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By Rolf R. von Oppenfeld

Onsite hazardous waste processors often find obtaining a Treatment Storage and Disposal (TSD) permit one of their first major challenges. Some processors may spend the time and money required by the permitting process, only to find out later that a permit was not necessary. This paper will present and analyze four strategies that processors may use to avoid obtaining a TSD permit. Some facilities will be able to remove their waste streams from RCRA's oversight by ensuring the material is not "hazardous" waste. Parties that treat waste while it is in process may be able to avoid generating "waste" altogether. Certain treatment facilities have been specifically exempted by EPA. Finally, treatment of waste while it is in generator storage tanks may be allowed without a RCRA TSD permit. Hazardous waste point of generation, an important determination relating to these strategies, will also be discussed. Generators and processors will find this paper useful when evaluating their permit exemption potential

Jan 1, 1996

Physical and chemical properties of the salt flux phase play a significant role in the recycling of UBC in Aluminum melting processes. Particularly knowledge of several properties such as salt vapor pressure, melting temperature, loss of aluminum, corrosion of refractories are useful for the process control decisions in order to attain a good quality of aluminum produced. A literature review and analysis of several salt flux systems for the selection of a flux for the Aluminum melter (low temperature natural gas bath melting) process were made. Based on these analysis two salt flux systems are recommended for further studies. These are NaCl?KCl?LiF system and NaF?LiF?KCl system with small amounts of other salt additives. Application of these fluxes to Al industrial processes are discussed.

Jan 1, 1996

By T. DebRoy

In recent years rapid technological advances have been achieved in the application of high energy density heat sources such as lasers and electron beams in diverse metals processing operations such as metal refining, fabrication, coating, surface modification and alloying. However, our phenomenological understanding of these new and emerging processes has not kept pace with the technological achievements. Inadequate understanding of plasma-metal interactions, the complexity of the component physical processes, and the scarcity of thermophysical data at temperatures much higher than the melting points of metals are the main difficulties in the comprehensive analysis of these processes. Several unique contemporary issues related to metals processing with high energy density beams such as rapid evaporation of alloying elements during processing and the role of plasma in influencing vaporization rate interfacial tension and species solubility in metals are discussed in this paper.

Jan 1, 1993

By J. D. Sunderkötter, M. F. Stroosnijder, V. A. C. Haanappel

"TiAI-based intermetallic compounds have attracted considerable interest as structural materials for high-temperature applications due to their low density and substantial mechanical strength at high temperatures. However, one major drawback hindering industrial application arises from the insufficient oxidation resistance at temperatures beyond 700 °C. In the present contribution some general aspects of high temperature oxidation of TiAI-based intermetallics will be presented. This will be followed by a discussion of the influence of alloying elements, in particular niobium, and of the effect of nitrogen in the oxidizing environment on the high temperature oxidation behaviour of such materials.Extended AbstractIntroductionTiAI-based intermetallics are being considered as construction materials for high temperature components, e.g. in aircraft and car engines, due to their low density and substantial mechanical strength at high temperatures, see e.g. [1,2]. The best ductility can be attained with alloys consisting of y-TiAI with around 5-15 vol.% Q2-Ti3AI. However, one major hindrance to industrial application arises from the insufficient oxidation resistance at temperatures beyond 700 aG. In spite of their high aluminium content, TiAI-based intermetallics do not generally form long-lasting protective alumina scales. After longer exposure times the scales, which are initially rich in alumina, deteriorate and scales consisting of mixed alumina and titania predominate, with high growth rates similar to pure titania.It is not the intention of the present paper to present a general overview of the high temperature oxidation behaviour of TiAI based intermetallics, for which the reader is referred to the literature [3,4]. In the present contribution some general aspects of high temperature oxidation of TiAI-based intermetallics will be presented. This will be followed by a discussion of the influence of alloying elements, in particular niobium. The effect of nitrogen in the oxidizing environment on the high temperature oxidation behaviour of these intermetallics will also be considered."

Jan 1, 1996

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 Guy Xueyi

The environmental impact assessment of the Imperial Smelting Process for metallic zinc and lead production in Shaoguan Smelter, China, was carried out by the life cycle assessment method. The detailed inventory analysis of the Input/Output in the process during 1998-2000 was conducted and the allocation was done among the main products of zinc, lead and sulfuric acid, according to the system expansion and substitution principle, The environmental impacts were assessed by using the following five Eco-indicators: Gross Energy Requirement (GER), Global Warming Potential (GWP), Acidification Potential (AP), Heavy Metal Toxicity' (HMT) and Solid Waste Burden (SWB). The results from this study are useful to address the environmental situation of the technology practice in this smelter, and provide a scientific basis for the further improvement.

Jan 1, 2003

By Samantha Moodley, Rauf Hurman Eric, Cevat Kucukkaragoz, Aditya Kale

"Two titania slags, rutile and synthetic rutile were chlorinated with petroleum coke and CO in a small bubbling fluidized bed reactor. The study aims to identify differences in chlorination mechanism, compare conversion rates, blowover and the chlorination of impurities for the various titania feedstocks at different temperatures.Chlorination rates were highest at 1000ºC; rutile chlorination significantly increases as temperature increases from 800ºC to 1000ºC. At 1000ºC, synthetic rutile had the highest chlorination conversion rate; this was followed by Slag B which in turn was more reactive than Slag A and rutile. The mechanism for slag, synthetic rutile (SR) and rutile chlorination differs. Synthetic rutile feed is porous, providing a larger surface area for the chlorination reaction, hence the highest conversion rates was attained. Titania slag becomes porous with the initial chlorination of FeO and MnO whilst rutile remains solid. As the porosity of slag particles increases so does its tendency to be elutriated. Ti2O3 is oxidized within the early stages of chlorination during the chlorination of FeO and MnO. Ti2O3 not oxidized is then rapidly chlorinated.IntroductionTitanium dioxide (TiO2) is the most common compound of titanium, about 95 - 98% of extracted titanium minerals is processed into TiO2 white pigment [1]. Two processing routes exist for the production of TiO2 pigments, i.e., sulphate and chloride based processes. In the chloride process, titania feedstock is fed to a fluidized bed reactor together with reductant and chlorine gas. A temperature of 1000 - 1300ºC is maintained in the reaction zone and apart from silica, zirconia, uranium and thorium, virtually all the metal oxides in the feed are converted to their respective chlorides [2]. Chlorine is recovered and recycled back to the reactor."

Jan 1, 2012

By Yuhsuke Mizukami

Crude high Cr containing steel such as tool steel, heat-resistant steel or stainless steel is produced by dissolution of high carbon ferro-chromium into molten crude steel. In the refining process, decarburization is performed at the first stage, and deoxidation is followed in the next stage. Therefore, the equilibrium relation between dissolved Cr and 0 in molten Fe-Cr alloy after decarburization is very important when yield of deoxidizer is considered for the ovemll control and optimization of the process. It is well known that the yield of deoxidizer does strongly depend on the kinds of refractories of furnace in the secondary refining process. In the present work, the equilibrium relation between dissolved Cr and O in molten Fe-Cr alloy has been measured in a Cr2O3, MgO or Al2O3 crucible at steelmaking temperature. O contents at given Fe-Cr components have been lower in order of Cr2O3, Al2O3 and MgO crucible. The present results have been discussed based on the activities of the constituents in pure solid Cr2O3, and FeO-Cr2O3, MgO Cr2O3 and (AI,Cr)2O3 solid solutions.

Jan 1, 2003

By Olusegun J. Ilegbusi

"A two-fluid model is used to calculate flow and heat transfer characteristics of a plasma jet. This model accounts for both gradient-diffusion mixing and unmixing that may result from pressure-gradient-body-force imbalance in the system. The unmixedness is considered to be essentially a Rayleigh-Taylor kind instability. Separate transport equations are solved for the plasma and ambient gas velocities, temperatures and volume fractions. The two fluids allowed to exchange mass, momentum and energy through empirical interaction parameters. The empirical coefficients are first established by comparison of predictions with available experimental data for shear flows. The model is then applied to an Argon plasma jet ejecting into stagnant air. The predicted results show the significant build-up of unmixed air within the plasma gas, even relatively far downstream of the plasma torch. By adjusting the inlet condition, the model adequately reproduces the available experimental data on the temperature profile.IntroductionPlasma jets have important applications in materials processing, some of which include spray deposition, melting and refining, heat treatment and materials synthesis. In a typical reactor, the hot plasma stream entrains a surrounding gas and the resulting heat and mass transfer and the condition of operation of the torch, determines to a large extent, the performance of the unit. The entrainment may prevent uniform mixing and produce regions of unmixed hot/cold gases and non-uniform deposits as a result of insufficient melting of deposit in cold regions. This phenomenon may also affect chemical reaction rate in plasma systems for NOx reduction in exhaust gases.The study of plasma phenomena is often conveniently divided into three parts namely, the plasma torch, the plasma jet and analysis of the particles carried in the jet. The present work concerns processes occuring in the near-field of the plasma jet i.e. just downstream of the torch."

Jan 1, 1994

By Jerome P. Downey

The Indium Corporation of America - Colorado School of Mines Indium Separation Technology was evaluated as a potential means of treating smelter flue dusts stockpiled at the Pintlar Corporation property in Kellogg, Idaho. The patented technology represents a method for segregating the contained indium, lead, and other metals in forms acceptable for downstream processing and recovery. Separation is effected by treating the dust with metallic sodium in a bath of molten lead. Process effectiveness was measured by determining the relative distribution of key metals between the bullion and dross products at small pilot plant scale. The study indicated that application of the technology to the Pitlar samples results in a highly efficient concentration of lead in the bullion, while indium is collected in the dross. The distribution of other key metals between the bullion and dross products and the effect of varying selected process parameters are also discussed.

Jan 1, 1994

By Pesic. Batric

A novel chitosan-pyridoxal-epichlorohydrin was synthesized and evaluated in our laboratories. The evaluation was achieved by performing kinetic and equilibrium studies of copper sorption. The parameters examined were pH, temperature, concentration of copper, particle size and selectivity of copper sorption against iron, zinc, cadmium and cobalt. It was found that pH was the most important parameter, and sorption of copper increased with pH increase in the range pH 2.5-6.0. The low activation energy of the sorption reaction, 1 1.13 kJ/mole (2.66 Kcal/mole), showed that temperature was not an important parameter. The synthesized chitosan was selective against iron, zinc, cadmium and cobalt. The selectivity with respect to last three metals was achieved by the kinetic difference of sorption, as sorption of copper was much faster than for other metals. Iron (Fe2+) does not adsorb on chitosan. The mechanism governing the sorption of copper is intraparticle diffusion. This finding was supported by the dependance of copper sorption on the square root of time, the low activation energy, and the fit of experimental data in the diffusion through the product layer equation.

Jan 1, 1994

By J. V. Atwood

The U.S. Bureau of Mines has developed a novel Double Membrane Electrolytic Cell (DMEC) that exhibits unique features for recycling contaminated metals and metal alloys. The DMEC incorporates two anionic ion exchange membranes, separating anodic and cathodic regions of the cell. The ion exchange membranes prevent significant transport of unwanted cationic impurities to the catholyte from the impure anolyte while the anion/cation balance in cell compartments is maintained through the free movement of anions between compartments. The membrane barrier makes it possible to electro refine highly contaminated materials or to electrowin from solution while utilizing alternate anode reactions. Sinceanolyte and catholyte cross contamination has been eliminated, premium cathode products are produced. The DMEC has been tested at bench, pilot, and commercial scales. Configuration of the DMEC, cell operation, scale, up efforts, and significant design factors are discussed. Two separate recycling investigations utilizing DMEC technology are presented. The first investigation examines recovery of high purity cobalt and nickel from severely contaminated super aIloy scrap. The second involves? upgrading contaminated cobalt in the U.S. Government's National Defense Stockpile. Capital and operating costs for both potential applications are presented.

Jan 1, 1995

By Daniel K. Kim

The charge for the copper refinery is a mixture of anodes produced at San Manuel from BHP source concentrate and copper purchased from external sources. Control of unwanted impurities in the tankhouse - is very important and beneficial. Currently available removal/recovery technologies were reviewed for the control of bismuth and antimony levels in the electrolyte. Recent studies have focused on solvent extraction (SX) technology and generated successful results for the removal and subsequent recovery of bismuth and antimony. The SX system employs the reagent, ACORGA SBX-50, in conjunction with a patented high chloride stripping system. The latter enables recycle of the eluant, avoiding the high costs associated with conventional systems, such as regeneration of resin. Concerns over potential transfer of organics and chloride ion to the electrolyte were readily addressed, solved and demonstrated using conventional, established technology. This paper describes the benefits of electrolyte purification, the flexibility afforded by the SX system, the operational practices necessary for maintaining adequate control of bismuth and antimony impurities in the electrorefining environment and possibilities for future development /exploitation of the Zeneca SX system at the San Manuel refinery.

Jan 1, 1998

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 J. L. Holman

The Bureau of Mines is investigating recovery of Ni, Co, Cr, and other metals from mixed contaminated supera110y scrap. The scrap is melt-refined and cast into anodes for electrodeposition of recyclable Ni-Co alloy. Melt oxidation using roasted superalloy grinding sludge as oxygen source can divert the Cr to the slag but with excessive Ni-Co loss. Melt oxidation-carburization or direct melt carburization retains -95 pct of the Ni-Co in the anode alloy. With direct carburization, -90 pct or more of the Cr and other refractory metals report to the anode alloy, largely as carbide phases insoluble in electrolysis. Electrorefining data relate parameters such as controlled cathode potential, Fe and Cr impurities, pH, and compartmented cell use, to current efficiency and Ni-Co deposit quality. Recovery of -90 pct of the Ni-Co in the scrap can be achieved. Preliminary experiments to recover Cr, W, and other metals from the anode sludge and other byproducts are discussed. 347

Jan 1, 1987

Microstructural investigation has shown that grain splitting or deformation banding ( DB ) develops progressively with increasing strains during cold rolling. Of particular significance to simulating texture development in cold rolled BCC polycrystals is the operation of higher order slip systems other than 110 and, the occurrence of DB in the rolling plane since the latter allows a new relaxation of the shears. Deformation banding ( DB ) model includes grain subdivision in the rolling plane and applies the Relaxed Constraints ( RC ) mechanism for the other shears. An energy criterion for deciding whether deformation banding occurs or not has been postulated, referred to as Deformation Banding Criterion ( DBC ). This paper reports the results of the investigations into the effects of different slip systems, i.e., those based on 110, 112 and 123 slip planes and their combinations using RC, DB and DBC models, in developing simulated BCC rolling textures.

Jan 1, 1999

By A. Mezei

A process has been developed to recover cobalt, gold and bismuth from the NICO deposit in Canada. The process consists of a bulk rougher flotation followed by an optional separation by flotation to produce a bismuth concentrate and a cobalt concentrate, grading on average 12.8 % Bi and 1.8% Co, respectively. Cobalt is leached by pressure oxidation at 97% efficiency, producing a pregnant solution suitable for further processing. Before optimization, about 38% of the bismuth is recovered in the selective concentrate, wherefrom it is recovered by ferric chloride leaching followed by cementation, at overall efficiencies exceeding 98%. The gold is recovered from the cobalt and bismuth leach residues by cyanidation, at 95% efficiency. Previous work described the results of the leaching of the concentrates, recovery of gold (Part I) and the recovery of bismuth (Part 11). This work describes the results of the cobalt recovery testwork and the resulting conceptual flowsheet. The sulfur dioxide-oxygen system was the most efficient for the oxidationlprecipitation of iron and arsenic from cobalt bearing pregnant leach solutions, producing purified solutions assaying <1 mg/L As and <8 mg/L Fe. The efficiency of cobalt solvent extraction (from the resulting purified PLS containing about 1 g/L Co) ranged from 9 1 to 98%; the co-extractions ranged from 88 to 100% for copper, from 28 to 33% for magnesium, from 6 to 7% for calcium and from 96 to 98% for zinc. Sulphide precipitation processes (using either sulfur dioxidelelemental sulfur or sodium sulfide) produced residual copper concentrations in the cobalt strip solution ranging from 0.1 to 2 mg/L Cu. About 90% of the calcium and magnesium were separated by scrubbing the organic with cobalt sulfate, producing residual concentrations of 12 mg/L Ca and from 180 to 330 mg/L Mg in typical feed solutions directed to cobalt carbonate precipitation tests. Cobalt carbonate precipitation efficiencies ranged from 75 to 78% when calcium and magnesium co- precipitations were restricted from 8 to 17% and 0.3 to 0.4%, respectively. The limits required by most stringent specifications on commercial grade cobalt carbonate products were met or exceeded.

Jan 1, 2002

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 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 Metehan Erdogan, Orhan Gökçe Göksu, Ishak Karakaya

"An experiment (mixture) design was created to optimize the process parameters of the electrochemical reduction of CaW04 to W in molten CaCl2-NaCl eutectic mixture. Temperature, applied voltage and the length of Kanthal wire winding of the CaW04 pellets were selected as the process parameters that were allowed to vary between the predetermined minimum and maximum values. The rates of the electrochemical reductions were interpreted from the variations of current and total charge vs. time graphs under different conditions. The analysis pointed out that 640°C and 2.81 V resulted in the fastest reduction. Itwas seen that the effect of Kanthal wire winding on the output current was less pronounced when compared to the other two parameters.IntroductionFFC Cambridge Process [1] has been applied to a number of metal oxides in laboratory experiments to produce metals. In nearly all of these studies, the electrolysis temperature was around 900°C, the electrolyte was pure CaCl2 or CaCl2 containing salt solutions and the anode was graphite. However, it was recently shown that the electrochemical reduction process of metal oxides in CaCl2 containing electrolytes at the mentioned high temperatures was not suitable for tungsten production [2], It was reported that as soon as WO3 contacts CaCl2, the following reaction occurs:"

Jan 1, 2012