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By G Hope, C Young, R. N. Gow

"The presence of enargite (Cu3AsS4) is problematic in gold processing as it is refractory, increasing cyanide and oxygen consumption, and enviromnentally hazardous. Selective leaching and treatment of the arsenic would prove advantageous to conventional gold leaching methods. The reactivity of enargite samples from Montana, US and Quiruvilca, Peru were studied under alkaline conditions, pH range of 8-13, using a cyclic voltammetry corrosion cell setup. Raman spectra of the surface were taken during and after cycling to compare surface species against theoretical predominance diagrams. Under slightly oxidizing conditions, covellite (CuS) peaks were found on the surface in a short matter of time, above - 200m V vs SHE for pH 9-13, suggesting arsenic leaching, but for longer conditioning times, elemental sulfur peaks were also found, which created a passivating surface layer. By operating above pH 12, under reducing conditions, ~-500mV vs SHE, arsenic can be leached as a thioarsenate (AsS4-xOx3-), without sulfur formation.IntroductionEnviromnental limitations on pyrometallurgical processing of arsenic has pushed the desire to process enargite-, Cu3AsS4, bearing concentrates towards a hydrometallurgical solution. Attempts to process can be broken down into two categories - the co-dissolution of arsenic and copper under acidic conditions or the selective leaching of arsenic under basic conditions. The selective leaching of arsenic would preferably leave behind a chalcocite, Cu2S, or covellite, CuS, phase that would be more amenable to conventional processing methods of the copper and gold industries. These methods employ bi- or poly-sulfides to leach arsenic as Assl· [1-4], hypochlorite leaching [5-7], ammoniacal leaching [8] or fine grinding to mechanically activate the enargite surface and increase normally slow reaction kinetics[9]. This study looked into the surface formations of an enargite electrode under alkaline conditions, in a pH range from 8-13, as it cycled from -1000 mV to 1000 mV vs SHE. The understanding of the formations and under what conditions they form will be helpful in further development of any of the aforementioned processes."

Jan 1, 2012

By M. Drozd

Multi-use pad operators require an efficient and economic method to destroy cyanide in their process residues so new material can be stored on the pad and leached. Operators of the dedicated or single-use pads require an effective cyanide destruction method for pad closure. Cyanide destruction can be accomplished by utilizing oxidants such as hydrogen peroxide or calcium hypochlorite, or by utilizing ferrous sulfate which sequesters the cyanide in strong acid dissociable complex. Ferrous sulfate can be the preferred method of cyanide destruction because it is a less costly chemical, reaction rates are almost immediate and unlike oxidants, it can penetrate the total depth of a pile without being destroyed by side reactions. Literature indicates that the (Fe(CN)6)-4 com~lex is produced slowly but it appears that complexes such as Fe(CN)4(H20)2-or Fe(CN)4(OH)2)-4, are formed quickly and should have no U.V. sensitifity, unlike (Fe(CN)6)-4. Stoichiometry of the testwork indicates that Fe«CN)4(OH)2)-4 complex may be the species formed. The usage of ferrous sulfate has the advantage of being able to bring ~ level down that divalent metal ions such as Cu++, Cd++, Hg++, Pb++ and Zn will form insoluble complexes and precipitate from solutions does not destroy weak acid dissolvable complexes and can leave a heavy metal problem behind after cyanide destruction.

Jan 1, 1990

By Weyman Dunaway

This paper will present a description of the development and commissioning of the world?s most efficient process for manufacturing high purity aqueous zinc bromide. The method for making aqueous zinc bromide from metallic zinc and bromine comprises contacting zinc with bromine dissolved in a reaction solvent containing a metal halide salt. The reaction temperature is maintained at less than 60°C. The reaction solvent preferably comprises an alkali, alkaline earth, or transition metal halide; the halide salt preferably comprises a chloride or a bromide. One preferred method includes the step of recirculating the zinc bromide product stream back to the reaction vessel. The reaction vessel can be either a one stage or a multiple stage reactor. The resulting product stream is a high density aqueous zinc bromide solution. The process is so novel that Tetra Technologies, Inc. was awarded US Patent Number 6,036,937.

Jan 1, 2006

By Jan Petter Maehlen

Solid H-absorbing materials are in focus of ongoing R&D to offer viable solutions for the hydrogen storage and supply systems aimed on use of hydrogen as energy carrier for automotive transportation. Low operating pressures, combined with high gravimetric and volumetric efficiencies, together with fast kinetics of hydrogen release at ambient temperatures (providing conditions for a low energy loss due to decomposition), are the most important features of the ?ideal? H storage material. Hydrides of the light elements are the only possible candidates to build systems with an overall efficiency similar to those accommodating liquid or compressed (700 bar) hydrogen. One promising material from this point of view is aluminium trihydride, alane AlH3 with a gravimetric storage capacity of 10 wt.% H. This work was focused on studies of the crystal structure and thermal decomposition of alane by application of powder synchrotron X-Ray diffraction.

Jan 1, 2006

By A. Gibson

Most methods for the treatment of scrap printed circuit boards do not reclaim the components in working order as the boards are either fed to a copper smelter, to recover the valuable elements, or, simply landfilled. This work reports the dissolution of the solder in fluoroboric acid containing Ti4+ ions which was particularly selective for solder, allowing the components to be recovered. The solder was subsequently electrowon from the leachant. The boards were then shredded and the copper dissolved in ammonium sulfate and, then treated via solvent extraction to give an electrolyte suitable for electrowinning. The remainder of the metals were dissolved aqua regia, silver remained unattacked by the aqua regia, palladium precipitated as Pd(NH4)Cl6 in the presence of zinc and nickel, the gold was removed by solvent extraction and precipitated as nanoparticles. The aqua regia was then diluted and the zinc and nickel separated by solvent extraction.

Jan 1, 2009

By Sunil Jayasekera

This paper describes the results of a study carried out to examine the feasibility of electrolytic recovery of silver from cyanide leach liquor generated from a Western Australian silver mine tailings using a novel high mass transfer electrowinning cell. The proposed circuit involves heap leaching and electrowinning in a closed loop. The filter-press-like closed electrode arrangement of the cell allowed much improved mass transfer of metal ions to the cathode surface, making direct electrowinning of metals from dilute solutions feasible. The tests were conducted both in the laboratory and at large scale using a prototype with ~1.0 m2 cathode area. The results showed that the recovery of silver from as low as 250 mg L-1tenor was feasible. The silver deposit produced with the prototype cell was non-adherent and powdery and could be readily removed from the closed cell. A system was developed so that silver powder was discharged continuously during the run.

Jan 1, 2003

By Anita E. Lam

The thiosulfate leaching of gold generally requires the presence of a catalyst such as cupric tetraammine, Cu(NH3)42+, to obtain reasonable leaching rates and gold extractions. Unfortunately, this same catalyst that accelerates gold leaching also tends to accelerate thiosulfate oxidation to tetrathionate and other species. It is therefore imperative that a detailed understanding of the role of this catalyst and the factors affecting it is obtained. It is equally important for plant application that a method of assessing the catalyst be developed. In this work the role of the cupric tetraammine catalyst was studied using geochemical modeling for speciation prediction, thiosulfate leaching of gold ores, and chemical analyses of resulting leach solutions. It was found that the variables of pH, temperature, and the concentrations of ammonia, thiosulfate, and total copper all work in concert to affect the concentration of the cupric tetraammine species. It was also found that the presence of sufficient thiosulfate and cupric tetraammine was critical to the success of the leach.

Jan 1, 2003

By S. J. Kohut

Until recently SX-EW technology has only been used to produce conventional cathode for the cyclical commodity marketplace. Unlike electrorefining, SX-EW lends itself to the integration with the downstream manufacturing technologies for direct mine site production of value added products. The integration of SX-EW and downstream manufacturing results in the elimination of redundant process steps, the cost savings, and the access to value added product markets which can buffer the producer from swings in the cathode market. SX-EW production of copper powder and powder-based products has been demonstrated at the pilot plant level. The SX-EW process has been successfully redesigned to meet the more specific demands of engineered products. Challenges include the solution purity, the cell ventilation, the high current density operation and the product handling. Successful demonstration of mine site production of value added SX- EW products opens up new non-commodity marketplaces to the mining industry.

Jan 1, 1999

By Masatsugu Morimitsu, Tian Zhang

"This paper presents a novel anode for oxygen evolution in acidic aqueous solutions to produce non-ferrous metals by electrowinning. The method to prepare the anode was thermal decomposition of a precursor solution, and the obtained anode consisted of Ru02-based oxide catalytic layers formed on a titanium substrate, in which the catalytic layer contains nano-oxide particles as the active component. The oxygen evolution potential was lower than amorphous lr02-Ta20s coated titanium anodes so that the cell voltage of electrowinning was further reduced with the amorphous Ru02-based electrode.IntroductionElectrowinning (EW) is used to produce high purity of non-ferrous metals, and the primary metal production of copper, zinc, nickel, and cobalt by EW consumes huge electric energy worldwide, which tends to increase with increasing demand of such metals. The reduction of electric energy consumption is a significant issue for electrowinning industry, which means that the cell voltage reduction is needed to realize more energy-efficient EW processes. Another issue is also indicated from environmental perspectives; i.e., an improvement in EW plant environment by eliminating hazardous byproducts and wastes. Such byproducts and wastes include lead oxide, manganese oxide, and acid mist.We have been developing the anodes for energy-efficient and environmentally friendly electrowinning processes [ 1-11]. The development has been successfully done with the invention of the smart anode, MSA TM (Morimitsu Smart Anode) [ 1-5], which has low polarization for the main reaction and high polarization for the side reaction, in which the main reaction is oxygen or chlorine evolution, while the side reaction is the anodic deposition of each or both of lead oxide, manganese oxide, and cobalt oxide. The anode consists of a valve metal substrate coated with amorphous or less crystalline oxide catalytic layers. One of the typical examples of such oxides is amorphous lr02-Ta20s, and the substrate is normally titanium plate or mesh. The most important point of the oxide is that the amorphization or less crystallinity induce the increase in the active surface area only to the main reaction, not to the side reaction, thereby the polarization of the main reaction being reduced.In this paper, we present the smart anode consisting of RuO2-based catalyst formed on titanium substrates for oxygen evolution in electrowinning. The preparation, characterization, and polarization behaviors of the anodes are shown, and the cell voltage data for zinc or copper electrowinning using the anodes are also presented."

Jan 1, 2012

By David G. Dixon, Ahmad Ghahremaninezhad, Edouard Asselin

"In this study pertaining to the electrochemistry of chalcopyrite, the active/passive behavior of a chalcopyrite electrode in 0.5M sulfuric acid solution was investigated. Potentiostatic and potentiodynamic polarization and multi-cyclic voltanunetry were conducted to analyze the electrodissolution parameters of the electrode.The potentiodynamic and potentiostatic polarizations of chalcopyrite revealed the formation of a passive film on the surface of chalcopyrite. From the potentiostatic study in the passive potential region, a decrease in the dissolution current density by increasing the potential was observed. From this, it was concluded that the passive film is an n-type semiconductor and cation interstitial defects or anion vacancies are the charge carriers. From multi-cyclic voltammetry studies, four cathodic peaks at - 0.37, 0.30, -0.10 and-0.20 YsHE were detected on the surface of a passivated chalcopyrite electrode. The cathodic peaks at 0.37 and 0.30 V were connected to ferric to ferrous reduction and copper sulfide formation, respectively. The peaks at -0.10 and - 0.20 were related to chalcopyrite reduction. The products of the chalcopyrite reduction reactions were suggested to be Cu2S, Cu9fesS16 and Cu5feS4 and evolution of hydrogen sulfide gas (H2S).IntroductionChalcopyrite is the most abundant copper bearing mineral in the world and its dissolution behavior represents the most important technological consideration in the hydrometallurgical extraction of copper [I]. Since the current pyrometallurgical methods for copper extraction from chalcopyrite have environmental issues, many studies have considered the leaching and dissolution of CuFeS2 in different aqueous media [2-5]. The main problem associated with leaching processes is the slow dissolution rate of the mineral [6]. During the dissolution process, increasing the potential of the chalcopyrite in the anodic direction will cause the formation of surface layers which hinder the dissolution rate of the mineral [7]. The precise composition of the layers is in dispute. Previous studies have concluded that these layers could be sulfur [8-9], precipitated iron compounds [8], a solid electrolyte interphase (SEI) - which slows the rate of electron transfer- [10], a metal deficient sulfide [ll], or polysulfidic in nature [12-13]. In order to increase the leaching kinetics of chalcopyrite, the characterization of the layers formed during dissolution is essential and electrochemical methods are important to this end. Studies by Biegler [14] show nucleation and growth of a thin two-dimensional sulfide phase on the surface of chalcopyrite during the exposure of a polished sample in HzS04 solution or air. More studies by Biegler and Swift [15] have shown evidence for nucleation and growth of a 3-dimensional phase at low anodic potentials (around 200 mV vs. OCP). The current-time behavior of the dissolution process in this potential area has the characteristics of expansion and overlap of localized dissolution centers."

Jan 1, 2012

By Daniel Helm

The first industrial application of direct solvent extraction of nickel from hypersaline sulfate feed solutions has highlighted the need to investigate the influence of chloride on the extraction behaviour nickel in the presence of calcium using Versatic 10 and the solubility characteristics of gypsum. Temperature-solubility curves for gypsum in various aqueous electrolytes were prepared. The solubility of gypsum is increased significantly by the presence of sulfate ions, while chloride ions decrease it for a given temperature. The anion effects of chloride and sulfate on the extraction of calcium and nickel by Versatic 10 corresponded well with the complexing ability of the anions. It was shown that the presence of chloride shifts the extraction isotherms for both metals significantly to the left, while decreasing the selectivity of Versatic 10 for nickel over calcium. The loading of nickel onto Versatic 10 in this system was shown to be at a maximum within 3 seconds, while calcium extraction took between 4 ? 5 seconds to load to a maximum. Chloride ions had no influence on loading kinetics of nickel, but depressed the rate of calcium loading. It was shown that in the presence of an excess of nickel, calcium loading is effectively eliminated, and that calcium is scrubbed from Versatic 10 within 2.5 seconds of contact with nickel electrolyte.

Jan 1, 2003

By Lloyd Robert Nelson

The historical progression in installed electric furnace smelting capacity of some 1650 calcium, chromium, manganese, nickel and silicon ferro-alloys furnaces is reviewed. Key increases in the inherent installed electrical capacity, often achieved through uprating furnaces, are identified. Possible factors facilitating such advances are explored, including: specific process engineering and pyrometallurgical enhancements (e.g., improved control over the consistency, size and chemical form of raw materials, extents of preheating and pre-reduction delivered into the furnace; and patterns of feed distribution); furnace electrical configuration (AC or DC; immersed, submerged-, shielded- or open-arc); form of electrode (graphite, self-baking or composite); furnace configuration (circular or rectangular; closed or open and 1-, 3- or 6- electrodes); better engineering and equipment designs (e.g., high-intensity cooling) and state of furnace electrical and metallurgical control systems. A view is presented on the prevailing state of evolution of the Mega-scale in ferro-alloy smelting and opportunities for still further improvements.

Jan 1, 2014

By Maria Cristina Ruiz

The removal of iron from the leaching circuits is a common problem in the hydrometallurgical processing of non ferrous metals. Among the currently available processes, hematite precipitation is the most recommendable from an environmental point of view. This paper is concerned with the batch precipitation of hematite from ferrous sulfate solutions. One of the main objectives of the study was to determine the effect of the experimental conditions on the extent of iron precipitation as well as the purity and the particle size distribution of the precipitates. The main variables studied were temperature (180 to 220 ºC), concentration of sulfuric acid (1 to 10 gpl), initial iron concentration (1 to 15 gpl) and partial pressure of oxygen (3 to 7 atm). The results showed that increasing the oxygen partial pressure from 3 to 7 atm produced a very small increase on the rate of hematite precipitation indicating that a large partial pressure of oxygen is not needed for an effective ferrous to ferric oxidation. An increase in the temperature produced finer precipitates with lower sulfur contents. On the other hand, an increase in sulfuric acid concentration and initial iron concentration produced precipitates with larger particle sizes and higher sulfur contents.

Jan 1, 2006

By Luciano B. Oliveira, Alexandre M. Stumbo, Luis G. C. Marques, Valdo S. Marques, Sergio N. Monteiro

"Similar to the ethanol program, initiated more than 30 years ago, the recently created biodiesel program in Brazil is expected to rely on private initiative based on agribusiness for vegetable oil production. Campos dos Goytacazes is a large county in the northern of the state of Rio de Janeiro with land still available for oily vegetables plantation in addition to the land traditionally occupied by sugar cane plantation, which is used to produce ethanol. In order to extend the biodiesel program to Campos dos Goytacazes, the State University of Northern Rio de Janeiro (UENF) is conducting a technical project for the development of the infrastructure for biodiesel production. In this work, the infrastructure based on versatile equipment for biodiesel esterification built in the Center for Alternative Energy of the UENF is presented.IntroductionBiofuels are gaining worldwide attention as a possible economical solution for the prediction of declining reserves of petroleum and related increase in price of barrel. However, nowadays, a more relevant question is the climate changes caused by burning fossil fuels. This is especially the case of coal and petroleum based fuels, mainly gasoline and diesel that propel the majority of vehicles and generate a large amount of CO2 emissions responsible for global warming. This combination of economical an environmental problems is already providing a strong motivation to substitute conventional fossil fuels by renewable biofuels. More than just the interest of the market financial forces, government legislation is imposing a new order that obliges the use of biofuel. Many countries including the USA, the European Community, Japan and Brazil are committed to gradually substitute biofuels into their fleet of vehicles."

Jan 1, 2008

By Marcio Toshio Tanaka, Marcelo Breda Mourao, Cyro Takano, Cesar Yuji Narita

"The concerns in questions related to the environmental impact in the steelmaking industries caused mainly on the gas emissions such as the dioxide carbon are due to its raw material such as the coal, a fossil and non renewable resource. The purpose of this paper is to replace from 10% to 50% of the coal used in cokemaking by mixing it with a renewable source (wood charcoal). The powder (- 325 mesh) from both raw materials (coal and wood charcoal) were mixed in order to obtain a briquette that was then heat treated at 1100°C to obtain the biocoke. Results of usual analysis (coke reactivity index, coke strength after reaction and cold crushing strength test) were employed to compare to regular coke briquettes. It was found that biocoke with different amounts of wood charcoal present features enabling it to be used in some ore reductionprocesses.1. IntroductionThe iron and steelmaking industry is a heavy emitter of carbon dioxide; according to the World Steel Association, 6.5% of global emissions of this greenhouse gas is due to the production of ferrous materials [ 1]. This is due to the fact that the fuel and reductant employed in the blast furnace is metallurgical coke, obtained from fossil coal. There are some projects aiming to reduce or even eliminate the emission of fossil GHG in the iron and steelmaking process [2]. Most of them propose the capture and storage of the gas (CCS) [3], a technology not yet proven. Other studies point out that the coke consumption in the blast furnace could be reduced by using high reactivity coke; this could lead to lower temperatures in the thermal reserve zone of the blast furnace and consequently less fuel rate in the furnace.The use of biomass in the iron ore reduction process is known as an environmentally accepted solution, as biomass does not release already fossilized carbon."

Jan 1, 2013

By Alexandre Bonan

The paper reports on the results of a kinetic study on the oxidation reaction of aqueous free cyanide ions with H202, in the presence of Cu(2+) catalyst. The variables and respective ranges studied were the following: (CN) ° = 10 -100 mg/l pH = 10 -11 (H202/CN) mol ratio = 1 -3 (Cu/CN) mol ratio = 0 -0.25 The results lead to the development of a semi-empirical model whish incorporates both the useful oxidation reaction and the parallel alkaline decomposition of H202.

Jan 1, 1992

By D. J. Burkhardt

Newer copper SX/EW facilities often incorporate hot water heating for the cell feed electrolyte to obtain the necessary plating temperatures of 40 to 50°C. Heating is most necessary in oxide heap leaching, however it may also be required in bioleaching of secondary sulphides in colder climates or higher altitudes where most of the heat gain in the heap is lost to the environment. Given that the solution flows in the leach, organic circuit and electrolyte circuit are circular in nature, and the fact that the hot lean electrolyte is often exchanged with cooler rich electrolyte, it can be difficult to access the heating requirement for the cell feed. There are energy losses in piping, tankage, raffinate, and energy gains through the PLS and electrowinning process itself; some of these are significant and others are not. This paper discusses the overall heat balance, the relative significance of the various energy gains and losses, and describes a methodology to develop a heat balance to assist the engineer in sizing the heating equipment.

Jan 1, 2003

By Yuuki Hagio, Hiroyuki Tobo, Michihiro Kuwayama, Yasutaka Ta

"Reduction of CO2 emission is necessary to remedy global warming, however, promising approaches of CO2 separation require a large amount of energy. Molten slag, which is generated as by-product of steel production, has high temperature, but its energy has not been harnessed. To recover the thermal energy from the slag and to apply to separation of CO2 are economical and environmental conscious ways. We propose a new heat recovery system, in which, molten slag is solidified continuously on water-cooled roll and the solidified slag plates are charged into counter-current heat recovery equipment. In laboratory scale experiments, heat recovery ratio of more than 30% was acchived by controlling the thickness of slag.IntroductionThe steel industry in Japan has been working on the projects of ""Environmentally Harmonized Steelmaking Process Technology Development (COURSE50)"". COURSE50 aims at developing technologies to reduce CO2 emissions by approximately 30%. One of the main technologies is to capture and recover CO2 from blast furnace gas using chemical absorbents to regenerate CO2-laden chemical absorbents by separating CO2 from the absorbents. As one of the solutions, JFE Steel Corporation has been developing sensible heat recovery process from steelmaking slag. It is effective to recover and use unutilized high temperature waste heat within a steel plant as the thermal energy required."

Jan 1, 2012

By Junfeng Shen

Geosynthetic clay liner (GCL) is a kind of waterproofing material used widely in engineering. The waterproof mechanism is understood in terms of bentonite particles becoming a water-obstructcolloid layer after they absorb water and swell. The swell stress, however, has not been determined directly till now. In our experiment, the swell stresses of the GCL under saturated and water absorbing conditions are measured directly using a custom-made instrument. The results show that (1) the instrument designed by the authors performed satisfactorily and the test results are reproducible; and, (2) The trend line of swell stress variation with time can be divided into three segments. The first segment is characterized by a quick increase of the swell force in the first 0?50 hours. The swell stress increases by 7.00×10-4?1.00×10-3 Mpa / hour. The second segment shows a slow increase of the swell stress during the 50?1730 hours. The swell force increases by 7.54×10-6?2.02×10-5Mpa / hour. The third segment is characterized by little variation in the swell stress after 1730 hours. In this segment, the average value of the swell stress measurements is 0.0719Mpa and the maximum value is 0.0729Mpa. It is suggested that the swell stress is mainly raised by water entering the pores among montmorillonite particles and the interstitial layers in individual montmorillonite crystals, leading to an increase in volume and manifested as a stress on the surrounding materials.

Jan 1, 2006

By Toshiyuki Hiranami, Keizou Uematsu

"AbstractionSpray freeze drying method was proposed to fabricate ·ceramic: powder granules for high performance ceramics. Obtained granules and their green compact were characterized by SEM and immersion liquid technique. Granules have a spherical shape of about l 00 µ m in diameter, ·and no binder segregation was found with the immersion liquid technique. The granule had sufficient strength for usual handling, while the strength was much lower than that of granules prepared by conventional spray-drying. Unlike the conventional green compacts, granule interfaces were not observed in the green body made with the spray-freeze dried granules.IntroductionIt was well kn9wn that spray-dried granules have binder segregation layer on their surfaces. The trace of this segregation layer survives in the later processes i.e. compaction and firing, and behaves as fracture origins in the sintered bodies. The origin of this problem is solvent drying process from slurry droplet surface in spray drying system. As alternative method we propose a freeze drying process for granule preparation, in which solvent is remove by sublimation though the process, binder segregation can be prevent.In this study, we applied spray freeze drying method to fabricate alumina powder granule, and characterized the obtained granules, and their green compacts and sintered bodies.Experimental procedure.Alumina powders and additives aqueous solution were mixed for 24 hours using a ball mill to· prepare the slurry for spray freeze drying. .The solid loading of the slurry was 30vo1%. Deflocculant (PAA-NH4 type) was added 0.5mass%, and the binder (PVA). 1.0, 2.0 or 3.0mass% of alumina. Obtained slurries were sprayed into liquid nitrogen to make frozen granules. The granules were freeze dried.For the characterization of the granules, immersion, liquid technique observation and single granule strength test were carried out. Strength of individual granule wa5 measured using micro compression testing machine (MCTM, SHIMADZU). Granule strength was calculated from following equation."

Jan 1, 2000