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By E. Dendy Sloan

An overview of hydrate properties is given, with emphasis on unusual deviations from ice, the most common solid water form. Reliable sample preparation and reproduction of in situ hydrates provide the foundation for all hydrate science and engineering. Relations are given to connect the three domains in the title: (1) micro-scopic properties measured with Raman, NMR, and diffraction spectroscopy, (2) meso-scopic properties measured with single crystals, and (3) macro-scopic properties measured with pressures, temperatures, volumes, etc. A principal illustration relates micro-scopic and macro-scopic domains. Experiments provides the basis for improving statistical thermodynamics model for these compounds. To date, this model is one of the most commonly used industrial statistical thermodynamics applications, based upon the classical model of van der Waals and Platteeuw (1959). Microscopic measurements and simulations indicate model assumption improvements, resulting in the next generation of the statistical thermodynamics for improved macroscopic property prediction.

Jan 1, 2002

By Jingwei Lou, Bing Li, Suzhen Li, Miao Shen, Jianguo Yu

"As a main impurity in primary lithium metal, magnesium is difficult to remove because of the very close relative volatility of the two metals. Electrochemical refining provides a possibility to completely remove Mg in the LiCl-KCl melt prior to Li reduction. MgCl2 reduction processes in LiCl-KCl- MgCl2 melt were investigated by cyclic voltammetry (CV), square wave voltammetry (SWV), chronoamperometry and chronopotentiometry. Then potentiostatic electrolysis was carried out and Mg (II) ion was reduced onto a liquid lead cathode from the LiCl-KCl-MgCl2 melt at the Mg deposition potential. The results show that Mg ( II ) is reduced in one step with two-electron transfer. The reduction potential of Mg ( II ) was well defined. The reduction of Mg( II) results in Li ( I ) underpotential deposition at 0.2V more negative potential than that of Mg( II) reduction. Therefore, in order to prevent Li ( I ) from codeposition with Mg, accurately controlling Mg ( II) reduction potential during the potentiostatic electrolysis was necessary. Ninety three to 99 % removal rate of MgCl2 was achieved after 8-12 h electrolysis when liquid lead was used as cathode.IntroductionMetallic Li has been widely used in batteries, light weight alloys and in fusion reactors because of its excellent properties. Currently, the only way in industry to produce metallic Li is by electrowinning from molten LiCl-KCl at about 450 °C [l-5]. LiCl-KCl is the only electrolyte used, because they presents a lower eutectic temperature and KCl shows a slightly higher theoretical decomposition voltage than LiCl, as shown in Table l .The produced metallic Li generally contains 1-2 wt% impurities including Na, K, Al, Ca, Mg, Si, etc. [6l, which are derived from the corresponding metal chloride compounds or metal oxide compounds existing in the LiCl and/or KCl raw materials. These impurities have to be removed by subsequent vacuum distillation at high temperatures to meet the requirements for metal Li purity in the final products. Separation of Mg from Li by vacuum distillation is difficult because their relative volatilities are very close, as shown in Table 2."

Jan 1, 2011

By E. James Quinn

Solvent extraction technology using EHEHPA (2-ethylhexyl phosphonic acid, 2-ethyhexyl mono ester) is the norm for industrial separations of rare earth elements. This process has some shortcomings, including a large number of stages compared to most SX processes and high acid requirement for stripping of the heavy rare earths. In this work, we examine a number of alternative mixed solvent extraction systems: (i) Mixtures of organophosphonic and phosphinic acids such as EHEHPA/Cyanex 272 or Cyanex 572; (ii) Ionic liquid mixtures of EHEHPA with quaternary ammonium chloride (Aliquat 336); and (iii) Mixtures of carboxylic acids for yttrium/lanthanide separations. We discuss and compare the efficacy of these systems with reference to the Nd/Sm separation, which is of industrial significance. Based on the extraction chemistry and the use of modelling tools to define the counter-current solvent extraction circuit, we present a techno-economic analysis of a separation plant and discuss the impact of various solvent systems on the capital expenditure (CAPEX) and operating costs (OPEX).

By Xinli Wang, Matthew Andriese, Jiann-Yang Hwang, Zhiwei Peng, Byoung-Gon Kim

"The microwave reflection loss (RL) of ferric oxide is studied in the temperature range from 297 to approximately 1400 Kat frequencies of 915 and 2450 MHz. It is shown that the maximum microwave absorption with RL of -38.46 and -35.97 dB can be obtained for ferric oxide having thicknesses of 0.03 and 0.01 m at 915 and 2450 MHz, respectively. The maximum absorption peak with RL below -10 dB is in a 250 K temperature range from 723 to 973 Kat 915 MHz, which shifts to the range between 823 and 1073 K at 2450 MHz. This migration is in good agreement with the variation of the dielectric loss tangent of ferric oxide.IntroductionMicrowave irradiation has distinguishing characteristics such as volumetric and selective heating compared with conventional methods, leading to extremely broad applications in materials heating and processing [1-5].The efficiency of microwave heating was found to be dependent on various factors, such as microwave power [6], frequency [7,8], radiation time [8], applicator geometry [8], sample microwave absorption properties and position as well as dimension [9-11 ], etc. Among these parameters, sample dimension plays an important role but is usually neglected by researchers in microwave processing of materials. In fact, although numerous studies have been directed toward the utilization of microwave energy to assist materials heating and processing, few reports were released on the effect of sample dimension [12,13].This is because all aforementioned factors influencing microwave heating generally exert interactive effects to each other during the heating process, making clarification of the effect of sample dimension difficult. Therefore, it is necessary to propose a parameter or concept for quantifying the effect of absorber dimension on microwave heating, increasing heating efficiency."

Jan 1, 2013

By John W. Cash

The mineralogy and textures of cyclone dust, sludge, and occasional build-ups in the American Iron and Steel Institute (AISI) direct ironmaking pilot plant at Universal, Pennsylvania have been studied by reflected light, transmitted light, and cathodoluminescence microscopy, and phase compositions have been determined by SEM-EDS. The cyclone dust consists of particles of carbon, metallic iron, sulfur-bearing iron, and wustite. Measurements of particles in the sludge indicates that 69% are less than 2.5 um across, 21 % are 2.5-5 um, and 10% are larger than 5 um. Mineralogically the sludge particles are mainly carbon and metallic iron, with minor wustite and sulfur-bearing iron. Build-ups that sporadically develop in the furnace consist of olivine, hercynite spinel, metallic iron, wustite, pyrrhotite, pseudobrookite, akermanite-ferroakermanite and gehlenite. The microtextures shown by the build-ups indicate that much of that material has precipitated at the build-up loci. This study has been supported by AISI and the U.S. Department of Energy.

Jan 1, 1995

By Kenneth N. Ham

Hydrometallurgy covers a wide spectrum of areas and its knowledge base is enlarged and enhanced by contributions from many other fields. Dissolution of metals and alloys in aqueous media will be used to illustrate how rich the field of metal extraction can be. Comprehensive understanding of the fundamentals of metal and alloy dissolution in aqueous systems requires creative application of thermodynamic principles, solutions chemistry, ligand complexation theory, electrochemistry, transport phenomena and heterogeneous kinetics. In addition, recent developments in instrumentation in the fields of interfacial phenomena and corrosion have tremendously advanced the field of metal extraction in aqueous system. The close relationship between metal extraction in aqueous systems and various physicochemical phenomena occurring in corrosion and interfacial systems will be discussed and illustrated with examples.

Jan 1, 2002

By V. D. Tathavadkar

Natural chromite mineral is a solid solution of spinet end members namely: chromite (FeCr2O4), hercynite (FeA1204), magnetite (Fe3O4), magnesio-chromite (MgCr2O4), (MgA12O4), and magnesio-ferrite (MgFe2O4). A phase transformation in chromite minerals occurs in oxidising conditions during the soda-ash roasting reaction. This phase transformation plays an important role in improving the extraction efficiency of Cr3+ from mineral phase. The extraction efficiency of chromium (Cr3+) from chromite to a water¬soluble sodium chromate (Cr6+) salt depends upon the decomposition kinetics of the spinet phase. An investigation of the phase changes in chromite ores in the absence of sodium carbonate was carried out in air, argon, and in argon +5 % hydrogen gas mixture. The thermodynamics of phase transformation reaction in chromite solid solution phase is discussed using the solution model proposed by Sack and Ghiorso [1]. The microstructural changes and the changes in elemental compositions of different phases were examined by SEM and electron probe microanalysis (EPMA) respectively. The experimental results indicate that the solid solution spinet phase in chromite mineral undergoes spinodal decomposition under the influence of oxygen partial pressure and temperatures. The structure of phases formed and their morphologies suggest that the phase decomposition may be similar to those observed by Burkert et. a]. 121, although the scale of phase separation in chromite appears to be strongly dependent on oxygen partial pressure.

Jan 1, 2001

By Hu Long

In this, the first systematic study of the oxidation of orpiment (As2S3) in sulfuric acid solution under oxygen pressure at temperatures above 170°C, the effects of retention time, temperature, particle size, oxygen partial pressure, the concentration of sulfuric acid and pulp density were evaluated. The effects of cupric and ferric ions on the oxidation rate of As(III) to As(V) were also examined. The products of oxidation are As(III), As(V), SO42- and elemental sulfur. At temperatures ranging from 170 to 230°C, most of the arsenic was found to be in the trivalent state, and oxidation to As(V) with oxygen was very slow. This was confirmed by attempting to oxidize a synthetic arsenious solution. However, the rate of oxidation of As(III) to As(V) is rapid in the presence of ferric ion. Elemental sulfur was found at all temperatures investigated, which can be further oxidized to sulfate at high temperature.

Jan 1, 1999

By P. N. Anyalebechi

The effects of a cross-hatched grooved mold surface topography, casting speed, and superheat on the morphology of solidifying shells of aluminum alloy 3003 have been characterized by a series of immersion tests. The cross-hatched grooves were 0.232 mm deep with wavelength or spacing between 1 mm and 15 mm. The shells solidified at casting speed of less than 10 mm/s on the 1 mm spaced cross-hatched grooved mold surface were fairly uniform with little or no localized variations in thickness. However, the propensity for non-uniform shell growth morphology was exacerbated by an increase in casting speed, melt superheat, and the wavelength of the cross-hatched grooves. This is provisionally attributed to their effects on interfacial heat transfer and wetting of the mold surface by the molten metal.

Jan 1, 2008

By Pingchao Ke

A crystalline polyferric sulfate (PFS) adsorbent was synthesized by oxidizing and precipitating ferrous ions under atmospheric conditions. The morphology, structure, composition and specific surface area (SSA) and adsorptive efficacy to As (III) of the adsorbent were characterized by SEM/EDS and TEM images, XRD patterns, FT-IR spectra, BET SSA analyses and adsorption experiments. The adsorbent presents as morphology of near-spherical aggregate and good crystallinity. A small amount of goethite co-precipitated with PFS in the case of the initial ferrous concentration of 1 mol/L and increased the SSA of the aggregates. The absorbent with co-precipitation of goethite showed good adsorption to As(III) and good filtering performance in the high As(III)-content solution of 10–100 mg/L under acidic, neutral and alkaline conditions (pH 2.09–9.01), and its maximal adsorption capacity and adsorption efficiency were 7911 μg/g and 96% separately. After Adsorption, the stability of the absorbents adsorbing As(III) were evaluated by TCLP tests, and the results indicated that the absorbents adsorbing As(III) were extremely stable, and the concentration of arsenic in all leaching solutions were less than 0.01 mg/L.

By C. Kathryn Sole

The close proximity of cobalt and nickel on the Periodic Table and their frequent occurrence together in nature means that their separation in primary hydrometallurgical flowsheets is not only often necessary, but requires the use of innovative chemistry to achieve high selectivity. Today, increasingly stringent demands for the high-purity cobalt and nickel salts required for battery applications in consumer electronics, electric vehicles, and solar applications are again challenging the state of the art. The evolution of cobalt–nickel separations is traced from the basic precipitation technologies employed in 1960s, through commissioning of the first cobalt solvent-extraction plant in South Africa in 1974, to the commercialisation of organophosphinic-acid extractants (which provided a step-change improvement in selectivity) and their eventual widespread use in the 1980s and ’90s. This was followed later by their sulphur analogue, which enabled different possibilities for laterite processing in the new millennium. Separations in chloride media, which take advantage of the different speciation chemistries, and nickel extraction by oximes in ammoniacal systems are also discussed. More recently, chelating and solvent-impregnated resins have added further dimensions to the possibilities for flowsheet design and enabled higher purity products to be attained from both primary and secondary sources. Selected case studies and flowsheets are described.

By A. A. Hejja

The effect of composition on electrical conductivity, viscosity and liquidus temperature of the slags was investigated in the temperature range of 1300" to 1450°C. The synthetic slags containing CaO, MgO, SiO,, A1,0, and FeO were similar to those employed in the electric furnace smelting of sulphide Cu-Ni concentrates containing PGM (Platinum Group Metals) from the Merensky Reef of South Africa. FeO and SiO, were found to affect the viscosity and conductivity the most while liquidus temperature depended on MgO content in addition to these. The activation energy for electrical conduction was found to vary from 67 to 159 kJ/mol and that for viscosity from 125 to 209 kJ/mol. Optimization of the slag composition was attempted on the basis of opposite trend of the viscosity-electrical conductivity relationship with slag composition.

Jan 1, 1994

By Gaballah Djona M.

Spent hydrorefining catalysts contain about 5 % of CoO and/or NiO, 12 % of MoO3 and up to 10 % of V205. They are generally supported by alumina and contain up to 25 percent of C, S and hydrocarbons. Such materials are potentially hazardous to the soil and to water resources. Selective chlorination of raw unroasted samples with Cl2 + air gas mixture had been investigated. At temperatures lower than 600 °C, it was possible to recover more than 90 % of nickel and cobalt chlorides, about 99 % of the molybdenum and up to 75 % of vanadium chlorinated compounds. CoCl2 and Ni/Cl2 were extracted from the chlorination residues by their dissolution with acidified water. Molybdenum and vanadium chlorinated compounds were recovered by selective condensation from the vapor phase. The chlorination of Al2O3 could be limited to less than 6 %. The scale up of this treatment was successful and a flow-sheet is proposed.

Jan 1, 1995

By Ljiljana Solujic

The need for the removal of mercury from the precious metals extraction circuits may be influenced by process, environmental, as well as by occupational hazard reasons. In these circuits mercury is mainly present as cyanide complexes. The effectiveness of any stabilization method will be influenced by the high thermodynamic stability mercury-cyano species exhibit in an aqueous solution. In this study, we have investigated the utility of the trisodium salt of trimmercapto-s-triazine (TMT) for precipitation of mercury from the corresponding cyano-complexes. The influence of pH molar ratio of TMT to Hg, coagulant and flocculant additions, excess of free cyanide, as well as the presence of other metal-cyano species on the effectiveness of mercury precipitation were investigated in detail. Also, a "teal world" precious metals mill effluent initially containing ~7 ug/mL (ppm) of Hg was treated and A was found that greater than 99.8% of the mercury was removed from the solution as am insoluble Hg/TMT complex.

Jan 1, 1996

By Robert L. Stephens

"It can be argued that one of the most important property of any material is cost, since this property detennines the applications for which a material can be considered. Despite growing demand and production for commodity metals such as copper, nickel, zinc, lead, and tin, the cost of these metals has been steadily decreasing in real terms. The only way that metal miners and producers can remain financially viable in the long term is by continuing to lower their cost curve through the implementation of new metals production technologies. This paper reviews technological developments in the production of copper, nickel, zinc, lead, and tin that have or threaten to redefine the cost curves for these metals.DisclaimerThe opinions expressed in this paper the author's, and are not necessarily those held by the author's employer, Cominco Ltd.IntroductionThis meeting will discuss many novel technologies and processes for producing metals and materials with specific properties that will enhance the applications ranges for the material or will allow entirely new applications to be developed. However, in every real-world case, the cost of the new material or process is an important property that determines which applications the material or process can be used in. Other properties that are important depend on the applications.A recent press report (1) discussing the potential replacement of aluminum radiators with copper radiators in pickup trucks and sport utility vehicles provides an interesting example to reinforce the importance of cost in materials selection. In this case, the displacement of aluminum by copper is being considered because of the more favorable heat dissipation characteristics of copper. Heat dissipation has become more important due to the development of hotter-burning V-8 and V-6 engines. For this application, engineers also consider cost, weight, size, durability, and manufacturing process. The report stated that the development by the International Copper Association (ICA) of the ""CuproBraze"" manufacturing process for heat transfer products was an important development. This technology produces 845 radiators that weigh less, are more uniform in quality, and are potentially more compact. They are also expected to cost less in high production quantities than copper units produced in the past, last three to four times longer than soldered copper radiators, and the process also eliminates the use of lead solder from the manufacturing process."

Jan 1, 2000

Equilibrium calculational software programs can be effectively utilized to illustrate the importance of activity or concentration, solubility, temperature, solution pH, solution potential, and ligand complexation to students studying hydrometallurgy. The calculational program STABCAL will be demonstrated. illustrative examples for the creation of diagrams such as EH-pH, activity or concentration-pH and activity or concentration-EH will be presented to demonstrate the fundamentals of real hydrometallurgical systems. Speciation, titration and mixing will be used to simulate or predict operational processes. Applications will include treatment of Acid Mine Drainage (Berkeley Pitlake water and sediments), mass balance potential/pH diagrams, leaching and selective separation of metals from electroplating sludge, metal adsorption at femhydrite surfaces, and flowsheet development for treating mercury sulfide K106 sludge.

Jan 1, 2002

By Thomas P. Battle

Modern-day direct reduction of iron first developed as a small-scale, low capital and operating cost alternative to the blast furnace. Since commercialization of continuous DR technology in the late 1960s, the market for the products of direct reduction has grown to more than 74 million tonnes in 2012. The initial advantages of DR plants over BF facilities have grown over the years, for several reasons, including the increased size of DR modules, lower energy and emissions (particularly CO2), along with the flexibility to use a number of different reductants. The development of DR technology over the past forty years will be emphasized in this presentation, including recent developments that allow for even more direct sustainability comparisons with the iron blast furnace – and even combine the two technologies for improved synergies. Also briefly discussed will be the possibilities of using direct reduction for non-ferrous ores.

Jan 1, 2014

By Jorge Alberto Soares Tenório, Flávia Paulucci Cianga Silvas, Denise Crocce Romano Espinosa, Ivo André Homrich Schneider, Erika Gusmão, Daniella Cardoso Buzzi, José Roberto de Oliveira

"This study evaluated the Salvinia sp action on metals biosorption in a synthetic sample of acid mine drainage (AMD) in order to determine the time and amount of metals uptake. Biosorptives tests were realized varying the contact time of 5, 20, 60 and 240 minutes. And keeping constant the follow parameters: pH (2.6), biomass concentration (1g.L-1), temperature (25°C) and agitation (175rpm). In order to quantify the metals concentration captured by biomass, the AMD samples will be analyzed by ICP. Biosorbent, Salvinia sp., will be characterized before and after the biosorptives tests through analysis of SEM and IR. The micrographs indicate the occurrence of micro-precipitation and changes in biomass physical structure. The infrared spectra indicate changes in functional groups present in the biomass before and after the biosorptives tests.IntroductionThe current emphasis on environmental sustainability leads the industry in general, to treat their waste. The human activities are increasing, highlighting the industrial and mining activities, and have promoted the contamination of soil, waterways and groundwater by metals (1). The waste must undergo treatment processes aimed at reducing pollution, and therefore, less aggression ecosystems.This means the importance of studies of economic and effective methods to eliminate these metals from wastewater generated. The bioindicators are good investments in this area. The aquatic weeds are plants that inhabit swamps up from truly aquatic environments. They have several morphological and physiological adaptations that enable them to colonize the various aquatic environments. They are used as bioindicators of water quality and have also been used in decontamination of aquatic environments, production of biomass for livestock feed, fertilizers, soil and fish tanks (2)."

Jan 1, 2012

By Guanghui Li

In the paper, the recovery technology of gallium from zinc-leaching residue by cold-bonded coal-based direct reduction process following magnetic separation was developed. The results show that the scattered metal Ga can be concentrated obviously after the reduction of zinc-leaching residue briquette and magnetic separation of reduced product. At the same time, the volatilization of Zn in the residue is enhanced during the reduction. When the residue, bear¬ing 18.60% Zu.21.18% Fe and 527 g/t Ga, was reduced with coal at 1100°C for 150 min, the results of Zn volatilization of 9842% and Ga recovery of 89. 10% were obtained in reduction. After magnetic separation of the reduced product, the concentration of Ga in sponge iron is 2164 g/t, and the separation recovery of Ga reaches 92.42%. The enriched mechanism of Ga during reduction -separation process was studied by using electron microscope, scanning elec¬tron microscope, energy spectrum and mineralogical analysis. The investigations show that there is no formation of independent phase of Ga during reduction process. The Ga occurs mainly in metallic iron phase (the concentration of Ga in metallic iron phase is 0.04%-0,4%), in addition, there exists a little Ga in poorly crystalline sulphide (o.08%-0./5Y& Ow). But Go does not exist in most of glass and silicate phase. The affinity of Ga for metallic iron is the enrichment basis of Go in reduction, and it is also in favor of recovering Go during magnetic separation. Key Words: Gallium Zinc-leaching Residue Cold- Bonded Direct Reduction

Jan 1, 2003

By Kimio Itagaki, Torn Matsumoto, Makoto Ohtsuka, Kentarou Harada

"The structure and hydrogen-absorption properties of LaNis thin films were investigated in the present study. LaNis thin films were prepared by a sputtering method with a radio-frequency power, Ws, of 50 -400 Wat substrate temperature, Ts, of323 -573 K. Nickel content of the films decreased with increasing Ws, however, there was no dependence on Ts. At low Ws and low Ts, amorphous films were deposited. In other conditions, the films were polycrystalline. The films prepared at high Ws and low Ts, or at low Ws and high Ts, exhibited only a (h k · 0) peak in the X-ray diffraction profiles. This indicates that the c-axis of crystalline films was oriented parallel to the substrate plane. At high Ws and high Ts, the films with columnar structure were obtained. Hydrogen-absorption capacity of the thin films increased with increasing Ws. The pressure plateau did not appear on the pressure-composition isotherms. The films deposited at high Ts represented a higher equilibrium pressure.IntroductionThin films of hydrogen storage alloys can be applied for an electrode of rechargeable battery or fuel cell, a filter for H1 purification and various kind of sensor. Some studies on the preparation of the thin films of LaNi5 intermetallic compound, which is a typical hydrogen storage material, have been done hitherto. Adachi et al. , 2) and Sakaguchi et al. 3) prepared amorphous and crystalline LaNi5 thin films using flash evaporation of alloy powders and measured the pressure-composition isotherm for the prepared film utilizing a quartz crystal mass monitoring (QC:MM) method. It was found that the prepared amorphous film absorbed hydrogen without disintegrating into the powders and the hydrogen-absorption capacity of the films increased with the degree of crystallinity. Sakai et al. 4) reported that the maximum hydrogen storage capacities of amorphous and crystalline LaNi5 thin films, fabricated by a RF sputtering method using combination targets, were about 40 mA h g-1 (LaNisHo.7) and 160 mA h g-1 (LaNi5H2.6), respectively. Uchida et al. 5, 6) prepared LaNi5 thin films using flash evaporation of alloy powders and measured volumetrically the pressure-composition isotherm for the prepared film. It was reported that the hydrogen-absorption capacity of the films changed by the annealing treatment."

Jan 1, 1998