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By Boyd Davis, Vladimiros Papangelakis, Joshua LaMarre, Jan de Bakker

"HCl leaching using molten salt hydrates has the potential to improve the extraction of nickel from laterite ores. However, as in other HCl leaching applications, recovery of HCl is key to process economics. Spray pyrohydrolysis, which is used in current chloride-based flowsheets, is associated with a high energy cost. The authors have developed a proposed laterite leach circuit using an alternative HCl recovery route. The leach circuit envisions a leach by concentrated (33%) HCl in an MgCl2 molten salt hydrate (MSH) or brine medium, followed by Ni/Co recovery and iron precipitation. Magnesium and chloride are precipitated from solution as magnesium hydroxychloride; this hydroxychloride is thermally decomposed to produce HCl gas. The proposed flowsheet employs a chloride leach circuit with simpler equipment and lower energy cost than in the conventional practice of pyrohydrolysis. Laboratory work investigated key aspects of the flowsheet, including precipitation of magnesium hydroxychlorides and their composition; magnesium hydroxychloride thermal decomposition; and iron control.Introduction As sulphide nickel ores become harder to mine and more complex to process, laterite ores will increase in importance. Laterite ore deposits can be divided into two main mineralogies. Limonite ores consist mostly of hydrated iron oxide, FeOOH, with 1-3% nickel substituting for the iron. Saprolite ores consist of iron-magnesium silicates, (Fe, Mg)2Si04, again with some nickel substituting for the metal ions. Limonite ores can be treated using the HP AL (High Pressure Acid Leach) process, in which the ore is reacted with sulphuric acid at high temperature in an autoclave. HP AL, however, cannot in general be used to treat saprolite ores because the magnesium enters solution and consumes sulphuric acid, which results in excessive spending on lixiviant. It is therefore desirable to find a hydrometallurgical process specifically for saprolite ores that can provide better results than the treatment options currently available."

Jan 1, 2011

By K. Murayama, M. Kawakami, T. Takenaka, S. Yokoyama

"Cokes play an important role of spacer in blast furnace. However, they degenerate during Boudouard reaction. Blast furnace cokes are reacted with pure C02 at I 072 to 1673 K. Reaction rate was obtained by the weight change of spherical specimen. The specimen after reaction was examined by microscopic observation. The reaction rate increased with temperature and was expressed by two Arrhenius type lines. The activation energy was 126 KJ/mol at higher temperature than 13 73 K and 202 KJ/mol at lower temperature range. At the higher temperature range, the reaction proceeded from the surface leaving unreacted core, whereas homogeneously whole inside at lower temperature. The porosity increased from the center to surface at higher temperature, whereas it was almost constant at lower temperature.IntroductionThe cokes have the function of fuel, reductant and spacer to keep gas and liquid flow in the blast furnace. Thus, the reaction mechanism of coke with several gas and the strength after the reaction should be important factor to control the blast furnace operation. The reaction mechanism of coke with C02 has been studied extensively. The rate equations were derived by Gadsby[ I], Ergun[2] and Turkdogan and Vinters[3]. They were compared and discussed by Kobayashi and Omori [ 4]. Effect of crystallization degree on the reaction rate was examined by Kashiwaya and Ishii[5]. Catalytic enhancement effect of ash componets have been clarified by Kashiwaya et. al. [6]. Although degradation of coke in blast furnace has been examined recently[7], however, the degradation of coke after the reaction with C02 has not been well clarified yet. In the present work, the metallurgical coke specimen was heated in N2 and C02 and the reaction mechanism and degradation behavior after the reaction was investigated."

Jan 1, 2000

By Baozhong Zhao

Laboratory experiments have been conducted on the removal of As, Sb and Bi from molten copper by SF 6 injection. The results showed that the impurities can be removed by SF6 injection in the? sequence of Sb >As >,Bi and the rate of Bi removal is affected significantly by the concentration levels of As and Sb in the copper melt. Analysis of the experimental data indicates that the impurity removal process is under chemical reaction control rather than by mass transfer of impurity through the molten copper phase. On the basis of experimental results, a kinetic model was developed and the order of chemical reaction and the volumetric chemical reaction rate coefficients of impurity removal were determined.

Jan 1, 1996

By J. Brent Hiskey

The global copper industry faces a technological challenge to develop processing schemes for more complex and impure ores and concentrates. Group 15 elements (As, Sb, and Bi) represent impurities that are troublesome both in terms of environmental impact and metallurgical processing. The so-call "dirty" copper concentrates are either unacceptable for smelting and refining or incur high penalties. The behavior of the Group 15 elements is of critical importance in maintaining product quality and process performance. During copper electrorefining, these impurities are released to the electrolyte by electrochemical dissolution of the anode. Depending mainly on temperature, concentration, and oxidation state these elements can spontaneously coprecipitate from the electrolyte. Some of these precipitates are referred to as floating slimes and their formation can have extremely detrimental effects on cathode purity. In this paper, the mechanism of floating slimes formation will be discussed and the fundamental thermochemistry will be reviewed and analyzed in relation to solubility properties.

Jan 1, 2012

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 Tibor Zoltai

Asbestos is a generic term for industrially useful fibers recovered from exploitable deposits of the asbestiform varieties of five silicate minerals: chrysotile, anthophyllite, actinolite-tremolite, cummingtonite-grunerite, and riebeckite. Asbestos and asbestiformm fibers of some other minerals are known to be carcinogenic. Minerals crystallized in the asbestiform habit are characterized by unique properties (morphology, strength and flexibility, physical and chemical durability, and defect-free surface structures). The key to the unusual properties, and health effects, of asbestifarm fibers appears to be in their unusual surface structure. In contrast, non-asbestiform crystals of the same minerals, including the five so-called asbestos minerals do not have these properties and are not carcinogenic (1, 2).

Jan 1, 1989

By Kuniaki Murase, Tetsuji Hirato, Koji Nitta, Yasuhiro Awakura

"The redox behavior of copper species in an ""ammonium imide"" room temperature molten salt was examined in order to clarify the applicability of the salt to the electroplating media of various metals. Trimethyl-n-hexylammonium bis(trifluoromethanesulfonyl)- amide (TMHA-Tf2N), having an electrochemical window of 5.6 V (50 °C), and corresponding copper(II) salt were synthesized. In TMHA-Tf2N media monovalent copper ion, Cu(I), was stable and Cu metal was oxidized, or corroded, in the presence of Cu(II) species. Cathodic electrodeposition of copper metal and anodic dissolution of it were, thus, one-electron reaction and their current efficiencies were almost 100%.IntroductionElectrodeposition of metals from aqueous solutions is an important soft process for manufacturing thin-film materials, surface finishing, and extractive metallurgy. However, the electrodeposition of base metals, such as zinc, chromium, and nickel, from aqueous media inevitably accompanies hydrogen evolution, which lowers the cathodic current efficiency of metal deposition. Since the electrodeposition of aluminium, titanium, and rare earths from aqueous media is actually impossible due to their largely negative redox potentials, nonaqueous media such as aprotic organic solvent and high-temperature molten salts have been employed for the electrodeposition of these metals. Room temperature molten salts (RTMS),1, 2) or room temperature ionic liquids, have also been developed as a promising electrolytes for the electrodeposition of base metals. In this field, chloroaluminates of alkylpyridinium or alkylimidazolium cation have been well investigated for aluminium3) or alluminium-alloy4-5) electroplating media. On the other hand, in order to avoid high hygroscopicity arising from the use of aluminium chloride, attempts have been made to combine the alkylimidazolium cations with fluorine-containing hydrophobic anions, e.g. BF4-,6) CF3SO3- (TfO-),7) (CF3SO2)2N- (Tf2N-),8) and H(HF)n-ions,9) and investigated for electrodeposition media.'°) Recently, a new series of RTMS consisting of tetraalkylammonium cations and Tf2N- anion, sometimes abbreviated as TFSI- anion, was found independently by MacFarlane et al.11, 12) and Matsumoto et al. 13) This type of RTMS, which is commonly named ""ammoniumimide"" salt, has a wide electrochemical window of ca. 5 V and, thus, the RTMS seems to be suited for practical application as a solvent for the electrodeposition process. In this paper, we report the electrochemical behavior of copper species in an ammoniumimide RTMS, trimethyl-n-hexylammonium bis(trifluoromethanesulfonyl)amide (TMHA-Tf2N)."

Jan 1, 2000

By Rak-Jun Choi

Plasma-induced damage of InGaN/GaN multiple quantum well (MQW) light-emitting diodes (LEDs) has been studied in terms of forward turn-on and reverse breakdown voltages, together with etch rate and surface morphology. The physical degradation of sidewall along with rough surface morphology of n-GaN caused by increased ion scattering induced the deterioration of the forward and reverse voltages. It was found that the turn-on voltage is sensitive to the surface roughness of the etched n-GaN and the breakdown voltage is strongly affected by the sidewall contamination. Annealing under nitrogen after the mesa etching improved the electrical properties of the InGaN/GaN MQW LEOs. Efficient blue light-emitting diodes (LEOs) were fabricated using InGaN/GaN triangular MQWs. The LEOs with triangular QWs showed a lower operation voltage and 2.4 times higher light output power than those with the rectangular MQW LEOs at 20 rnA and 20 "C. The intensity of electroluminescence (EL) at 20 mA was almost independent of ambient temperature in the triangular QW LEO, but decreased substantially in the rectangular one.

Jan 1, 2003

By P. R. Taylor

Laboratory experiments have been performed to evaluate the kinetics of roasting pyrite and arsenopyrite in air at elevated temperatures, in the presence of lime. The effects of temperature, time, air flow rate, particle size, lime type, and mineral/lime weight ratio on the rates of oxidation, lime sulfation, and lime arsenation were studied. The reaction products were identified using chemical analysis, x-ray diffraction, SEM analysis, and optical microscopy. The results are discussed in terms of the utilization of lime to capture sulfur and arsenic during the roasting of refractory precious metal concentrates. More than 99.9% of the arsenic and 98% of the sulfur are contained when roasting pyrite and arsenopyrite with hydrated lime under typical roasting conditions.

Jan 1, 1991

By Suzzann Nordwick

The metallurgical treatment of mercury-containing materials for precious or base metals recovery imposes many processing and environmental challenges. Mercury is usually present as elemental or cinnabar. Historically, mercury has been removed from mined ores pyrometallurgically by roasting, but hydrometallurgical methods have also been employed. For example, alkaline sodium sulfide solution acts as an universal solvent for most mercury compounds. While, most other metals are highly insoluble in this solution. This allows for a high degree of selective separation of mercury from other metals with the exception of tin, antimony and arsenic. Mercury leached with a solution of sodium hydroxide and sodium sulfide or sulfur can be re-covered by cementation or stabilized through sulfide precipitation. Hydrometallurgical technology for the pretreatment of mercury removal from gold, silver, and base metal ores using alkaline sulfide leaching will be discussed with a focus on alkaline sulfide leaching of mercury sulfide-containing materials.

Jan 1, 2003

By D. C. Cupertino

Oxime based solvent extraction provides the user with a selective concentration process for copper prior to electrowinning. The selectivity required is largely for copper(II) over iron(III) and this is achieved by the preferential formation of the square planar copper-oxime complex in the organic phase. The copper/iron selectivity of oximes can however, be altered by modifiers or other types of oximes and may be enhanced in the presence of certain esters. Whilst the oxime based SX processes is important for operations leaching copper from laterite ores, the high selectivity will also be significant in processing streams arising from other leaching regimes which are currently under development, for example leaching of sulfide mineral ores. This paper presents some initial results using Molecular Modelling techniques to further our understanding of the nature of the copper/iron-oxime complexation processes together with some plant studies undertaken at a number of different mine sites investigating selectivity, and other properties, for some modified reagents. Some studies of the interfacial properties of the these systems are reported to explain in part the practical observations.

Jan 1, 1999

By Cong Wang, Siyang Long, Pengcheng Zhang, Haibin Zuo

This paper introduced the research progress of microwave treatment on coal. The mechanics of microwave treatment mainly include thermal effects and non-thermal effects. Thermal effects, which lead to cracks and changes of pore structure, attribute to the selective heating of microwave. Non-thermal effects involve the removal of oxygen functional groups, improvement of coal rank and decomposition of minerals. Therefore, microwave treatment of coal has a lot of potential applications, mainly including drying, desulfurization, improvement of grindability, enhancement of coal-water slurry property and change the combustion and gasification properties.

Jan 1, 2016

By Huimin Lu, Lian Zhou, Panpan Wang

"For the low concentration C02 exhaust gas from coal-fired power plant, steel plant emission trapping and recycle problem, a pressure swing adsorption process was studied, using a porous imidazolate framework materials (ZIFs) as adsorbent, separating carbon dioxide from fuel gas mixture. In the carbon dioxide reduction condition by electrochemical method, using ionic liquids as electrolyte, the oxygen and carbon products could be obtained, including carbon nanotube, nano carbon fiber and amorphous carbon. At last, a new C02 collection, recycling and reuse technology was formed.IntroductionDuring the combustion of fossil fuel in coal-fired power plant or steel plant, large amount of carbon dioxide has continuously emitted into the atmosphere. The phenomenon has resulted in the melt of arctic glacier and the frequent emergence of abnormal climate. How to reduce the emission of carbon dioxide and protect human living environment has become a worldwide challenge. Recently, there are three routes to resolve this problem: The first one is to adjust the energy structure and develop new energy, such as solar, wind, hydrogen; the second one is to improve energy efficiency and avoid waste; the third one is to research capture and sequestration of carbon dioxide (CCS). But many researchers have come to realize that the recovery and utilization of carbon dioxide are more important than the sequestration of it. Because the captured carbon dioxide just buried under the earth maybe cause secondary pollution if carbon dioxide leak out from the adsorbent."

Jan 1, 2013

By Honggang Zhong, Xin Cao, Qijie Zhai, Hongmei Song, Congsen Wu, Cheng Zhang, Jingzheng Ye

"The influence of superheat on the solidification structure and ferrite/austenite phase transformation of a novel lean duplex stainless steel (DSS) was investigated on a setup, which designed to thermally simulate the continuous casting process. The results showed that the macrostructure of the samples all exhibited chill zone, columnar zone and equiaxed zone. The distance from chill zone to position of columnar to equiaxed transition (CET) moved from 51.0 mm to 39.8 mm with an decrease of superheat from 70 °C to 10 °C, and that the grains in the chill zone tended to be finer. In equiaxed zone, the fme and uniform grains were observed when superheat higher than 40 °C; while, coarse grains were found in samples poured at low superheat. Generally, the volume fraction of ferrite increased along the dendritic growth direction, and stabilized in equiaxed zone. The high superheat decreased the volume fraction of ferrite in equiaxed zone, while it had indistinctive influence on chill zone and columnar zone.IntroductionDuplex stainless steel with approximately equal volume of ferrite and austenite, offering an attractive combination of corrosion resistance and mechanical properties. [ l]. The production of DSS, worldwide application in structural engineering[2] and petrochemical industry[3], have increase by more than 100% in the latest decade[4]. But due to the sharp prices increase of nickel and chromium, lean duplex stainless steels which have lower contents of alloy elements were developed. They perform well in both mechanical and corrosion resistance[S, 6] and even have TRlP(Transformation Induced Plasticity) effect[?]. Nonetheless , the mechanical properties of DSS was affected greatly by the solidification structure, such as columnar to equiaxed transition (CET), grain size and phase content[8]. So, the solidification behavior of stainless steel was investigated widely"

Jan 1, 2014

By M. Hashimoto

The equilibrium distribution ratios of sulfur between molten copper and CaO-fluxes containing caF2 and caC12 were determined in the range of 1300° to 1400° C under carbon monoxide. The rate of approach to equilibrium is rapid and increases with increasing CaCll concentration. In CaO-CaFl-CaCl2 fluxes, the distribution ratio varies in a complex way with temperature and CaFl concentration. The results are compared with those obtained with the binary fluxes of CaO with BaFZ and MgFl ?

Jan 1, 1983

By Pekka Taskinen

The converter-less nickel matte smelting technology (DON) adopted more than 20 years ago in Boliden Harjavalta smelter has been since that applied successfully to the processing of large number of nickel sulphide concentrates of various Ni-to-Cu ratios and MgO contents. The operational point of the technology is far from the conventional primary nickel smelting in the smelting-converting route. Therefore, a careful scouting of distribution equilibria of the base and trace elements in the smelting conditions of DON process has been conducted, in order to obtain quantitative information about the equilibria and thermodynamic properties of the nickel mattes at low iron concentrations, less than 10 wt% [Fe] in matte. The series of investigations has included novel experimental and analytical techniques for increasing the reliability and sensitivity of the phase equilibria as well as the element distribution observations carried out in typical high-grade nickel matte smelting conditions.

By Sang-Su Lee

This paper shows the application of the porous plug system in the Mitsubishi continuous copper smelting and converting process. This system has already been adopted and utilized in the steel industry to enhance productivity. Recently, some copper smelters have adopted this system but the results have not been satisfactory. The porous plug system was installed at the anode furnace in December 2001 to reduce the oxidation time and decrease the oil consumption. A good effect was that the nitrogen stirring of the melt through porous plugs improved the melt heat transfer. As the result of the enhancing heat transfer the oil consumption and the build up inside the furnace were actually decreased. But until now the oxidation time has not been sufficiently reduced. In the future, further research and tests are needed in order to increase the productivity and save costs.

Jan 1, 2003

By Eric J. Beckman

Recovery of metals from dilute solution, whether the matrix is solid, or liquid, remains a considerable technical and financial challenge. Methods currently exist whereby metals can be extracted from either type of matrix, yet these methods consume significant quantities of reagents and can also generate multiple waste ,streams in the process. Technology developed in our lab allows efficient application of environmentally-benign CO2 to a number of separation problems involving metals. For example, we have employed biphasic mixtures of C02 and water as a green acid leach medium. Metals have been extracted from a steelmaking process residue and then recovered as metal carbonates through depressurization. In this process, metals are extracted and recovered without the use of reagents other than CO2 and water, and CO2 is sequestered as a solid. In addition, through synthesis of Cal-miscible phase transfer agents, we have shown that CO2 can replace the organic solvent currently used in refining of precious metals, The sensitivity to pressure of phase behavior in a CO2-mixture may allow significant streamlining of the process as well. Finally, CO2 soluble chelating agents have been used to extract toxic metals from acidic effluent such as that found in plating facilities.

Jan 1, 1999

By Thierry De Nys

A direct leaching process of sulphidic zinc-based concentrates in aqueous sulphuric acid solutions has been developed by the V.M. R & D Department. By a very accurate control of the oxidation potential of the leach solution, this process enables a separate recovery of the zinc, copper, silver, lead and sulphur of the concentrate and makes it extremely attractive for treating more complex ores. The iron, solubilized during leaching, is eliminated out of the zinc solution by means of the V.M. goethite process. Alternative flow sheets for a conventional zinc electrolysis plant are presented.

Jan 1, 1990

By Vianey Garcia-Osorio

One of the problems in the carbothermic aluminum process is the substantial loss of aluminum compounds as vapors due to the high temperatures in the process. In order to solve this problem a Vapor Recovery Unit (VRU) is proposed. In this unit operation the aluminum vapor undergoes a series of heterogeneous non-catalytic reactions forming solid, liquid and gas products. In this work a model for the simulation of this unit was developed which includes heat and material balances as well as heterogeneous non-catalytic reactions. The model leads to a system of differential equations; its solution was implemented in Matlab giving as a result a stage-by- stage solid-fluid reaction model.

Jan 1, 2001