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By K. S. Raja, M. Misra, S. K. Mohapatra

"Ordered arrays of TiO2 nanotubular photocatalysts were prepared by a simple anodization process. Band gap states of the TiO2 were altered by controlling the anodization electrolyte composition and thermal annealing conditions that resulted in enhanced photo activity. These nanotubes were used for reducing CO2 to methanol either by photochemical or photo electrochemical routes. Pd nano-particle loaded TiO2 nanotubes were employed for photochemical reduction of CO2 to methanol that showed a conversion rate of 12 x 10-3 mol m- 2h-1. Carbon modified TiO2-xCx type nanotubes were used as photo anode and Ti as cathode for photo electrochemical reduction of CO2. The potential of Ti cathode was maintained at -0.5 V SCE. The formation rate of methanol was determined as 13 x 10-3 mol.m-2h-1.1. IntroductionGlobal warming due to emission of carbon dioxide is a serious environmental concern. The atmospheric concentration of CO2 is about 384 ppm by volume and about 3 x 1012 tonnes by weight. Burning of fossil fuels and deforestation are the leading causes for increase in the anthropogenic CO2. More than 32 x 109 tonnes of CO2 are released per year (based on 2006 data) worldwide from the fossil fuel. Pumping CO2 from the fossil fuel power plants into deep ocean basin is one of the most discussed disposal options. The other potential option is converting this green house gas into valuable fuels.Carbon dioxide feed stock can be converted into fuels of solid, liquid or gas phase by chemical, electrolytic, photocatalytic and photo-electrocatalytic methods. Reduction of CO2 to fuel form of any phase requires energy. The reduction process should be energy efficient so that we do not spend more energy and emit more (indirect) CO2 in the process of converting CO2. From this point of view, conversion processes occurring at room temperature look attractive.Electrolytic conversion of CO2 into various forms such as methane1, ethane2, ethylene3, methanol4,5, ethanol6, n-propanol, formic acid7, and formaldehyde has been widely reported. The standard equilibrium potential (at pH: 0) for reduction of CO2 to methanol is 0.14 VSHE and to methane is 0.2 VSHE which is thermodynamically more favorable than hydrogen reduction. However, the gas phase reduction is kinetically complex requiring effective electrocatalyst. The major issues with electrolytic conversion of CO2 to useful products are:"

Jan 1, 2010

By C. Alexandru Sonoc

Donnan Dialysis uses ion exchange membranes to extract and separate cations. The driving force is provided by differences in chemical potential, rather than by electric fields or pressure. A Donnan Dialysis based process to recover lithium, nickel, cobalt, manganese, and organic acid lixiviant from recycled lithium ion battery cathodes is under development. In this paper we present a model of Donnan Dialysis and results of simulations of the aforementioned process. The simulations show that 170 m2 of membranes can process 1000 L of leachate ([Li+] = 0.285 M, [Co2+] = [Ni2+] = [Mn2+] = 0.095 M, pH 2) in two days and recover 94.1% of the lithium (as lithium carbonate), 99.4% of the transition metals (as mixed sulphates ready for solvent extraction), and all of the organic acid using 423 mol of H2SO4 and 268 mol of KHCO3.

By Dennis J. Kemp

Laterite projects are found in the tropical and sub-tropical regions of the world. As a result severe meteorological situations accompany such projects, often in regions of high seismic activity and political uncertainty. Frequently, socio-economic development supported by political interest is a major driver for development, while environmental protection imposes numerous stresses on the project. This paper will review and examine the many social, environmental, technical and financial issues that a mining and extraction process is subject to during development. The options that must be evaluated will be discussed in the context of sustainable development. Issues of project standards and cultural impact through to long-term issues such as greenhouse gasses and climate change will be assessed in redirecting project environmental norms. Although a rationale for sustainable project can be developed many long- term uncertainties around issues remain. Keywords: sustainable development, communities, social issues, standards, energy, waste management, consultation, agreements

Jan 1, 2004

By Luiz A. Teixeira

This paper reports the results of kinetic studies involving the precipitation of arsenic from aqueous solutions as FeAs041 Fe(OH)3' using FeS04 as source of Fe ions, and Air or H202 as oxidizing agents. Both systems lead to an efficient removal of arsenic. The differences in oxidants performances are in the precipitation reaction rate -much faster using hydrogen peroxide. Mechanisms of reactions were suggested based on the following main steps:

Jan 1, 1996

By J. J. Moore

The application of plasma technology to process metallurgy is briefly discussed. Experiments involving in-flight reduction of minerals (taconite, chromite, in particular) with a solid-based carbon reductant are described. The resultant metallic and slag product analysis is discussed with respect to thermodynamic and kinetic considerations.

Jan 1, 1985

By Takeo Fujino, Nobuaki Sato, Yarong Wang, Kohta Yamada

"Ternary mixed sulfides of some transition metals MTS3 (M=Ba, ·Pb, T=Ti, Zr) were synthesized by a relatively low temperature process using sulfur melt. The mixture of starting materials, such as, metals and/or binary sulfides and a large excess of sulfur was reacted in a vacuum-sealed Pyrex or quartz ampoule at 350- 600 °C for one to three weeks. After the reaction, the remaining sulfur was completely removed by a process composed of filtration of sulfur melt and followed dissolution in CS2• The binary sulfides impurities coexisted in the products were removed by rinsing the products in water and acetone. By using the above method, BaTiS3, PbTiS3 and BaZrS3 'Were obtained in pure form. The effect of addition of halides on the yields of these ternary sulfides were also discussed.IntroductionThere have been a vast number of studies on the preparation and physical and /or chemical properties of mixed metal oxides. As is well known, some of such compounds exhibit excellent materials properties, causing them for use in mechanical, electronic, magnetic and chemical devices. Not a few mixed metal sulfides show similar physico-chemical properties to those of the corresponding mixed metal oxides. However, the study of the mixed sulfide crystals is rather sparse mainly due to difficulties in preparing these compounds. In various methods which have been adopted for preparing mixed sulfides, the simplest method would be the solid-solid reaction of the component binary sulfides or elements. However, there are always diffusional constraints with regard to the reactions in solid phases causing it necessary to heat the reactants at sufficiently high temperatures, viz. 800-1200°C. On the other hand, some mixed sulfides are unstable at high temperatures or to change their materials properties due to sulfur nonstoichiometry and structural modification depending on temperature, i.e., synthesis of such compounds needs to be made at lower temperatures. Processing in alkali halide melts is hopeful to overcome the above problems but to obtain the halide melts the temperatures above ~ 600 °C is needed. Low temperature reaction has been carried out for the preparation of Hg1.24TiS4, which was formed by the ·combination of TiS2 and molten Hg metal at 320°C[l]. Reaction of WS2 with LiBH4 melt at 350°C yielded LixWS2[2]. These sophisticated methods, however, can be applied only to the vary special cases."

Jan 1, 2000

By J. M. Floyd

Technology in use commercially and available for commercialisation for injection processing of base and precious metals in bath reactors is surveyed and compared. Differences between bath smelting and suspension smelting systems are highlighted in relation to important smelting criteria. The factors affecting the results achievable with various tuyere and lance injection bath smelting systems are discussed in relation to the various smelting, converting and refining operations involved in copper, nickel and precious metal processing steps. Process chemistry, process dynamics and heat and mass transfer rates are discussed for the different systems.

Jan 1, 1993

By Manfred K. Walther

"Tests were conducted on instrumented plates cast in the Abex Experimental Foundry to compare recorded solidification histories with results computed for corresponding models simulated with the C.A.S.T. program. The first plate was cast of low alloy steel and the second of carbon steel with a graphite chill at one end. Both were cast in molds of bonded silica sand. Temperature histories were recorded in the castings, molds and chill. Exceptionally good agreement was achieved between computed and experimental data. Other investigators will find the results useful as a benchmark against which they can compare the results of their own calculations.IntroductionSince the early 1970's our foundry engineers have used both two- and three-dimensional versions of the G.A.S.T. program to gain knowledge of the solidification process [1,2,3]. Study of the computed data gave insight as to how the rigging and risering of specific castings might be changed or adjusted to improve quality and yield. New schemes based on such analyses were then recommended for implementation on the foundry floor. The degree of success of the new practice was subsequently evaluated after the part had been poured, shaken out and examined. Similar conditions were noted in the sectioned castings whenever porosity and voids had been predicted by the computations. Appropriate modifications, when found successful in the model, were applied to the process. This led to a reduction, if not complete elimination, of the defects. Such results gave credence to the use of these programs as an aid in the production of better castings.Earlier investigations on simple shapes revealed excellent correlation between output derived with the G.A.S.T. program and exact solutions. Results also compared favorably with data calculated using other codes as reported in the literature [4] and summarized in the Appendix. However, since the computer program had not been verified by direct experiment, it was decided to run instrumented tests to check the theoretical predictions with actual measurements."

Jan 1, 1986

By J. M. Floyd

"Top submerged lance furnace developments started in CSIRO in the early 1970s and was given the name Sirosmelt. In the early work the technology was developed for tin smelting and processing tin slags but once a small pilot plant was established other slag processing applications were soon recognised and evaluated for various copper, nickel, zinc and cobalt-containing slags. The process was tried for copper smelting and converting, which was proven in the small pilot plant in 1978. In the same year the first commercial application of the technology was established for the recovery of tin from slags at Associated Tin Smelters, Sydney. Work on lead smelting was initiated by the CSIRO team in the late 1970s and laboratory work led to pilot plant trials by Mount Isa Mines.In the second decade of the technology the focus of development became commercial acceptance of the technology through marketing, development and application by Ausmelt and Mount Isa Mines; the former commercialising and developing the technology for a wide range of applications, while the latter concentrated on its own commercial needs of copper and lead smelting. This decade saw a number of commercial plants built in Australia, with considerable interest becoming evident from other parts of the world. Towards the end of this decade Mount Isa also entered into the business of marketing of the technology through rights dating to the joint work with CSIRO in the late 1970s.So far, after five years, the third decade of the technology has been characterised by diversification of applications of the technology to areas outside the non-ferrous and precious metals production industry. The waste processing and recycle industry and the iron and steel industry have recognised that the top submerged lancing system is a new type of reactor with many significant features which provide new opportunities for processing a range of materials under good environmental controls in a cost effective manner.I hope this audience will excuse my boldness in talking about the third decade of the technology when we are only half way through! I am aiming in this paper to not only talk about the past, but to try illustrate the future directions which I envision."

Jan 1, 1996

Pyrometallurgical reactors constitute a key processing component in the total primary and secondary resource cycle, being involved both in primary smelting, converting and extraction, as well as the reprocessing of scrap, from aluminum cans to end-of-life automobiles. To effectively control the overall resource cycle, one needs to take a systems modeling approach of the whole cycle, seeking to also understand the dynamic process behavior of the individual components of the cycle, and then especially the part that contributes most to the chemical conversion, namely the pyrometallurgical reactor. This paper highlights the role of pyrometallurgical thermodynamics, in the whole resource cycle and specifically places equilibrium thermochemistry in the context of process dynamics where large variable inventories are recycled or maintained within the system. This paper will therefore review the semi-empirical dynamic modeling tools, which are used to model complex systems with the specific goal of developing dynamic predictive models, which also include slag-alloy chemistry, towards controlling the recycling in a feed forward manner. To illustrate the primary processing side, high carbon ferrochrome will be presented as a brief case study. It also will show how the distributed nature of the chemistry of melts in the case of primary extraction, and secondary materials such as recycled end-of-Iife vehicles, have a significant impact on the process outcomes and model predictions. It is therefore argued that the fundamental thermodynamics and kinetics in metallurgical reactors playa final crucial role in modeling the closed material cycle, but only when it is used in conjunction with process systems theory based on reconciled data for parameter estimation and model calibration.

Jan 1, 2003

By C. Gasparrini

Mineralogy may be applied to the selection of appropriate separation techniques, as well as to assist in the evaluation of problems causing loss of metals and other economically important elements during plant processing. Mineralogic studies may thus help develop techniques to optimize metal recoveries. The present paper describes how such factors as the minerals in which the elements of interest are concentrated, their chemistry, the chemistry of the associated minerals, grain size and textural associations with other minerals in the ore, may affect decisions on separation techniques for the recovery of economic elements. A number of case studies are described in which the mineralogical observation of ore samples has revealed the cause of problems experienced in the extraction of select precious and base metals, or has been decisive in the choice of appropriate techniques for recovery.

Jan 1, 1981

By Jr. Napolitano, Jr. Sanders

"Morphological evolution of a dendritic growth front in a binary alloy is simulated using a cellular automaton approach to establish the feasibility of modeling such growth with a local rule-based scheme. The motivation for this work is derived from the need to predict the development of solidification structures within real components of complex geometry, where significant constraint of the thermal and solutal fields may exist. Such cases present complex boundaries and large domain sizes, which may preclude the effective use of more conventional methods. In this work, a model is presented which couples a two-dimensional alternate-direction-implicit finite-difference diffusion solution with a cellular automaton growth algorithm to simulate morphological evolution in alloys solidifying under directional growth conditions. Temperature, composition, and interface curvature are incorporated into a local growth potential which is used by the automaton, allowing the interface to evolve. Alloy solidification is simulated over a range of experimental conditions, producing various structures. Issues addressed include morphological instability, primary spacing selection, interface curvature, microsegregation, and tip conditions.IntroductionThe development of dendritic structure plays an essential role in alloy solidification. Virtually every microstructural feature, within a cast alloy component, is related to the interface morphology present during solidification. Conventional solidification theory, describing dendrite tip kinetics and mushy zone phenomena, provides a means for estimating overall microstructural parameters for an alloy solidified under steady-state conditions. Microstructural prediction for actual components, which are finite in size and complex in geometry, requires a description of the evolution of the interface morphology under transient conditions and geometrical constraint and an understanding of how the structure propagates through the mold. Any useful simulation tool must be equipped to handle these circumstances within the limits of computational feasibility."

Jan 1, 1998

By P. D. Ferro

The direct oxide reduction (DOR) of plutonium oxide generates significant amounts of contaminated waste. This waste primarily consists of calcium oxide-saturated calcium chloride salt. This investigation explores the possibility of recycling the salt, by the electroreduction of the calcium oxide. Fused salt electrolysis of a simulated salt mix (CaC12 + ~10 wt. pct. CaO) is being carried out to electrowin calcium, and the process is being optimized in terms of the calcium solubility, cell temperature, current density and cell design to maximize the current efficiency. This work identifies the major concerns in the development of a process to electrowin calcium from this simulated salt mix.

Jan 1, 1992

By Mingming Zhang, Ramana G. Reddy

"Carbon dioxide (CO2) is one of the most common by-products produced during light metals production. It is considered to be the cause of greenhouse effects. Efficient reduction of CO2 can help minimize the rate of global warming and improving energy sufficiency. In this paper, a novel light metal production process was developed using ionic liquid electrolytes. This process has significant advantages compared to the traditional high temperature processes such as zero CO2 and CF4 emission, low energy consumption due to the low temperature operation and nonconsumable electrodes. Two types of anode materials (graphite, extruded carbon) were tested in electrolysis experiment. The results showed that both anode materials were stable (negligible weight loss). However, the extruded carbon was found to be superior to graphite in terms of current density and current efficiency. The calculated energy consumption for aluminum production was less than 10 kWh/kg at current densities up to 300 A/m2.IntroductionGlobal demand for ultra-light, ultra-strong, recyclable metals is growing as the world switches to low-emission vehicles, energy-saving devices and sustainable products. Aluminum demand is forecast to climb by 30 percent; magnesium demand by 200 percent, while for the emerging industrial light metal, titanium, the demand is expected to be at least double in the next decade. However smelting of light metals is the most energy intensive among all the steps of light metals production. For example, on an average it takes about 15.7 kWh of electricity to produce one kilogram of aluminum from alumina [1, 2, 3]. Advancements in energy efficiency have been steady, but slow, and most U.S. aluminum smelting production operates at 95% current efficiency. Besides high energy consumption, another major concern of the light metals smelting process is the emissions of greenhouse gases (GHG). Electrolysis green house gas emissions in the Hall-Héroult process can be split into three groups: 1) reduction reaction emissions, carbon dioxide (CO2) and carbon monoxide (CO); 2) process upset perfluorocarbons emissions; and 3) hydrogen fluoride (HF) formed from the moisture (H2O) present in the raw materials [2, 3]. Hydrogen fluoride gas can be captured and returned to the cells by the alumina dry scrubbing system used in modern facilities. A total of 5.31 kilograms of CO2 is generated from the reduction process for each kilogram of aluminum produced in the average U.S. primary facility. The perfluorocarbon emissions are related to the “anode effect.” If the concentration of alumina in the bath becomes too low, other reactions between the carbon anode and the bath occur and tetrafluoromethane (CF4) and hexafluoroethane (C2F6) are generated. These gases have high global warming potentials (GWP), which is a ratio developed to compare the ability of each greenhouse gas to trap heat in the atmosphere relative to carbon dioxide"

Jan 1, 2008

By M. Giralico

Optimized mixer settler designs will now handle flows of over 25,000 GPM. The size and expense of the equipment hamper experimental settler optimization efforts. Computational Fluid Dynamics (CFD) is a timely and predictable tool for settler design development. In the past, CFD has been used to evaluate only the flow field in pumped and auxiliary tanks. A similar numerical analysis is used to evaluate settler flow and phase separation. Phase separation is analyzed using multiple species for the aqueous and organic phase. Experimental validation shows good agreement between the computational and experimental solutions in both flow field and phase separation. The computational model is used to show performance differences between various choices of settler geometry, liquid depth, with variable flow rates. Understanding the differences allows the development of optimized settler designs. System improvements are predicted to lower entrainment levels further and/or allow new smaller footprint designs. This paper focuses on the major design components of the settler and how future technological advances will lead to further improvements in their design. LIGHTNIN?s new designs will handle tomorrow?s production requirements, while maximizing profits.

Jan 1, 2003

By R. J. McClincy

The potential techniques for the direct smelting of copper sulfide concentrates to blister copper were evaluated from the standpoint of commercial application. Many existing smelters are adaptable to direct smelting practice but only with improved control of metallurgical performance. Modified and innovative procedures for slag cleaning and metal refining, prerequisites to direct smelting, are presented and discussed. The ability to smelt directly to blister copper using existing equipment and eliminating the need to convert matte offers ,significant advantages to traditional smelting practice from the viewpoint of cost, 'S02 control, and process simplicity.

Jan 1, 1983

By U B. Pal

Downsizing and decommissioning of nuclear facility operations is increasing the stockpile of various different grades of Radioactive Scrap Iron (RSI). Disposal of this material not only represents significant resource and value lost, but also necessitates long term monitoring for environmental compliance. The latter results in additional recurring expense. It is desirable to be able to decontaminate the RSI to a very low level that can be recycled or used for fabrication of containers for RSI disposal instead of using virgin metal to fabricate the container. Electro-Slag Remelting and Refining (ESR) is often used for decontaminating radioactive contaminated sources of scrap iron such as stainless steel. Non-radioactive oxides of cerium are used to simulate the radioactive oxide contaminants of Uranium and Plutonium. The success of the ESR process is strongly dependent on the capacity of the slag to rapidly incorporate the radioactive contaminant (simulant). In this study we have measured the slag-metal partition coefficient for cerium and investigated the reaction mechanism for the dissolution CeO, in the slag.

Jan 1, 2002

By Jerome P. Downey

Technologies developed within the field of extractive metallurgy to recover, concentrate, and purify metals and industrial minerals from ores, have served as the foundation for all of the subsequent environmental remediation, materials recycling, and waste management technologies. This paper discusses the application of classical extractive engineering principles to the development of a thermal process for the recovery of mercury from solid wastes. Process development is presented as a series of logical stages, which begin with a thorough characterization of the site-specific waste, move on to bench and pilot scale testing of the process options, and end with a functional process flowsheet. This paper also presents thermodynamic data on many mercury species of interest to the minerals, power, and chemical industries. These data can be used to model the speciation and recovery of the mercury as a function of various process parameters.

Jan 1, 2003

By Bo Björkman

Four different arsenic containing dusts from the Boliden plant, Boliden mineral AB, Sweden have been examined. A kinetic study of the As elimination was performed in a laboratory scale roasting furnace for roasting furnace ESP dust and smelting furnace ESP dust. Characterisation and thermodynamic calculations were carried out to determine the mineralogy, and the stability of compounds in the dusts studied. The characterisation methods used were chemical analysis, X-ray diffraction analysis and microprobe analysis. It was found in the experiments that a high degree of As elimination was obtained for roasting fumace ESP dust and a low degree for smelting fumace ESP dust. Derived kinetic models are given. A prediction of the As-elimation for settling furnace dust and converter ventilation dust is presented.

Jan 1, 1994

By Esher Hsu

On July 5, 1997, Environmental Protection Administration of Taiwan publicized the recycling regulation of waste home appliances that include four items, namely, television, refrigerator, washing machine, and air conditioner. It is believed that this regulation pioneers the law enforcement of waste home appliances in the world. The objective of this study is to provide helpful base for amending recycling rates of waste home appliances. This study investigates the collection and recycling costs of waste home appliances in accordance with these newly established routes and facilities, respectively. Cost survey was conducted among collectors and recycling plants of waste home appliances; consequently, the collection and recycling costs were analyzed, correspondingly. Results provide some suggestions regarding recycling route, recycling system, recycling rates paid by manufactures and importers, recycling subsidies to collectors and recyclers. Those suggestions may provide useful policy implications to EPA for the future decision-making regarding the recycling of waste home appliances.

Jan 1, 2003