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By Akihide Nagao

The behavior of impurity hydrogen that is contained in starting material or picked up during processing has been little investigated up to now. The hydrogen microprint technique is applied to determine the microscopic location of impurity hydrogen during deformation in aluminum without hydrogen charging. Three kinds of pure aluminum of 99.99% are prepared, in which hydrogen content is varied by changing the atmosphere when they are melted and heat-treated. After rolling, tensile specimens with a gage size of 4 x 4 rnm and 0.5 mm in thickness are stamped out from these three kinds of aluminum sheets. These specimens are covered with a liquid nuclear emulsion of silver bromide crystals, stretched by 5,10 and 15 percent plastic strain or fractured, developed and fixed. SEM micrographs reveal a number of silver particles on the slip lines and on the grain boundaries. Also shown is that the more hydrogen present in the specimen, the more silver grains appear on the slip limes and on the grain boundaries. Consequently, it is concluded that impurity hydrogen is transported to the surface with gliding dislocations during deformation.

Jan 1, 1998

By Juan Ruiz-Ornelas, Yousef Mohassab, Ricardo Morales-Estrella, Hong Yong Sohn, Noemi Ortiz-Lara

The effect of mechanical activation on the reduction kinetics of magnetite concentrate by hydrogen was studied. The magnetite concentrate was milled for 8 h using a planetary mill. After the milling process, the average particle size was reduced from 14 to 4.4 m resulting in a lattice microstrain of 0.30. Thermogravimetric experiments were conducted to focus on the chemical reaction as the rate controlling factor by eliminating external mass transfer effects and using a thin layer of particles to remove interstitial diffusion resistance. The onset temperature of reduction was decreased due to the mechanical activation, and the degree of conversion was decreased by sintering of particles which was confirmed by SEM analyses. In view of the results, a reaction rate expression is discussed from which the activation energy is calculated.

Jan 1, 2016

By Liu Zhonghua

Hydrogen reduction of cobalt sulfide (Co9S8) was experimentally investigated in the temperature range 813-1053 K. The results revealed that the reaction kinetics can be described by the shrinking core mod¬el in chemical control regime at low temperatures, it is of first order with respect to hydrogen concentration, and the reaction activation energy is 67.4 kJ/mol. The SEM second electron images of the samples before and after experiments showed that the swelling of the sample above 973 K is due to the formation of metallic cobalt whiskers.

Jan 1, 1992

By K. Osseo-Asare

Rate laws for the hydrogen reduction of metal ions are typically of the form: [r = -d[M(II)]/dt = k[M(II)]xPy2H] where k is an apparent rate constant, [M(II)] and PH2 represent dissolved metal concentration and hydrogen pressure respectively, while x = 0 - 1 and y = 0.5 - 2. Half-order dependences have been reported for some M(II)/H2 systems; however, no satisfactory explanations have been offered. In an effort to bridge this gap in our understanding, the published precipitation rate data (for M(II) = Cu(II), Ni(II), and Co(II)) are reviewed (with emphasis on the reported reaction orders) and compared with the corresponding but limited electrochemical polarization data. Based on the available literature on the electrochemical kinetics of the M/M(II) and H2/H+ systems it is demonstrated theoretically that, under certain conditions (e.g., in the presence of electron-conducting solids), the rate of the M(II)/H2 reaction can be expressed as: [-d[M2+]/dt = k[M2+]2/1P2/12H] It is concluded that electrochemical processes probably play an important role in the hydrogen reduction of metal ions, especially for systems that involve heterogeneous catalysis.

Jan 1, 2003

By Jürgen Antrekowitsch, Thomas Griessacher

"Heavy metal containing residues are typically hazardous wastes because on the one hand, a deposition gets more and more complicated and on the other hand, the large amounts of metals like Zn, Cu, Fe and Pb represent a significant value. Thus, a post-treatment of these materials with the recovery/recycling of the metals and stabilization of the waste is not only ecological but often also economical. The therefore typically applied recycling processes utilize pyrometallurgical steps, where carbon or carbon monoxide from fossil coal and coke is used as a reducing agent, which results in large amounts of CO2 emissions. An alternative option is the application of a hydrogen-rich gas emitted in biomass utilization processes as a carbon-neutral reducing agent. Investigations in a retort process which were done at different temperatures and times showed excellent results concerning the achievable reduction rates and final contents of the heavy metals for various residues.IntroductionNowadays heavy metal containing residues like electric arc furnace dust (EAFD), dust from cupola furnaces, waelz slag, etc. are declared as hazardous wastes in a growing number of countries due to the leachability of the heavy metals in these residues. For that reason it is no longer possible to landfill these materials or use them for road construction or disposal works. Some land filling activities, carried out until now, have only been realizable because of some process modifications or cost intensive post-treatment steps of these residues. But the disposal capacities for such materials are decreasing, therefore increasing the prices. The second point for the growing disposal limitations is the stringent environmental legislations and regulations, which restrict the number and amounts of materials which can be dumped [1 – 5].From the other point of view these heavy metal containing residues usually have high contents of zinc, lead, iron, etc., which represent a significant value and therefore a big potential to recover these metals. This is why in recent years the number of recycling processes and the amount of recycled heavy metal containing residues have continuously increased. These recycling processes have the target to recover the valuable metals from the residual materials in the form of a saleable product as well as the stabilization of the slag produced in these processes [5, 6]."

Jan 1, 2011

By Noriaki Kurita, Norihiko Fulcatsu, Teruo Ohashi

"An electrochemical sensing device for hydrogen in molten metal has now been available owing to the development of the proton conducting solid electrolyte made of ceramics of metal oxide. The structure of the sensor and the theoretical limitations of its applications are discussed based on the electrochemical properties of the electrolyte used. The practical performance of the sensor is reviewed from the results of test measurements at the plants of aluminum and copper melting industries. The effectiveness of the sensor to the process control of continuous casting of copper is also discussed.IntroductionSince the in-line monitoring of the amount of oxygen dissolved in molten metal was realized by using the oxygen concentration cell based on zirconia solid electrolyte a similar method has been expected to be developed for sensing of hydrogen, which is a very important element of gas species in liquid metals, especially, in aluminum and copper. In 1981; Iwahara and coworkers found the dominant proton conduction at a high temperature in some perovskite-type oxide (1). Since then, the effort has been made to apply this proton conducting material as the electrolyte of the hydrogen concentration cell for high temperature use. The hydrogen sensor for liquid aluminum of this kind was first produced in 1991 (2) and released commercially from TYK Co., Ltd. Recently, we have developed the mother one usable at higher temperature such as copper and silver melting processes (3). In this note we discuss their structure, design and applicable limitations based on the electrochemical properties of this new type electrolyte. The performance of the sensor and benefit to use it to control the melting process is also discussed"

Jan 1, 2000

By Ennio Bonetti

The technological applications of MgH2 hydrides for hydrogen storage demand the overcoming of some critical issues: an improvement of the reaction kinetics and a reduction of the desorption temperature. The synthesis of nanocrystalline MgH2 by reactive milling and inert gas condensation and a proper metal catalyst addition, constitute recently employed strategies. In the investigation of the hydrogen short and long-range dynamics, sorption kinetics and nanostructure stability, the mechanical spectroscopy offers some specific advantages. In the present research this technique was employed with other experimental approaches (XRD DSC) to investigate relaxational and structural damping processes in nanocrystalline MgH2 with added catalysts (Fe). Time/temperature variation of the dynamic elasticity moduli and mechanical quality factor are correlated to hydrogen anelastic relaxation processes and concomitant structural transformation of MgH2 to Mg associated to long range H diffusion. Results are discussed with reference to microstructural modification strategies able to assist hydrogen release.

Jan 1, 2006

By Bernard Bonnetot

The potentialities of hydrogen storage using borohydrides are presented and discussed especially in regard to the recoverable hydrogen amount and to the recovery conditions. A rapid analysis of storage possibilities is proposed taking in account the two main ways for hydrogen evolution: the dehydrogenation obtained using thermal decomposition of borohydrides or the hydrolysis of solid or dissolved borohydrides. The recoverable hydrogen is related to the dehydrogenation conditions and the real hydrogen useful percentage is determined for each case of use. The high temperatures required for dehydrogenation, even using catalyzed borohydrides, lead to poor outlooks for this storage technique. The hydrolysis conditions fix the yield of the recovered hydrogen and rule the storage capacity of the dissolved borohydride, the "fuel".

Jan 1, 2006

By Andre L. De Vegt

Hydrogen sulfide is an expensive chemical used in nickel, zinc and copper mining and metallurgical operations for selective recovery and concentration of metals, from leach water streams, acid plant blow down streams, refinery electrolyte bleeds and precious metal, plant bleeds. Hydrogen sulfide is either produced on site by catalytic reduction of elemental sulfur or transported to the site as liquefied hydrogen sulfide (H2S) or as a sodium sulfide solution (NaHS) Biologically produced hydrogen sulfide has economically very interesting, application possibilities in the mining and metallurgical industry. Converting sulfates from waste streams into usable hydrogen sulfide by biological reduction results in operational cost savings in existing lime treatment systems. H2S can be produced biologically for less-than $500/ton S. For the past ten years Paques has been engaged in the development and installation of treatment systems based on biotechnological processes to remove sulfur compounds from water, air and gaseous streams. Paques has designed and installed a groundwater treatment system for the Budelco zinc refinery in the Netherlands to remove sulfate and heavy metals. The hydrogen sulfide produced is used for recovery of metals,, mainly zinc, from the ground water stream. The system has been operating since May 1992 treating a flow of 5000 m3/d. At Kennecott's Bingham Canyon Utah copper mine, a pilot plant started operation in November 1995 to develop the process for selective recovery of copper from leach water using biologically produced hydrogen sulfide from sulfate containing groundwater. Other pilot plants are operated at DOE's Pittsburgh Research Center and at Cominco Research focusing on selective recovery of metals.

Jan 1, 1998

By Nobuyuki Higashiyama, Ikuo Yonezu

"Hydrogen-absorbing alloys containing rare-earth elements are used in high capacity nickel-metal hydride secondary batteries,' hydrogen storage systems for portable fuel cells, and refrigeration systems. New hydrogen-absorbing alloys containing rare-earth elements have also been developed and introduced into these applications. High performance in nickel-metal hydride secondary batteries is strongly demanded because of the remarkable advancements in portable electric appliances. A large hydrogen absorption capacity, high electrochemical reactivity and superior corrosion resistance in an alkaline solution are required for hydrogen-absorbing alloys used in nickel-metal hydride batteries. The aim of this investigation is to improve the performance of conventional LaNi5 type hydrogen-absorbing alloys. For example, Mm(Ni-Co-Al-Mn)„ type hydrogen-absorbing alloys with various non-stoichiometric compositions were developed. In addition, a new process of rapid quenching process was applied for preparing these hydrogen-absorbing alloys in order to improve their performance.IntroductionRecently, the trend in electronic appliances toward portability has increased the demand for high capacity of secondary batteries as power sources. Since nickel-metal hydride batteries were first commercialized in 1990 in Japan, they have become increasingly popular as power sources for cellular phones, portable computers, electric shavers, and other, products.The performance of a nickel-metal hydride battery, such as its discharge capacity, high rate capability, and charge-discharge cycle life, strongly depends on the characteristics of the hydrogen-absorbing alloy negative electrode. Many types of hydrogen-absorbing alloys have been developed so far. For a hydrogen absorbing alloy to be used as the negative electrode material, (1) it must allow a large amount of hydrogen to be absorbed and desorbed in an alkaline solution, (2) its reaction rate should be high, and. (3) it must have long term durability under repeated charge-discharge cycling. However, LaNi5, a typical rare earth-nickel type alloy, shows significant capacity deterioration during repeated charge-discharge cycling. Therefore the first step in its development was to obtain sufficient corrosion resistance of the LaNi5 alloy for its use as an electrode material. A partial replacement of nickel with cobalt and a substitution of the lanthanum- content with misch metal (Mm), a mixture of rare earth elements such as lanthanum, cerium, praseodymium and neodymium, were very useful in improving the charge-discharge cycle life. However, the discharge capacity of the alloy was still not sufficient for a practical battery. A study of the effect of the partial substitution of aluminum and manganese showed that the best alloy composition was Mm(Ni-Co-Al-Mn)x, as follows.The stoichiometry x of Mm(Ni-Co-Al-Mn)x largely affects the discharge capacity and cycle life. Theose alloys with non-stoichiometric alloys with the compositions of [Mm(Ni-Co-AMn)x: 4.7<x<4.8] have a large capacity and a long cycle life. Nogami' et al. reported that 'a non-stoichiometric alloy with a Mm(Ni-Co-Al-Mn)x (x=4.76) composition showed approximately 10% higher discharge capacity than the stoichiometric alloy (x=5) [1] and greater influence of x on the electrochemical properties of multi-component AB„ type hydrogen-absorbing alloys for batteries."

Jan 1, 2000

By Teruo Tanabe

The hydrogen-absorbing materials are expected to have the following properties at moderate conditions, (a) a large capacity of hydrogen absorption, (b) the absorption rate of hydrogen is large and (c) hydrogen-absorbed materials can easily desorb hydrogen. Thus the three concepts of capacity, rate and reversibility seem to be indispensable to clarify the mechanism of hydrogen absorption by the materials. In this work, the amount of absorbed hydrogen, the absorption rate and the reversibility of hydrogen absorption- desorption reaction were measured for binary R-M systems (R = Y, La, Ce; M = Co, Ni). These experimental results were discussed by the following three physical properties that were calculated by the extended Hückel method, i.e. the density of states unoccupied by electrons, the cohesive energy and the energy fluctuation. The major results are as follows: (a) the amount of absorbed hydrogen increases with the density of states in the energy range between -9 and -4 eV, (b) the R-M compounds of which energy fluctuations are large show a large value of rate of hydrogen absorption, and (c) when the cohesive energy is large, the compound has a tendency not to easily desorb hydrogen, i.e. its reversibility is poor.

Jan 1, 2006

By James A. Sommers

Hydrolysis of NbC15 is used to recover oxide values for ceramic and metals production. Reaction of NbC15 with water is rapid, exothermic and vigorous, yielding a gelatinous slurry. In contrast, dissolution of NbC15 in 12 N HCl is endothermic, resulting in a clear yellow solution. Such solutions can be de-hydrochlorinated by controlled contact with air, to precipitate a tantalum¬rich solids, depleting the liquid of its tantalum content. In this way, cheap, useful Nb-Ta partial separation is achieved. The separation is based upon differential oxide-chloride stability. Nb2O5 with <200 ppm Ta/Nb has obtained from starting levels of 2000 ppm. Observations are made on the different types of hydrolysis.

Jan 1, 1992

By Konstantina Chalastara

Mixed phase titanium dioxide (TiO2) nanoparticles synthesized through hydrolysis of TiCl4 solution at different conditions, namely concentration, pH, and residence time are characterized and evaluated as photocatalysts. The process is operated in a continuous stirred-tank reactor, CSTR giving blends of anatase, brookite, and rutile nanoparticles that were further evaluated to find the optimum mixture for a photocatalytic sorption material. The titania nanoparticles are first characterized in terms of photocatalytic activity under UV light illumination using an organic model compound (methyl orange) and after that are tested for removal of toxic selenate and selenite species from simulated effluent waters.

By Toshihiro Kuzuya

A hydro metallurgical process has been developed for the recovery of metal values such as Co, Ni and rare earths from the electrode materials of spent nickel metal-hydride(Ni-MH) secondary battery. MmNis_xCo. (Mm : Misch metal) intermetallic compound could be separated from the electrode materials mixture by sedimentation. A typical chemical composition of MmN5-xCox was approximately, in mass%, 56.0%Ni, 13.4%Ce, 10.6%La and 7.9%Co. The time dependency of leaching intermetallic compound with sulfuric acid solution was examined with processing factors such as sulfuric acid concentration, temperature and agitation intensity, The leaching of rare earth metals proceeded very rapidly, reaching completion in less than 1.8ks. On the other hand, the slow leaching of nickel was observed. The percent of nickel leached at 328K could only reach about 70%.

Jan 1, 2003

By Alex Mezei

Experimental rheology data are needed to produce design criteria for mass and energy transfer processes. Large throughput plants operate under continuous flow mode. The capital cost is determined by the accuracy of the rheology data used for design. The operating cost is dictated by the energy required to sustain the flowing conditions of various process slurries. Typically, rheology investigations are carried out during the final stages of metallurgical testwork, which is too late to set the design criteria for the pilot plant. This leads to increased testwork cost, and sometimes lowers confidence in the quality of the data produced. In addition, the engineering and feasibility studies are often delayed because of the lack of pertinent rheology data. One of the objectives of this paper is to emphasize the importance of timely planning and execution of the rheology study, which is shown to be a critical component of the overall testwork program. Various applications are discussed, including elaboration of process and equipment design criteria. In this paper, the emphasis is placed on gold and nickel laterite hydrometallurgy applications.

Jan 1, 2003

By Jeong-Soo Sohn

Physical treatment and chemical treatment of spent lithium-ion battery were studied in our research team. Especially we developed two types of acidic leaching for crushed powders containing LiCoO2 of spent lithium ion battery. One of them is sulfuric acid leaching with H2O2 as a reducing agent. The leaching rates of cobalt, lithium and the other metals were above 99 % at the condition of 2 M H2SO4, 10 vol. % H2O2, 75 °C, 300 rpm agitation speed, 250 g/5L solid liquid ratio and 75 minutes reaction time. And the other leaching process is the oxalic acid leaching. In this process more than 99% of Li and less than 1% of Co were dissolved at the condition of 3M oxalic acid, 80°C reaction temperature, 300rpm agitation speed, 50g/L initial solid/liquid ratio and 90min extraction time. Each process has its advantage and disadvantage. In sulfuric acid leaching, leaching reagent is very cheap and cobalt could be recovered into cobalt hydroxide. On the other hand, oxalic acid is more expensive than sulfuric acid but lithium could be dissolved selectively. Also cobalt could be recovered into cobalt oxalate and it could be changed into cobalt oxide after heat treatment. In order to select the effective recycling process, recovery rate and purity of cobalt hydroxide and cobalt oxalate were compared and it was investigated which process was more environment-friendly and economical.

Jan 1, 2006

By G. Gao

Flyash from municipal solid waste (MSW) incinerators is frequently classified as a characteristic hazardous waste due to its lead and cadmium content. Extensive investigation has therefore been carried out to detoxity the flyash by leaching and to recover lead, cadmium and zinc. Detoxification can be accomplished by leaching in HCI/NaCI solutions. Optimization of leaching conditions for effective detoxification and subsequent metal recovery can be achieved by controlling the acidity of the lixiviant and flyash to lixivaint ratio. Lead and cadmium In the leaching solution is recovered by cementation with zinc dust. Leaching and cementation experiments have shown that zinc concentrations suitable for electrowinning, > 15 g/liter, can be achieved. Experiments have also been performed to determine the effects of pH, particle size of the zinc dust used, quantity of zinc added and dissolved impurities on the cementation kinetics. After recovery of lead and cadmium, electrowinning or electrowinning coupled with solvent extraction can be used to recover zinc. A process flowsheet is presented.

Jan 1, 1991

By R. Rajiv Srivastava

Brine leaching of a TSL processed zinc-plant residue (ZPR), containing 83.3% anglesite, has been investigated for lead recovery. A prior treatment of ZPR in acid solution did not show any significant effect of acid concentration in zinc dissolution. The study reveals that the solubility limits of PbCl2 is as an important factor with respect to the brine concentration and pulp density in lixiviant. The dissociated sulfate ions hinder the formation of PbCl2 on prolong leaching (above 60 min), while exhibiting the reverse solubility of lead as PbSO4. A 3-step leaching process could yield >92% leaching efficiency when the parameters were maintained as: 10% pulp density in a 250 g/L NaCl solution, 80 °C temperature, and 60 min time. This leaves the insoluble ferrite, sulfides and oxy-sulfates of zinc and lead in the final residue as revealed by the XRD characterization.

By Niels Verbaan, Ralph Fitch, Charlotte Forstner, David Dreisinger

A process has been developed to extract gold, silver, indium, gallium, lead, copper, zinc, and other metals from a large resource using an oxidizing acid chloride heap leaching technology. The ore is crushed and/or ground to improve reactivity and then contacted with a solution containing NaCl-HCl-NaOCl. The value metals are leached into solution as chloro-complexes. The leachate is treated in a series of separation and recovery processes to produce separate saleable or disposable products. The paper will provide a summary of process development and application to a silver-indium ore from Bolivia. The possible application of the process to other ore types will be presented for discussion.

Jan 1, 2015

By Rick Honaker

Rare earth elements (REEs) contained in coal and associated mineral matter exist in several forms including micro-dispersed minerals, ion adsorption onto clay surfaces, and chemically bound. Tests found that REEs can be effectively recovered from certain components of three coal sources by leaching under mild conditions followed by solvent extraction. A range of pH values were evaluated at solution temperatures of 25 and 75 °C. When using 1.2 M of sulfuric acid, nearly 85% recovery of the REEs was extracted from the middlings material collected from an operating plant. Acid leaching of a second middling source from another plant resulted in 60% of the total REEs being recovered under the same leaching conditions. Solvent extraction treatment of the leachate produced from six different coal sources resulted in products containing up to 50% total REEs from feedstocks starting with around 300 ppm.