial phenomena and mass transfer in the melt were found to be responsible for the overall dissolution process. While mass transfer in the melt is governed by the concentration gradients, melt composition and temperature; impurities present in ash play a significant role in the interfacial phenomena. For less ordered forms of carbonaceous materials, carbon atom dissociation rate depends strongly on the degree of long-range order and is an important rate controlling mechanism in the overall dissolution process. A systematic comparison of dissolution rates for a variety of coal-chars, natural and synthetic graphites has been carried out in an attempt to identify rate-controlling mechanisms. The structure of the carbonaceous material appears to be an important underlying factor in the carbon dissolution process.

Jan 1, 2003