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By Simon Lekakh, Von Richards, C. Hank Rawlins, Kent Peaslee

"Batch aqueous leaching and carbonation tests were conducted using industrial steelmaking slags to determine the effect of carbonic anhydrase enzyme as a catalyst. Calcium leaching is a strong function of particle surface area, and the extent can be expressed as a function of time and particle size. Carbonic anhydrase did not affect the calcium-leaching rate, however, it did catalyze calcium carbonate formation to achieve a neutralization time near the theoretical rate. Additionally, carbonic anhydrase modified the precipitate morphology due to accelerated particle nucleation. Time controlled tests in which the pH dropped to ~6 decreased the amount of carbonate produced, and this effect was exaggerated by carbonic anhydrase, while pH controlled tests (>8.5) exhibited the highest rate of carbonation. Because the leaching rate was ~50% faster than the carbonation rate, a further increase in the amount of carbonation may be realized by using carbonic anhydrase however pH must be >10.3.IntroductionSteelmaking slag contains high fractions of alkaline earth oxide based phases (i.e., CaO and MgO) that exothermically form carbonates. Thus, it is being considered as a means of permanent carbon dioxide sequestration. At current U.S. steel production rates, approximately 13-17 million tons/year of slag are generated from basic oxygen furnace (BOF), electric arc furnace (EAF), and ladle metallurgy furnace (LMF) processes [1]. BOF and EAF slag is used as high quality mineral aggregate or cement clinker, while LMF slag, produced at ~15% the rate of BOF and EAF slags, has limited use as blast furnace flux or acid mine neutralization with the majority going to landfill [2]. Based on slag’s chemical nature and immediate availability as a co-product from steel production, the steel industry initiated a project to investigate hydrous carbonate formation in steelmaking slag as a method of sequestering carbon dioxide emitted in steelmaking offgas [3]. The goal of this project is to determine the reactor parameters suitable for the design of an industrial system for treating steelmaking offgas with raw or minimally processed slag."

Jan 1, 2009

By P. M. Tait, N. A. Warner

"The refining of thermally produced zinc is currently performed using a highly energy intensive and arguably outmoded process, distilling zinc under atmospheric pressure at temperatures of 900°C to 1000°C. In order to produce refined zinc more profitably and with less environmental impact a new process has been proposed. This process is generic to all thermal zinc smelters and aims to match the purity of zinc from current technology (99.99%-99.999%). The objective is to perform all separation processes using only the heat contained in the smelter product stream. Vacuum conditions are extensively used lowering operating temperatures and enhancing separations. As part of this process zinc is distilled under vacuum from high concentration obtaining a refined product with respect to lead content. A mathematical model has been developed from fundamental principles to describe this stage, the distillation of zinc across a temperature difference between two circulating zinc streams in open channels under vacuum. Heat for the distillation is supplied by the liquid phase, necessitating a large recycle to maintain high operating temperatures, and keep zinc concentrations high. In determining this model and the operating conditions required, relationships between temperature, pressure and composition are considered.IntroductionCurrent technology (the Refluxer) used to refine thermally produced zinc is both expensive and highly inefficient. At present 80% of the worlds zinc is produced via the electrolytic process reflecting the poorer performance of the thermal route, the zinc-lead blast furnace and Refluxer. A new process is proposed to overcome the drawbacks of current processes. These drawbacks are both economic and environmental. The Refluxer requires 6.6 GJ of energy to refine one tonne of SHG zinc 1, other disadvantages of the Refluxer stem from high operating temperature, around 900°C, and liquid zinc being highly corrosive towards ferrous metals. The Refluxer is constructed from silicon carbide sections which join together by means of flat machined faces making liquid metal leaks inevitable. The Refluxer columns are very sensitive to thermal cycling, thermal shock and mechanical vibration, which easily lead to structural failure. To avoid thermal stress on the columns the feed rate and feed temperature need to be kept constant which means the feed baths to the columns must be able to accept solid and liquid feed as the Refluxer has to operate when the smelter is shut down."

Jan 1, 1998

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 Jerry L. Smith

Industry on a whole has not been very receptive to government prodding to implement waste minimization programs. Waste minimization has the appearance of substantial benefits, however, there are underlying difficulties and suspicions that need to be addressed before industry will support pollution prevention initiatives. They can be summarized as follows: - Human behavior resists change, uncertainty, and unknowns. - New waste minimization techniques are difficult to find and research. - Calculating the true cost of present waste practices as well as new techniques being considered is difficult and time consuming. - Getting a consensus opinion of all the individuals affected on the course or technique to be employed in a pollution prevention program. New software products have addressed many of the problems associated with implementing pollution prevention programs: They contain research on a large number of pollution prevention techniques and case studies; they generally are accessed by EPA ID number, chemical name, or synonym; and some programs have the option to print a comprehensive written user-specific pollution prevention program.

Jan 1, 1994

By C. D. Chapman

Current regulations regarding the landfill disposal of asbestos containing wastes are inadequate to ensure there are no ground water or airborne emissions. Accordingly, there is growing recognition that asbestos wastes can only be safely disposed of by using techniques that destroy the hazardous fibres. An innovative high-temperature plasma arc technology (The MAGRAM Process) is being developed for the recovery of magnesium metal from asbestos together with supplementary magnesia containing feedstock. The furnace will operate in. open bath mode with aluminium and/or ferrosilicon being employed as reductant. An important advantage of the process is that magnesium vapour within the furnace will be generated close to atmospheric pressure rather than at reduced pressure under which existing processes operate. Thermodynamic modelling work has been undertaken to define the range of slag composition and furnace temperature under which magnesium production at atmospheric pressure is feasible. The effect of slag chemistry, reductant addition, and temperature on product quality and yield have also been investigated and key aspects have been tested on bench scale. A 300 kW pilot plasma furnace unit has been employed for the treatment of calcined asbestos wastes. Aspects of design and operation of the unit are detailed. Acknowledgement: This work is substantially financially supported by the European Communities under the Industrial and Materials Technologies (Brite EuRam H) Research and Development programme.

Jan 1, 1995

By Von L. Richards

Rapid Freeze Prototyping (RFP) is a novel solid freeform fabrication technology that creates parts by depositing water droplets and freezing them rapidly to form layers. An investigation into the smallest thickness that can be achieved by the RFP process was conducted. The factors that could significantly affect the thickness of the part built by this process including substrate temperature, volumetric feed rate, table velocity, nozzle frequency, nozzle standoff distance, and head pressure were considered. A shell building technique for use with the RFP system has been developed. Thin wall ice patterns have been invested using production shell building techniques and an alcohol-based slurry. The finished shells were quantitatively evaluated by inspecting their total shell thickness, mold cavity dimensional reproducibility, and shell strength. Pattern loss is influenced by not only the alcohol / water interaction but also the starting thickness as it relates to thermal mass.

Jan 1, 2008

By Xun An

Slag from an electric slag cleaning furnace was injected with methane and air mixtures to facilitate the recovery of copper and cobalt. The effects of methane-to-air ratio, gas flow rate and temperature on the reduction and metal separation were investigated. The results showed that over 90 percent copper and up to 60 percent cobalt could be recovered from the slag with a gas utilisation of around 70 percent, as calculated by thermodynamic simulation. Methane-to- air ratio was a major factor affecting the rate of reduction under the present experimental conditions. Further, injection of gaseous reductants greatly enhanced the coalescence and settling of entrained metal droplets. A reduction mechanism is proposed and the factors influencing the coalescence of copper droplets are discussed.

Jan 1, 1998

By W. Drummond

The cooling of smelter gases by air dilution, adiabatic evaporative cooling and indirect heat exchange is discussed with reference to the ,process, to the subsequent cleaning of the gas and to the use of the heat extracted from the gas. The method of reducing the effect of acidic ,sulphide formation on the corrosive properties of the gas and the dust and the development of surface cleaning mechanisms are discussed. The development of indirect recuperators using air, water or steam cooling, made 'possible by the control of surface fouling is traced. The application of the modern Waste Heat Boiler to the new sulphide smelting processes is discussed with respect to the natural and forced circulation concepts. Case histories are presented to illustrate mistakes made with respect to designs produced without recourse to sensitivity analysis and without an appreciation of "worst process conditions".

Jan 1, 1992

By W. Drummond

The cooling of smelter gases by air dilution, adiabatic evaporative cooling and indirect heat exchange is discussed with reference to the process, to the subsequent cleaning of the gas. and to the use of the heat extracted from the gas. The method of reducing the effect of acidic sulphide formation on the corrosive properties of the gas and the dust and the development of surface cleaning mechanisms?are discussed. The development of indirect recuperators using air, water or steam cooling, made possible by the control of surface fouling is traced. The application of the modern Waste Heat Boiler to the new sulphide smelting processes is discussed with respect to the natural and forced circulation concepts. Case histories are presented to illustrate mistakes made with respect to designs produced without recourse to sensitivity analysis and without an appreciation of "worst process? conditions".

Jan 1, 1992

By James C. Barker

Recent investigations of a 55-km long trend of intrusive complexes on southern Prince of Wales Island have identified significant resources of Nb, Y, REE. U, Zr, and a host of potential by-product metals. The northwesterly trend comprises multi-phased sodic alkaline and peralkaline diorite, monzonite, syenite, and riebeckite granite. There are at least three significant deposit types recognized, two of which, 1) pegmatite dikes/vein-dikes that zone laterally from the intrusions and 2) concentrically zoned pegmatites, contain most of the lithophile metals. A third, epigenetic replacement-type mineralization, contains much of the U resource. Other deposit types with minor or unknown resource potential include diatremes, carbonatite, and placers. This report summarizes the deposit evaluations, characterizes the mineralization, and estimates the resources. To date a total of 40.7 million tons of mineralized material is estimated as indicated or inferred. Most of the Y203 plus REO is at a grade exceeding 0.5% and half of the Nb20S exceeds 0.125%. Tonnage estimates would likely be substantially lncreased with additional exploration. Mineralogy is generally fine-grained and complex, and consists of more than a dozen principal REE-Y-Nb-U-Th-Zr phases, the sum of which may compose up to half of the rock. Approximately half of the REE-Y content comprises the heavy yttrium subgroup which is uncommon compared to deposits elsewhere. Although the Alaskan deposits are likely subeconomic at today's metal prices and consumption levels. recent technological advances suggest future demand may increase.

Jan 1, 1988

By Ian Baker, Xavier Pierron

"Iron aluminides hold great promise for intermediate temperature applications (to ~ 600°C) because of their excellent oxidation and sulphidation resistance and good strength. However, they have poor low temperature ductility, a feature which is exacerbated by water-containing environments. This paper presents an overview of the effects of environment on the ductility of iron aluminides, including the effects of iron aluminum ratio; ternary alloying additions, particularly boron; strain rate; and temperature. The mechanisms involved in water-induced embrittlement are discussed.IntroductionOver the last few years, it has became increasingly evident that the ductility and fracture toughness of many intermetallic compounds, particularly aluminides, are reduced dramatically if they are mechanically tested in either air or in hydrogen-containing atmospheres (1-5). For FeAI and Fe3AI, it has been shown that water vapor, for example in air at room temperature, can form atomic hydrogen by reacting with the Al atoms (1, 2). As a result in iron aluminides, the environmental embrittlement process is quite similar to traditional hydrogen embrittlement. This can be easily demonstrated by either testing an iron aluminide in an environment free of the deleterious species or by testing at high strain rates, both of which result in greater ductility. The purpose of this paper is to review recent progress in understanding environmental embrittlement in FeAI and Fe3AI, and to consider possible environmental embrittlement mechanisms. Greater understanding of this phenomenon will lead ultimately to remedies to this problem which is a major reason for preventing the practical application of these materials. First, some background on the iron-rich aluminides."

Jan 1, 1996

By Marcello M. Veiga

Informal gold mining operations in the Amazon emit about 100 tonnes of mercury annually because of poor amalgamation practice. Lack of information and the complexity of mercury transformations hinder effective action to prevent such pollution and/or monitor its extent. In the past, mathematical equations have been formulated to deal with the correlation of natural variables and mercury in biota but often, the error range is too great to provide useful models. Projection of physico-chemical variations in an environment subjected to mercury emissions onto the extent of bioaccumulation is fraught with many uncertainties and unknowns such as internal correlations between variables and the site-specific nature of biota contamination. Often assumptions about closed systems are invalid when applied to natural environments. This work presents a heuristic approach to this problem in which amalgamation methods and natural variables are dealt with using an IF-THEN rule-based system that concludes about levels of emission and risk of bioaccumulation. The system is able to handle uncertain or vague data and yet still provide useful output. Belief in mercury oxidation or dangerous conditions are examined using Fuzzy Logic techniques and Inference Equations. These belief levels are derived from thermodynamic equilibrium data together with field observations of natural variables. This procedure can reduce the need for sophisticated analytical equipment and can provide information and diagnosis to non-technical people.

Jan 1, 1994

By D. B. Dreisinger, V. van der Pas

Zinc sulphate electrolyte used for zinc electrowinning must be purified for cObalt ions. The cobalt is removed in a cementation stage by the addition of zinc dust. Copper arid antimony are frequently used additives which enhance the cementation of cobalt. This paper aims at a better understanding of how copper and antimony promote the removal of cobalt. Initial experiments were done in a batch cementation reactor. Copper and antimony precipitated in the early stages of cementation indicating that a preferential substrate was formed. The individual role of copper and antimony was further investigated in an electrochemical cell. On a microsca1e, the , growth process, morphology and the composition of the precipitates were examined with SEM and XRD. It was found that cobalt could not be deposited in its pure form but as a cobalt-zinc alloy with zinc as the prime constituent. Copper increases the cathodic surface area of zinc dust by precipitating as numerous dendrites. Antimony acts as a cathodic surface onto which a cobalt-zinc alloy with an increased cobalt content is deposited.

Jan 1, 1997

By Batric Pesic

Reactions of metallic iron were studied in several different aqueous solution systems: water, medium salt solution used for the growth of T ferrooxidans, ferric iron solution and solution containing T ferrooxidans. Each system was studied under abiotic and biotic conditions in the presence of T ferrooxidans and as a function of pH, particle size of iron powder, temperature, ferrous and ferric iron concentrations. It was found that metallic iron reacts with water differently than does with ferric iron in water. Surprisingly, T ferrooxidans were non-functional in the dissolution of metallic iron. Also, the reactions of metallic iron with pure water were indistinguishable from the reactions with water containing medium salts for bacterial growth. The reactions with ferric iron were also independent of medium culture compounds. The mechanisms of metallic iron reactions with ferric ions are different from the mechanisms of metallic iron reactions with water.

Jan 1, 2001

By F. D. S. Marquis

An investigation of the mechanisms of formation of two types of porosity-primary and secondary-their characterization, evolution during processing, and effects on the mechanical behavior (fracture, fatigue, and failure) of 7X50 and 2X24 alloys has been conducted. The mechanisms of formation of three forms of primary or cast porosity were investigated, and each form was characterized: (a) macroscopic shrinkage porosity-MSP); (b) microscopic interdendritic porosity (MIP); and (c) hydrogen gas porosity (HGP) or primary hydrogen porosity (PHP). The mechanisms of formation of four forms of secondary or thermal/thermomechanical porosity were investigated, and each form of porosity was characterized: (a) high temperature oxidation (HTO). internal hydrogen precipitation (IHP), or secondary hydrogen precipitation (SHP); (b) preheating blistering porosity (PBP); (c) eutectic melting porosity (EMP);and, (d) dissolution micro void formation (DMF). The evolution and interactions of the primary and secondary types of porosity (w.ith special emphasis on PHP and SHP) during industrial and laboratory processing and their effects on the fracture and failure behavior of both types of alloys (with special focus on fatigue crack initiation and propagation) were investigated.

Jan 1, 1996

By Pengfu Tan

In order to understand and control the formation of dioxins and furans in iron ore sinter plants and to possibly avoid expensive end-of-pipe removal stages, thermodynamic calculations on the stability of PCDD/Fs have been combined with sinter process modeling by means of kinetic simulations and computational fluid dynamics. Three thermodynamic databases of PCDD/Fs, derived using the Group Additivity approach and two computational molecular modeling methods, MNDO and PM3, respectively, combined with the SGTE database have been used to model the PCDDIF formation and the PCDD/F isomer distributions in iron ore sintering. The results show very similar conditions for the PCDD/F formation using the different databases. Concerning the isomer distributions of toxic PCDD/Fs, the calculated data derived from the MNDO method showed optimum agreement with measured values from industrial furnaces. The thermodynamic calculations also proved that the isomer distributions found in combustion processes are equilibrium values, while the concentration ratio of PCDDs and PCDFs in the wind boxes does not represent an equilibrium state. A CFD model of iron ore sintering was developed including the kinetics of 15 relevant chemical reactions with the aim of describing the temperature fields and the gas flow patterns in the sintering bed. On the basis of these information and experimental observations reported in the literature possible pathways for the PCDD/F formation in sinter plants have been identified: PCDD/Fs are formed in the critical temperature region of 250 to 450°C below the combustion zone, are then carried downwards with the gas and condensed close to the bottom of the sinter bed. Transported to the discharge end with the solid mixture, they are again released into the gas phase when the flame front approaches the bottom. PCDD/Fs are also formed in the last wind boxes when the hot off-gases cool down and reach the critical temperature range. Consequently, methods to reduce the dioxin formation reactions are proposed including inhibitor addition to the sinter feed and off-gas quenching.

Jan 1, 2003

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 H. H. Kellogg

The thermochemical properties of molten solutions in the binaries Cu-Bi, Cu-Sb and Bi-Sb, as well as the ternary Cu-Bi-Sb, have been correlated and described in mathematical form by use of the associated species concept combined with the three-suffix Margules equations to account for the non-idea 1 behavior of the solution species. Agreement of the correlations with experimental data is excellent (relative deviation of less than 2.5% in the values of the activity coefficients) in most cases. The correlations are applicable over the entire composition range of each system, and in the temperature range 700°-1250°C.

Jan 1, 1985

By D. Papazoglou

This work was undertaken to investigate the thermodynamic and kinetic feasibility of using hot sulfur dioxide bearing gases from smelting processes to selectively sulfate the nickel in nickel laterite ores for subsequent extraction in water. The environmental benefits ofthis approach, as opposed to releasing the gas to the atmosphere, and the economic benefit of directly utilizing the S02 rather than converting it to sulfuric acid are strong drivers for such a process. A thermodynamic analysis indicated that selective sulfation of the nickel could be feasible under appropriate conditions and these were explored through a series of laboratory scale experiments. Laterite samples were reacted at temperatures between 500 and 800°C with an equilibrated mixture of sulfur dioxide, oxygen and nitrogen in a fixed bed reactor. Tests were conducted on saprolitic ore from Bulong, Western Australia, limonitic ore from New Caledonia and garnieritic ore from Indonesia. Nickel extractions were highest from the limonite and relatively low from the other ores. The maximum selective extraction of nickel from the limonite in a single stage sulfation was 73%. Sulfation of other elements present in the laterites was also examined. A two-stage process was also identified which involved sulfation using a strong sulfation potential followed by weaker sulfation potential to attempt to convert ferric sulfate formed in the first stage to ferric oxide. This increased the extraction for the limonite ore to around 84% Ni, 95% Co and 2% Fe. Direct sulfation of laterite could be feasible in locations where sulfide smelting or roasting operations are relatively close to laterite deposits.

Jan 1, 2003

By D. Papazoglou

This work was undertaken to investigate the thermodynamic and kinetic feasibility of using hot sulfur dioxide bearing gases from smelting processes to selectively sulfate the nickel in nickel laterite ores for subsequent extraction in water. The environmental benefits of this approach, as opposed to releasing the gas to the atmosphere, and the economic benefit of directly utilizing the SO2 rather than converting it to sulfuric acid are strong drivers for such a process. A thermodynamic analysis indicated that selective sulfation of the nickel could be feasible under appropriate conditions and these were explored through a series of laboratory scale experiments. Laterite samples were reacted at temperatures between 500 and 800°C with an equilibrated mixture of sulfur dioxide, oxygen and nitrogen in a fixed bed reactor. Tests were conducted on saprolitic ore from Bulong, Western Australia:, limonitic ore from New Caledonia and gamieritic ore from Indonesia. Nickel extractions were highest from the limonite and relatively low from the other ores. The maximum selective extraction of nickel from the limonite in a single stage sulfation was 73%. Sulfation of other elements present in the laterites was also examined. A two-stage process was also identified which involved sulfation using a strong sulfation potenrial followed by weaker sulfation potential to attempt to convert ferric sulfate formed in the first stage to ferric oxide. This increased the extraction for the limonite ore to around 84% Ni, 95% Co and 2% Fe. Direct sulfation of laterite could be feasible in locations where sulfide smelting or roasting operations are relatively close to laterite deposits.

Jan 1, 2003