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By James P. Bennett

The U.S. Bureau of Mines, Tuscaloosa Research Center, is conducting a review of the usage of different types of refractories, the current industrial practices to recycle/dispose of spent refractories, and the concerns associated with these practices. This information will serve as the technical basis for initiating a research program to recycle or find alternate uses for spent refractory materials. Approximately 1.6 million metric tons of clay based and 1.2 million metric tons of non-clay based refractory materials were manufactured in the United States in 1992 alone, representing a value of almost 2 billion dollars. Landfill has been and remains the disposal means of choice. Issues such as environmental regulations, concerns over landfill disposal, future liability, and product stewardship programs have brought about increased emphasis for recycling or alternate material use. Information on refractory consumption and the issues associated with recycling or disposing of used materials will be discussed, including current recycling practices.

Jan 1, 1995

By George P. Demopoulos

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

Jan 1, 1999

By G. R. Palmer

The success of future electric vehicles will depend greatly upon the power supply choices made today. Research is presently being conducted by automotive engineers and electrochemists to determine what battery type may be the most promising. Not only are product production and application efficiencies being evaluated but also environmental concerns of reclamation and recycling. Rechargeable batteries using nickel-metal hydride electrodes are strong candidates for these electric vehicle applications. The U.S. Bureau of Mines is investigating hydrometallurgical technology that separates and recovers purified metallic components present in nickel-metal hydride battery scrap. Sulfuric, hydrochloric, and nitric acids are all capable of dissolving the battery electrode alloys given the proper operating conditions. Solvent extraction of the leach solutions using D2EHPA removes iron, and selective precipitation shows promise of recovering the other metals in the H2SO4 and HNO, systems.

Jan 1, 1994

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

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

Jan 1, 2010

By John W. Graydon

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

Jan 1, 1992

By R. Cavanagh

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

Jan 1, 1996

By Matthew C. Binsfield

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

Jan 1, 1996

By Matthew John M. Krane, Christopher J. Vreeman, J. David Schloz

"A continuum mixture model of the direct chill casting process is used to model the transport phenomena and solidification behavior in the Direct Chill casting of an Al - 6 wt% Cu billet using Wagstaffs AirslipTM process. The model, which includes the transport of free-floating solid particles, can simulate the effect of a grain refiner on macrosegregation and fluid flow. Numerical predictions of sump profiles and composition and temperature fields are presented. Two 45 cm diameter billets were cast under production conditions with and without grain refiner. Temperature and composition measurements and sump profiles are compared to the numerical results. The comparison shows excellent agreement for the grain refined case. It is believed that an incorrect model assumption prevents good agreement in the non-grain refined billet. IntroductionDirect chill casting is a semi-continuous process in which molten aluminum enters the top of a water-cooled mold, is cooled, and forms a solid ingot drawn out below (Figure l(b)). The molten aluminum begins to solidify due to the cooling effect of the mold wall. As the ingot is withdrawn from the bottom of the mold, water jets impinge on the surface, directly cooling the billet and forming a solid layer around a liquid melt, commonly referred to as the sump.A particular defect that occurs in a wide range of casting processes, including the direct chill (DC) casting of aluminum alloys, is macrosegregation, the uncontrolled redistribution of alloying elements on the scale of the ingot during solidification. Macrosegregation in DC cast ingots can produce non-uniform mechanical properties [l], which affects the behavior of the metal during downstream forming and heat treat operations."

Jan 1, 2001

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&apos;s reduced chaotic temperature &apos;tj to describe external interactions, and reaction extent Ilj as independent variable, this equation covers the whole domain of the system&apos;s possible states from true thermodynamic equilibrium through the open equilibrium to bifurcations and chaos depending on the &apos;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 Godwin J. Igwe

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

Jan 1, 1994

By Sang Han Son

The vapor pressures of FeCI2 and ZnC12 in the FeCl2-ZnCl2 system were measured by the transpiration method at 873K and 917K. The vapor pressure data were interpreted to indicate the formation of complex ions in the FeCl2-ZnCl2 melts. It is presumed that the complex molecule FeZnCl4 as well as FeCI2 and ZnCI2 exists in the vapors in equilibrium with molten FeCl2-ZnCl2 mixtures. The activities in the FeCl2-ZnCI2 system are shown a negative deviation from Raoult&apos;s law. These results suggest the formation of complex ions such as ZnCl42- in molten FeCI2-ZnCI2 mixtures.

Jan 1, 2003

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

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

Jan 1, 2000

By B. J. Beaudry

The effect of various levels of purity of the rare earth fluorides and the calcium reductant used to prepare rare earth metals were determined. Metals which have low melting points such as La, Ce, Pr and Nd are not purified by distillation or sublimation. Impurities in the reactants remain as contaminants in these metals. Gd, Tb, Y and Lu which have slightly higher vapor pressures at their melting points than the first four metals are usually distilled to remove the Ta or W impurity introduced by the crucible and are purified slightly with respect to 0 and N by distillation. Rare earth metals that have high vapor pressures such as Sc, Dy, Ho and Er can be purified with respect to 0, N, C, as well as Ta or W by sublimation. The most volatile rare earth metals Sm, Eu, Tm and Yb are readily purified by sublimation and are usually prepared by a reduction-distillation process directly from the oxide. The importance of each step of the processes in determining the final purity of the individual rare earth metals is discussed.

Jan 1, 1989

By K. Moriyamo

Operation improvement efforts at Hyuga Smelting Co., Ltd. have focused on calcining capacity in the reduction rotary kilns ("the kilns"), whose limited feed rate capacity had capped production at around 18,000t-NiN since 1995. To improve the kilns&apos; feed rate capacity of 80 wet t/hr, attempts were made to increase the gas flow in the kilns by increasing the capacity of the off-gas fans. However, as the increased gas flow resulted in only limited improvement of the kilns&apos; feed rate, a scoop feeder was installed on each kiln to add coal to the middle of each kiln&apos;s interior to gain a higher efficiency of thermal supply and conversion. With these gas flow and coal charge addition operations, the kilns&apos; feed rate capacity increased up to 120 wet t/hr, with burner fuel efficiency increasing by approx. 10% (approx. 5% in total with the additional coal included). As a result, production was raised to a level of 22.000t-Ni/Y Keywords: reduction rotary kiln, scoop feeder, additional coal charge.

Jan 1, 2004

By James E. Hoffmann

Oxidative pressure leaching is gradually supplanting other techniques for the decopperizing of slimes. The reasons for this include: much more rapid reactions, more compact equipment, a reduced environmental burden, and perhaps most important, a much lower final copper concentration in the decopperized slimes. This paper will discuss the reactions occurring during decopperization, the acidity and temperatures encountered and the techniques employed for discharging non condensable gasses. A spreadsheet is provided which allows adjusting the operating conditions depending upon raw (undecopperized) slimes composition, solids concentration and lixiviant composition. A typical process equipment flowsheet is provided along with a process narrative.

Jan 1, 2000

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

Jan 1, 2001

By Christoph Beckermann, Kai Liu, Richard A. Hardin

"A two-dimensional heat transfer model for transient simulation and control of a continuous steel slab caster is described. Slab thermal and solidification conditions are computed by the model as a function of time-varying casting speed, secondary spray cooling water flow rates and temperature, slab thickness, steel chemistry, and pouring and ambient temperatures. A solidification model that includes the effects of steel chemistry, cooling rate and mierosegregation on the solidification path is incorporated directly into the caster model. Comparisons between measured and predicted liquidus and solidus temperatures are given for two low alloy steels, and show good agreement. Predicted and measured slab surface temperatures recorded on an operating caster are compared with this transient model and show that the model can predict the temperature response at the slab surface. Results of several simulations are given to demonstrate the effects of changing casting conditions on the slab thermal profile and the solidification end-point. A control methodology suitable for online control of a continuous casting machine is described, and its ability to control the surface temperature profile by dynamically adjusting secondary spray cooling flow rates is demonstrated using the simulator. IntroductionIn order to remain competitive in today's world-wide market for continuously cast steel products, steel producers are finding that it is ever more important to implement process control and to develop a more thorough technological understanding of their casting process. By integrating process control and monitoring into both production and quality control, producers are better able to meet customers' demands for steel of the required quality, quantity, size, grade, and properties at the lowest cost. Computer models used for real-time/on-line prediction and control of continuous steel casters are fundamental tools to accomplish this. Accurate on-line prediction and control of steel solidification and heat transfer allows for more flexibility in caster operation by giving operators the ability to change casting speeds while keeping critical process parameters within required ranges. Such control 'capability also results in more uniform quality throughout an entire casting sequence from startup to shutdown. Furthermore, due to the unreliability of temperature sensors, and the lack of good sensors for important process parameters such as solidification end-point and liquid pool depth, computer-based control models are often the only available option."

Jan 1, 2000

By Renato G. Bautista

"The chemistry of the separation of metals from each other and from the other undesirable components involve multiple simultaneous chemical reactions. In the case of leaching, the heterogeneous chemical reactions between the solid and the liquid phase may be limited to a few reactions. In the homogeneous liquid phase, the number of simultaneous chemical reactions could be double or triple that of the number of heterogeneous reactions. The rate of dissolution becomes very dependent on the changing concentrations of the significant chemical species taking part in the multiple reactions in both the heterogenous and homogeneous phase. The rate expression developed for the process must take into account the mechanism of chemical reactions in order to best represent the actual process. This paper also examine the role of mass transfer with chemical reaction in the develpoment of the rate equations for dissolution, liquid-liquid extraction, membrane separation, precipitation, and electrodeposition.IntroductionThe understanding and the elucidation of the mechanism of the rate phenomena for a specific chemical reaction system is of prime importance in the development of a successful chemical process. The development of successful emerging technologies for metals separation will depend on the accurate interpretation of the intrinsic chemical reaction kinetics and the rate of mass transfer of the desired metal species during its separation from the undesirable chemical species. This is the case whether the process application is for separation, concentration, and /or purification.The chemical processes that will be examined in this presentation will include leaching, solvent extraction, membrane separation, precipitation, and electrodeposition."

Jan 1, 1996

By KNona C. Liddell

Goethite is an important naturally occurring sorbent for divalent heavy metals and has often been used as a model compound in studies of adsorption on oxide mineral surfaces. Surface complexation modeling, surface spectroscopy, and electrochemical techniques have all been applied to goethite adsorption. Modeling studies have shown that usually several different sets of fitted parameters are equally successful in representing surface charging and adsorption data. Surface spectroscopic data are proving valuable in determining the nature of the surface sites, and refined models now incorporate structural information on interatomic distances and coordination numbers. Multisite surface complexation models can give very good fits to surface charging and adsorption data, but further improvements are needed to better represent surface reactions involving exchange of protons and divalent cations. Recent experimental and modeling studies on adsorption of divalent transition metals on goethite are described and the present status of the field is assessed.

Jan 1, 1999

By Renato G. Bautista

The chemistry of the separation of metals from each other and from the other undesirable components involve multiple simultaneous chemical reactions. In the case of leaching, the heterogeneous chemical reactions between the solid and the liquid phase may be limited to a few reactions. In the homogeneous liquid phase, the number of simultaneous chemical reactions could be double or triple that of the number of heterogeneous reactions:. The rate of dissolution becomes very dependent on the changing concentrations of the significant chemical species taking part in the multiple reactions in both the heterogenous and homogeneous phase. The rate expression developed for the process must take into account the mechanism of chemical reactions in order to best represent the actual process. This paper also examine the role of mass transfer with chemical reaction in the develpoment of the rate equations for dissolution, liquid-liquid extraction, membrane separation, precipitation, and electrodeposition.

Jan 1, 1996