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By M. L. Free

Electrowinning is directly impacted by many parameters that include electrolyte composition, voltage, current density, contact resistance, temperature, electrode spacing, and fluid flow as well as many other interrelated factors. The effects of these parameters are primarily related to thermodynamics, mass transport, and electrochemical kinetics. In this study thermodynamic, mass transport, and electrochemical kinetic equations are simultaneously solved to determine the effects of such parameters on electrowinning current efficiency, power consumption, electrodeposit morphology, and electrodeposit distribution. Modeling predictions will be compared with experimental results.

Jan 1, 2006

By N. M. Komkov

The main operation of obtaining zinc from sulfide raw materials by hydrometallurgical technologies is the oxidation roasting of zinc concentrates in fluidized bed furnaces. The technical-economic parameters are determined by the parameters of the roasting process, which depend on the composition of the initial raw materials, the temperature of the bed and on other factors. The predetermined roasting temperature is maintained due to the change of specific efficiency as well as to the quantity of the heat removed from the bed. The efficiency of caissons depends at a high degree on the composition and the thickness of the accretion formed on the surface of the caissons. Forecasting the roasting results is impossible unless we know the mechanism of the accretion formation. The aim of the present paper is the thermodynamic analyses of the behavior of the charge compositions under roasting and the determination of the potential mechanism of the accretion formation. The thermodynamic analyses show that under conditions of the oxidation roasting the thermodynamic probability of the formation of zinc sulfate is higher than the probability of the oxide formation until a temperature of 873°K is reached. The thermodynamic probability of the formation of the lead sulfate is higher than the probability of oxide formation in the entire temperature range of roasting. The probability of formation of ferrites and silicates of zinc decreases only insignificantly the sulfate stability. The results of the investigation of the accretions composition formed under roasting of concentrates with particle sizes less than 0.02 um (60%), containing 65% of sphalerite (ZnS), 12% of pyrite and chalcopyrite (FeS2 and CuFeSz2 each, 3% of galenite (PbS), 7% of silica and other non-ore minerals, have shown that the composition of accretion varies depending on the depth of the accretion layer. The accretions on the caissons and the thermo-siphons consist mostly of zinc sulfate (more than 50%). The accretions of forchamber consist mostly of zinc oxide. They also contain ferrites and silicates. The formation of the sulfate zinc accretion in the cold parts of the fluidized bed furnace (the caissons and thermo-siphons) may be explained by a lower temperature on the surface and probably by a catalytic influence of the present oxides in the formation of S02 and sulfates. The nature of the structure of the accretion in the hotter parts of the furnace may supposedly be explained by the formation of elemental vaporous zinc during roasting.

Jan 1, 2003

By Helfried Nafe

"For about a century thermodynamically absurd facts have been propagated in conjunction with the iron-carbon phase diagram. These facts concern fundamental relationships of chemical thermodynamics. Attention is turned here to the discussion of only one of the relevant aspects of the subject, i.e. the definition of the thermodynamic activity of the solute and its implications for the iron-carbon solution.IntroductionThe view on the iron-carbon solution is characterized by the assumption that the solute may appear in two different forms, i.e. graphite and cementite. Accordingly, two carbon solubilities are differentiated, on the one hand for graphite and, on the other hand, for cementite. As a consequence, two versions of the phase diagram exist simultaneously, the application of which depends on the prevailing conditions, (i) the so-called stable phase diagram with graphite as solute and (ii) the metastable one that is based on the cementite-in-iron solution. These diagrams are joined together in the double phase diagram that originates from Heyn [l ], with the first ideas mainly going back to Stansfield [2] and Charpy [3].Thermodynamically, the most inadequate implication of the Fe-C double phase diagram is that the carbon activity may take values larger than unity. With the standard state of the activity being that of the pure substance, i.e. the Raoultian one, such a value implies the nonsensical existence ofa state purer than pure. The explanation of this physical state, ifthere is any, vaguely refers to supersaturation and, in the wider sense, to the physico-chemical phenomenon of metastability. Other aspects of chemical thermodynamics are likewise involved. Therefore, the comprehensive investigation into the present subject requires more topics to be considered than only one separate issue. Not only should the criticism of the present view be in the focus but also the discussion of new ideas capable of reconciling the experimental facts, known about the F e-C system, with the fundaments of chemical thermodynamics. All this, however, cannot be provided here because of the limited space available. As a consequence, in what follows only a part of the whole problem is under scrutiny, i.e. the definition of the thermodynamic activity and its role for the interpretation ofrelevant experimental facts."

Jan 1, 2014

By V. D. Tathavadkar

Chromite ore is of immense importance for the extraction of metallic chromium and chromium chemicals. The mineralogy and crystal structure of chromite phase are therefore important part of our investigation on the extraction chemistry of chromium species. In this investigation, we have studied the effect of the processing parameters, i.e., the temperature and the oxygen potential on the microstructure and composition of mineral phases formed in the Cr2O3 ?Al2O3 -FexOy -MgO system. In particular the importance of the spinodal decomposition reaction is emphasized in the extraction of chromium as sodium chromite and sodium chromate. Experiments were carried out in order to study the differences in the crystallography of different chromite minerals. Phase equilibria in natural chromite minerals were investigated by calcining chromite mineral in air, argon, and 5% hydrogen + argon atmospheres over a temperature range from 200 to 1200 °C. The effect of the oxygen partial pressure and temperature on the phase constituents of the calcined product has been discussed. The microstructural changes were examined using scanning electron microscope (SEM) and the changes in elemental composition in different phases were analysed by electron probe micro analyser (EPMA). The results obtained from EPMA studies were used to calculate lattice parameter of the spinel lattice, and these values were compared with the values obtained from X-Ray powder diffraction data. On the basis of the experimental data, the mechanism of the spinodal decomposition of complex spinel phases is described under the influence of oxygen partial pressure and temperature.

Jan 1, 2000

By Andreas Siegmund

During the decade of the nineties the conventional method of primary lead smelting (sinter machine/blast furnace) was successfully challenged by the introduction of novel direct and continuous smelting processes. In combination with a significant shift in market structure, as well as more stringent government regulations these modem technological innovations like the QSL, Kivcet, and Isa/Ausmelt processes became more than major competitors. They have proven to be economically and environmentally viable. The intensification of the metallurgical reaction by applying oxygen enriched or pure oxygen bath or flash smelting principles resulted in cost savings and a higher flexibility with respect to raw materials and additives usage. By synchronizing individual auxiliary plant sections with the smelting process a virtually waste-free production and low-emission mode of operation with nearly optimum energy exploitation is achieved. The primary lead industry will gradually substitute the sinter -blast furnace operation with novel high-energy efficient technologies in the new millennium.

Jan 1, 2003

By Saeid Pournaderi, Ahmet Geveci, Ender Keskinkilic, Yavuz A. Topkaya

There are mainly three commercial nickel laterites in Turkey: Gordes, Caldag and Sivrihisar. The first two appear in Western Anatolia. The third one, Sivrihisar (Yunusemre) laterites have been found in the first decade of the millennium, in the Central Anatolia region of Turkey. Since then, mining facilities have been continued in Yunusemre. Calcination, prereduction and smelting of Sivrihisar laterites have been extensively studied and published. In the current work, some results of the studies related to characterization of Sivrihisar laterites will be presented.

Jan 1, 2016

By Luciano E. Ramírez, Jesús L. Valenzuela, José R. Parga

"An innovative process for removing copper cyanide complexes including silver and zinc from cyanidation circuits has been developed. The technology was based on the inducing the nucleated precipitation of copper and silver in a tube serpentine reactor, using sodium sulfide as the precipitate and sulfuric acid as pH control. The results showed that pH had a great effect on copper cyanide removal efficiency and the optimum pH was about 3 to 3.5. At this pH value copper cyanide removal efficiency could be achieved above 97 and 99 % ,when influent copper concentration ions were 650 and 900 ppm respectively. In this process (sulphidizaton-acidification-recycle-thickening), the cyanide associated with the copper cyanide complexes is released as HCN gas under weakly acidic conditions, allowing it to be recycled back to the cyanidation process as free cyanide. This system was successfully commercial applied at Minera William in Mexico.IntroductionThe recovery of gold and silver from minerals and concentrates with cyanide is an important hydrometallurgical process, which has been studied for more than 124 years. Patented by MacArthur in 1888 [1], the process relies on the fact that gold dissolves in aerated cyanide solutions to produce the gold cyanide complex. The stoichiometry by wich this reaction occurs is known as the Elsner equation as shown here. Silver is accomplished in the same fashion."

Jan 1, 2012

By A. McLean, Y. Uchida, M. Iwase, M. Myochin, K. Wiikimoto

"Phase diagrams of FeO-containing ternary systems could be derived from experimental data for the activities of FeO. The systems investigated are CaO-CaF2-FeO, SrO-SrF2-FeO; BaO-BaF2-FeO, CaO-CaCl2-FeO, SrO-SrC12-FeO, BaO-BaC12-FeO, CaO-A12O3-FeO and BaO-SiO2-FeO.IntroductionThe importance of phase diagram cannot be overemphasized. In a book, ""Alloy Phase Equilibria""[l], the author, Professor A Prince, states, ""A metallurgist has been defined as a person who thinks in terms of phase diagram"". Whether one accepts this statement or not, it is self-evident that an ability to interpret phase equilibria is essential to the professional metallurgists.The physical chemistry studies of iron and steelmaking process often require phase diagrams of FeO-containing slags. Iso-thermal section of the phase· diagrams of such systems can be derived from experimental data for chemical potentials of FeO. Due to the recent developments in the area of solid state electrochemistry, rapid determinations of the FeO activities have become possible. The present paper is aimed at documenting the derivation of the phase diagrams of FeO containing slags.Experimental AspectsAn electrochemical method incorporating stabilized zirconia can be used for the measurements of the activities of FeO in various slags and fluxes[2]. For the details of the experimental technique, reference should be made to reference 2"

Jan 1, 2000

By F. E. Pawlek

Copper concentrates can be comminuted in an attritor within a very short time to a particle size of 1 - 0.1 um. Addition of sodium hydroxide enhances commninution. The concentrates, suspended only in water, can be completely dissolved under oxygen over pressure and temperatures ranging from 120 - 180°C (248 - 356°F), because the surface area of the concentrate has been significantly increased by the ultra fine grinding. Addi¬tion of a small amount of silver ions to leach liquor containing sulfuric acid acted as a catalyst for the dissolution of chalcopyrite, because of the formation of local elements on the surface. The addition of C1- ions was also catalytically very effective. With this method it is possible to completely dissolve the copper contained in chalcopyrite concentrates after ultra fine grinding within 30 min at 110°C (230°F) under an oxygen partial pressure of 1 atm (14 psig). Several flowsheets demonstrate the industrial feasibility.

Jan 1, 1976

By Yasuo Kudo, Wu, Hayato Sato, Hiroshi Nakazawa, Shouming

"In order to recover copper from a waste nickel condenser powder, bioleaching experiments were carried out using Thiobacillus ferrooxidans in a shaking flask. The content of nickel and copper in the waste nickel condenser powder in this study were 8.0% and 3.5%. X ray analysis showed the peak of barium titanate. In the preliminary study using metal nickel and copper powders , the dissolutions of nickel and especially copper were accelerated with the addition of ferric iron in the bioleaching of nickel and copper powders while not in the absence of ferric iron. Ferric iron oxidizes both metals, and Thiobacillusferrooxidans oxidizes ferrous iron resulting from the oxidation of metals, whereby the dissolutions of metals proceeds. The dissolution rates of nickel and copper increased with increase in the concentration of ferric iron in the bioleaching of the waste nickel condenser powder.1. IntroductionNickel condensers rejected from manufacturing plants are crushed and landfilled. Waste nickel condensers contain nickel and copper and could be considered as nickel and copper ores. Since the capacity of landfills is diminishing, it is required to recycle metals of waste nickel condensers in order to reduce the amount of wastes landfilled. Conventionally, metals in the waste were recovered by dry metallurgy after the incineration.Nickel has been refined by solvent extraction - electrowinning method (SX-EW method). Recently the amount of copper refined by SX-EW method has increased (Takahashi, et al. 1994). This method is cleaner and consumes less energy than conventional methods. Nickel dissolved well in acid solutions, but copper is not. If copper is leached efficiently from a waste nickel condenser powder, SX-EW method will be applied to recover copper from them"

Jan 1, 2000

By H. Masuda

The lijima Zinc Refinery started operation in 1972, and has today an annual capacity of 200, 000+-Zn. The hematite process was employed for the first time and the ideal of waste-free refinery has been pursued for 30 years. In recent years, however, only half of the hematite produced would be sold to the cement industry and hence a reduction of arsenic level has been necessary in order to sell the entire amount produced, The arsenic cementation process with zinc powder, developed through a long time laboratory research was found among some options as the best for the hematite process. The construction work started in 2000 and the facility was put into operation in 200 I. As a result in the same year all hematite were sold to the cement industry. The outline of this project, present operations and technical issue are reported in this paper.

Jan 1, 2003

By Hassan Saalman, Mahmoud Mahmoud, Omneya El Hussaini

The Ferruginous sandstone ore was obtained from Ramlet Hemeyir area, Southwestern Sinai, Egypt, was found to contain 10% rare earth elements (REE). A representative sample has been subjected to sulfuric acid agitation leaching. About 93% of the REE content was released by mixing the ground sample to -100 mesh with concentrated H2SO4 at solid/liquid (S/L) ratio of 1/2 for 5h at a temperature ranged from 250 to 300o C. The REE was precipitated from the prepared sulfate leach liquor of pH 1.0 by adding 35% oxalic acid at 25o C. The precipitation yielded 98% REE. For selective separation of yttrium, the rare earth cake was leached with 31.5% nitric acid. Next, the aqueous solution was contacted with di-(2-ethylhexyl) phosphoric acid (D2EHPA) where 98% yttrium extraction was achieved. Stripping was done with hot H2O (80o C). Finally, a precipitation with oxalic acid was done followed by ignition at 950o C. A yield of 95% yttrium oxide was produced.

Jan 1, 2014

By Keiji Okumura, Jiayi Shan, Jian Yang, Masamichi Sano

"A new method of deoxidation and desulfurization of molten iron with magnesium vapor has been developed. An immersion tube, which was filled with pellets of the mixture of magnesia and carbon powders, was put into the molten iron. Magnesium vapor produced by carbothermic reduction of magnesia inside the tube was injected directly into the molten iron with argon carrier gas. The effects of temperature and carrier gas flow rate on deoxidation and desulfurization were investigated. A mathematical model of the reactions was developed. The rates of deoxidation and desulfurization were controlled by mass transfers of magnesium vapor in the gas-phase and oxygen and sulfur in the liquid-phase. This method may offer high efficiency for magnesium deoxidation and desulfurization of molten iron.IntroductionMagnesium is a strong refining agent in steel-making processes1 • At steelmaking temperatures, magnesium has a very low solubility in liquid iron, and a very high vapour pressure2 • Deoxidation and desulfurization with magnesium take place essentially through the interaction of magnesium vapor with oxygen and sulfur dissolved in molten iron, and magnesium can change chemical composition of nonmetallic inclusions3 • However, addition of magnesium to the steel bath is dangerous and does not give high efficiency in the refining process4 • Furthermore, as a refining agent, the price of magnesium is higher than aluminium and CaO fluxes. In the present study, a new method of the deoxidation and desulfurization of molten iron was developed using magnesium vapour in-situ produced by carbothermic reduction of magnesium oxide. Pellets made of mixture of magnesia and carbon powders were charged into an immersion tube, which was made of alumina or graphite. The magnesium vapor was injected directly into the melt. The effects of pellet mass, experimental temperature and carrier gas flow rate were studied on the refining rate. A mathematical model of the refining reaction was proposed on the basis of the experimental results."

Jan 1, 2000

By Arpad E. Tonna

Recycling of materials from lithium-oxyhalide batteries is a complex task, since the dismantling of batteries is associated with many hazards. The electrolyte and the lithium anode metal are extremely reactive in the presence of water or water vapor. Therefore, the dismantling process is a complex task. In this process, the lithium battery is electrically discharged, then frozen in liquid argon, and cut into small size pieces. These are fed into an incinerator, where the unreacted portion of lithium metal, thionyl chloride, plastic separators and carbon paste are decomposed and burned to gaseous products. The aluminum, iron (steel) and nickel pieces are recovered as saleable scrap metals. The off-gases are scrubbed with an alkaline sodium carbonate containing solution. The clean gases are released to the environment. The particulate mater recovered from the scrub-suspension would be available as additive to the cement industry . The recycling of battery decomposition products improves the economic viability of the disposal processes. Work is in progress to develop safe handling, processing and recycling large size lithium batteries.

Jan 1, 1995

By Qingchun Yu, Bin Yang, Yong Deng, Heng Xiong, Fei Wang, Minxiu Chen

"Metal aluminum produced by non-electrolysis process received much attention due to its lower energy consumption. In this paper, carbothermic reduction and carbothermic-chlorination of alumina in normal pressure and vacuum were studied. The products were examined by means of XRD, EDS and SEM. During the carbothermic reduction process using carbon reductant in normal pressure, no metal aluminum was found. However, when coal was used as reductant, a mixture containing metallic aluminum, A14C3, and silicon was obtained, but metallic aluminum couldn't be separated from the mixture. During the carbothermic-chlorination process in vacuum, Al404C and Al4C3 were produced by the reaction between alumina and carbon, and Al Ch gas reacted with Al404C and Al4C3 to produce Al Cl gas. Metallic aluminum was produced due to the disproportionation of A!Cl gas and condensed on the collecting plate. Meanwhile, the initial temperature of carbothermic reduction of alumina reduced in vacuum compared with that in normal pressure.IntroductionIndustrial production of primary aluminum is carried out in alumina cell by the so-called Hall- Heroult process, necessitating the use of very high currents of low voltage. The alumina from which metallic aluminum is gained must be chemically pure, otherwise impure metal results. The main drawbacks of the electrolytic production are its very high energy consumption, the release ofperfluorocarbons, and the high specific C02 emissions [1]. During the past years, there were a lot of attempts to produce metallic aluminum by carbothermic reduction of A1203 [2, 3]. Cox [4] determined the vapor pressure over the A1203-C system and performed X-ray diffraction analysis of condensed products. It was demonstrated that an increase in the carbon content in the system leaded to the sequence of transitions: A1203~Al404C~A1zoc~A14C3 ~AI [5]. In any carbothermic reduction process for aluminum, extremely high temperatures (2000 °C ) were required [6]. In spite of considerable effort, the carbothermic reduction of alumina to aluminum remains a formidable technical challenge, due to the high temperatures required, and to the formation of aluminum carbide and oxycarbide byproducts [7]."

Jan 1, 2013

By Mingming Zhang, Ramana G. Reddy

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

Jan 1, 2008

By Fei Ruan, Chang Jie, Jieyu Zhang, Jifang Xu, Kuochih Chou

"Viscosity is an important physical parameter of slag in metallurgical processes. Most studies of aluminosilicate and aluminate systems assume that aluminum occurs in tetrahedral coordination. In this case, the O/Al value was utilized to describe the slag structure in terms of the network character of aluminosilicate and aluminate systems. Composition and viscosity data from the literature and the trends were analyzed according to the O/Al value and temperature. It is shown that the O/Al value explains the trends in more than ten systems, containing more than 200 data points. In aluminosilicate system, the trend that viscosity value changed with the O/Al value which implies that alumina works as network modifier such as basic oxides or works as network former. In aluminate system, irrespective of the system and temperature, viscosity decreased steadily when O/Al value increased.IntroductionMetallurgical slags, which are made of oxides and many also contain fluorides, play an important role in metallurgical processes such as iron making, steel making and secondary refining processes. Aluminosilicate slags are applied in a wide range in metallurgical processes. A polymerizing effect of the addition of aluminum and an association of aluminum with low-field strength cations is further supported by the physical variations in aluminosilicate and aluminate systems. The behavior of alumina in silicate melts has been studied by various authors [1-6]. It is generally accepted that Al2O3 is amphoteric [7] because Al3+ ions can behave in profoundly different ways in a silicate melt. When added to a pure silica melt, Al2O3 acted as a network modifier, breaking the bridging oxygen of the pure silica network, thereby decreasing the viscosity in a similar manner to other network modifiers, such as CaO, MgO etc. to form [1/2Ca (AlO4)]4- complexes. However, when added with alkali or alkali-earth metal oxides, some of the Al3+ ions assumed tetrahedral coordination and replaced Si in the liquid network, the missing charge was compensated by Me+ or Me2+ ions. Therefore Al2O3 acted as network former [8, 9]."

Jan 1, 2011

By Michael G. Mayer

Since its invention in 1859 various designs of lead batteries have evolved to meet commercial needs for traction applications and standby power. In recent years major developments have taken place in lead alloys and the chemistry and mechanical design of industrial lead batteries. These are reviewed in relation to their commercial application together with the new type of maintenance free gas re-combination lead-acid batteries which are opening so many new markets for lead.

Jan 1, 1990

By W. Drummond

The cooling of smelter gases by air dilution, adiabatic evaporative cooling and indirect heat exchange is discussed with reference to the process, to the subsequent cleaning of the gas. and to the use of the heat extracted from the gas. The method of reducing the effect of acidic sulphide formation on the corrosive properties of the gas and the dust and the development of surface cleaning mechanisms?are discussed. The development of indirect recuperators using air, water or steam cooling, made possible by the control of surface fouling is traced. The application of the modern Waste Heat Boiler to the new sulphide smelting processes is discussed with respect to the natural and forced circulation concepts. Case histories are presented to illustrate mistakes made with respect to designs produced without recourse to sensitivity analysis and without an appreciation of "worst process? conditions".

Jan 1, 1992

The oxidation of zinc vapour plays a very important part in the operation of the Imperial Smelting Process. The kinetics of the reoxidation of zinc vapour by carbon dioxide and water vapour onto quartz and zinc oxide substrates is qualitatively understood and this pertains to the conditions found as the gases are being transferred from the furnace to the splash condenser. However, re-oxidation also occurs in the shaft of the furnace where the solid substrates are sinter and metallurgical coke. It was found that there was a threefold increase in the rate of oxidation on sinter, compared to quartz and a 30 to 300 increase in rate on the coke. This was attributed to the high surface area offered by these materials.

Jan 1, 2003