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By O. Barbosa F.

The thermochemistry of the systems SCN-H2O, Au-SCN-H2O and Ag-SCN-H2O is discussed. Potential-pH diagrams at 25°C are drawn for each system considering several sets of concentrations of the species involved. The information provided by the potential-pH diagrams is.complemented by distribution curves for each series of gold and silver complexes with thiocyanate. The analysis includes comparisons between the thiocyanate systems and the analogous cyanide systems, pointing out analogies and differences between the leaching of gold and silver with thiocyanate and with cyanide. The possibility of using soluble oxidizing agents such as ferric ions, hydrogen peroxide and Caro's acid is evaluated. The thermodynamic data used in the calculations and the chemical reactions represented in the Pourbaix diagrams are all reported in three Appendices. The overall results indicate the thermodynamic conditions for gold and silver leaching by thiocyanate.

Jan 1, 1989

By Anxiang Wang, Kunhua Wu, Yifu Li, Junjie Xu, Yongnian Dai, Bin Yang, Lingxin Kong

In this study, the saturated vapor pressures of tin (Sn) and antimony (Sb), the separation coefficient and the vapor-liquid phase equilibrium of Sn-Sb alloy were theoretically analyzed, which demonstrate that it is possible to separate Sn and Sb by vacuum distillation. The process parameters of vacuum distillation, including the distillation temperature, distillation time and alloy mass (thickness of raw materials) on the direct yield of Sn and the content of Sn in liquid phase were investigated by using single factor experiments. The preliminary results show that the direct yield and the content of Sn are 98.77 wt.% and 96.01% with the optimized distillation conditions of a distillation temperature of 1473 K, a distillation t ime for 45 min and a Sn-Sb alloy mass of 125 g ( thickness o f 8 mm). The distillation parameters in the study provide effective and convenient conditions on separation of Sn-Sb alloy.

Jan 1, 2016

By Zhang Chuanfu, Tan Pengfu

"A thermodynamic model is developed to predict the distribution behaviors of Ni, Co, Sn, Pb, Zn, As, Sb, Bi, Au and Ag in copper pyrometallurgical process. In this model, as more as 21 elements (Cu, S, Fe, Ni, Co, Sn, As, Sb, Bi, Pb, Zn, Au, Ag, 0, N, C, H, Ca, Mg, Al, and Si) and 72 compounds (in fayalite-slag-making system) or 74 compounds (in ferrite-slag-making system) are considered. Accessory-element behavior is studied for two types of slag , fayalite and ferrite, and two levels of oxidation. The allowance is also made to account for physical entrainment in the melts.-Model simulations are carried out to study the effects of controllable process parameters such as feed composition, smelting temperature, degree of oxygen enrichment and volume of oxygen enriched air. The model can be used in copper flash process, Mitsubishi process and Noranda process. The predictions by the present computer model are compared with the known industrial data from Gui Xi Smelter in China, Home Smelter in Canada and Naoshima Smelter in Japan and excellent agreement between calculations and industrial data is obtained. In this paper, the effects of oxygen enrichment, matte grade, smelting temperature, and types of slag on accessory-element behavior among matte, slag and gaseous phase have been elucidated.I . IntroductionThe presence of trace quantities of minor elements such as As, Sb and Bi in copper significantly reduces its ductility, electrical conductivity, and lowers its thermal conductivity. Embrittlement of copper also occurs due to impurity-phase precipitates at the copper grain boundary interfaces. They deteriorate not only the electrical conductivity of copper but its workability in hot working."

Jan 1, 1998

By Wenjun Duan, Qingbo Yu, Qin Qin, Junxiang Liu

In the study, the coke-oven gas (COG)-steam reforming process using hot blast furnace slag (BFS) as the heat carrier is explored for producing hydrogen and recovering high-grade waste heat of hot BFS. The method of the Gibbs energy minimization approach through Lagrange multiplier is adopted in the thermodynamic analysis of reforming process. The simulation is carried out to study the operation pressure, temperature and steam to carbon ratio (S/C) based on the chemical equilibrium calculations. The optimal operation conditions are determined to improve the yield and fraction of hydrogen in the COG-steam reforming process. The results suggest that the preferential operation conditions for COG-steam reforming process to produce hydrogen are achieved at 600ºC, 1.5MPa and S/C (5.0). Due to the CaO and other melts in BFS, CH4, CO and CO2 in COG are converted and removed efficiently, especially CO2. The hydrogen fraction reaches to 86.7% and its production is about 1.22mol with 1mol of the COG.

Jan 1, 2016

By Maryam Ghodrat, Bijan Samali

Disposal of waste syringes in a safe and eco-friendly way has been an issue of considerable scale for decades. The generated amount of waste syringes has escalated with the rapid growth in population and wide acceptance towards single-use medical devices. Some hospitals have their own on-site incinerators ,but recent tightening of air quality regulations and landfill levies led to the closure of manyon-site incinerators. The solution to this problem implicates the development of an environmentally-sound method that would employ these waste materials. This work investigates a thermodynamic modelling approach for incineration treatment of waste plastic syringes in Electric Arc Furnace (EAF) steelmaking. Mass balance was obtained from HSC Chemistry thermochemical package. The results indicate that the rate of iron oxide reduction in the slag is higher when coke is partially replaced by waste plastic syringes. Furthermore, the amount of dust and stack gas emission was reduced by around 0.4% and 1.25% respectively by replacing 20%-weight of pure coke with waste plastic syringes. The study demonstrates part of the coke can be successfully replaced by waste plastic syringes in electric arc furnace to provide additional energy from combustion without affecting the main process.

Mar 1, 2018

By E. V. Bratygin, E. G. Dmitrieva

The aim of the research was to study the thermodynamic characteristics of high-temperature processing of ilmenite concentrate deposits "Central" in a neutral and oxidizing atmosphere, as well as its interaction with alkaline additives. The research was conducted using a scanning colonoscopy on thermogravimetrical analyzer NETZSCH STA 449 F3. A sample of the test material weighing 10 mg was placed in a crucible and heated at a rate of 10 °C/min to 1200 °C in argon or air. Studies have been conducted pure ilmenite concentrate and its mixtures with 5 % and 12.5% of sodium carbonate. The results of the analysis of the thermogravimetric curves it was found that the recovery of the concentrate carbon will come from ulvospinel, not pseudobrookite, and the reaction recovery is possible at temperatures above 900°C. While removing produced in the decay ilmenorutile of iron oxides in an inactive form, for example, iron (III) oxide, it is possible to reduce the quantity of the solution of ilmenite formed during the restoration of the melt anosovite. The analysis of data obtained during heating of ilmenite concentrate with sodium carbonate in concentrations of 5 and 12.5% transition pseudobrookite in ulvospinel is missing, it just breaks down into hematite and titanium oxide, which, in turn, react with N?2??3. It should be noted that increasing the concentration of sodium carbonate in the sample contributes to more complete interaction of iron oxides and N?2??3 with formation of ferrites of sodium. This can ensure full recovery of iron oxides in the concentrate, which is part of secondary ilmenite can not be dissolved in the melt formed by the lower oxides of titanium. In addition, the increase in the content of soda in the mixture significantly reduces the temperature of the initial melting point of the slag and facilitates the coagulation of metallic iron.The obtained results were used for laboratory studies of the solid-phase sintering of briquettes from ilmenite concentrate with additives of sodium carbonate and a reducing – coal, as well as for the development of technological mode of solid-phase sintering of the concentrate with the aim of obtaining product recovery with a titanium dioxide content of more than 75 %.

Jan 1, 2018

By Senlin Cui, In-ho Jung

Significant amount of commercial aircrafts will be retired in 2020, and the recycling of Al components in such aircrafts becomes an important issue in aerospace and Al industry. Recycling of Al from obsoleted Al products can effectively reduce the energy consumption and CO2 emission which is more economical and ecofriendly. In the present study, thermodynamic analysis for the various recycling technologies of Al alloys were performed based on the comprehensive and accurate thermodynamic database. The recycling technologies reviewed in this work include the vaporization process to reduce Zn, precipitation process to reduce Fe, Mn, Si, Ti, Zr, flux treatment for Al 2O3 and MgO, etc. Several key issues and limitation of the recycling of the aircraft Al were discussed. The recycling technologies discussed can also be utilized to recycle other Al alloys for common usage. All the thermodynamic calculations were performed using the FactSage FTlite database.

Mar 1, 2017

By Xiang-dong XING, Zhen-yang wang, Jian-Liang Zhang

Distribution behavior of titanium between CaO-SiO2-MgO-Al2O3-TiO2 and hot metal was studied between 1350 °C to 1600 °C. Experimental results indicate that the reaction temperature influenced the activity coefficients of titanium and resulted in the variation of equilibrium constant. Finally, the Gibbs free energy formula of titanium carbothermic reduction was fit out using the thermodynamic model of Wagner and congregated electron phase models.

Jan 1, 2015

By Shu Yamaguchi

The behavior of halide impurities in pyrometallurgical processes such as Wealtz kiln and MF process has been discussed based on the thermochemical data and the reported data of PbO activity in PbCl2-PbO melts. The role of PbCl(g) has been estimated to be significant in the chloridization evaporation reaction. From reported data on the PbO activity in PbC12-PbO melts, activity of PbCl2 has been calculated by the numerical integration of Gibbs-Duhem equation, and the stability domains and the composition of the liquid phase as well as the vapor pressure of PbCl2 have been estimated as functions of log P2HCI/PH2O and temperature. From the discussion of the path during cooling process on the log P2 HCI . PH2O vs. temperature diagram, the authors proposed a possible dechioridization process that utilize water vapor as a dechloridizer for the direct precipitation of PbO from gas phase.

Jan 1, 2003

By O. Alonso-Gonzalez, F. Nava-Alonso, A. Uribe-Salas, C. Jimenez-Velasco

"Most of the gold produced worldwide is still obtained by cyanidation, in spite of the difficulties encountered in the processing of some gold ores such as the dissolution of copper-bearing minerals in cyanide solutions. The leached copper forms complexes with cyanide and causes several operating problems, which have led to the development of copper removal/recovery processes, among them the industrially accepted SART process (sulfidization, acidification, recycling and thickening). Although the SART process is in use in gold production plants around the world, new challenges are appearing with the continuous varying of the mineralogy of ores (such as higher copper grades, changing the solution composition and complexity). The optimal SART operating conditions for a specific solution are not the same when the composition of the solution changes; consequently, the efficiency of this process can decrease.The present study is a thermodynamic approach, corroborated by laboratory experiments, to explain how the main variables of the process affect the efficiency of copper precipitation as cuprous sulfide (Cu2S). The variables considered were pH value, copper concentration, cyanide/copper molar ratio and sulfur/copper molar ratio, all of which werevaried within the limits encountered in typical cyanidation solutions presenting the problem of copper.It was found that the variable that most affects the efficiency of the process was the pH value, since poor or no control of it can cause cuprous sulfide redissolution. The S/Cu molar ratio is also important: raising this ratio increases copper removal, but high ratios will also cause sulfide and cyanide losses. The effect of changing the CN/Cu molar ratio was negligible between 4 and 8. For a solution containing 300 mg/L copper and 490 mg/L cyanide, copper removal as high as 98.8% can be obtained with the addition of 0.6 moles of sulfide per mole of copper at pH = 6.IntroductionThe main process for gold production is cyanidation, because it is the most economical and efficient process so far. Precious-metal leaching occurs when the ore is placed in contact with a dilute alkaline cyanide solution. The dissociation of cyanide salts provides free cyanide ions, which allow the formation of the aurocyanide complex Au(CN)2 -. This complex can be retrieved from the solution by adsorption on activated carbon or by zinc precipitation. Although the use of cyanide represents an issue to health and the environment, there are technologies for its management and treatment that can be easily applied. Furthermore, it is a low-cost process compared with other methods that are available or under development."

Jan 1, 2015

By Lloyd R. Nelson

The feasibility of producing low carbon (LC) ferromanganese (FeMn) by lime-'ore' melt refining of high-grade ferromanganese silicon (FeMnSi) was investigated. Thermodynamic simulations demonstrated significant benefits in moving from a single-stage ladle operation to a two-stage counter-current reladling operation (to emulate the commercial Penin Process). The theoretical alloy silicon content was predicted to be refined from 1.57 to 0.005 per cent silicon, at a 6.2 per cent higher manganese yield (yield predicted to increase from 82.3 to 88.5 per cent). Extension of this counter-current refining principle, to a multistage Counter-Current Reaction Launder (CCRL) was investigated using the Slag Metal And Gas Klnetics (SMAK) software to model the mass transfer kinetics of the multicomponent coupled reaction system. Simulation results suggested that commercial production of 50 000 tonnes per annum (tpa) of refined LC FeMn, containing less than 0.5 per cent silicon, at manganese yields of up to 90 per cent, should be feasible in a compact CCRL (7 m long by 0.7 m wide).

Jan 1, 1994

By RIINA SALMIMIES, ANTTI HAKKINEN, PAULA VEHMAANPERA

Better understanding of the mechanisms and kinetics of dissolution can benefit several industrial processes. For example, iron can be leached from clays, which can be further used as a raw material in the ceramic industry. Another important application is the regeneration of ceramic filter media, which are used in the dewatering of iron ores. Dissolution of iron oxides in mixtures of acids is fairly uncommon and a less well-understood phenomenon, but it can result in a more efficient process. This work also shows that the determination of dissolution mechanisms and kinetics is not straightforward in different acid systems.

By Víctor Vázquez, Guillermo Tiburcio, Martin Encinas, Jesús L. Valenzuela, Erick Montaño, Alejandro Valenzuela, José Parga

Merrill-Crowe is the primary process used for the concentration and purification of silver in a cyanide solution. The Langmuir Adsorption model for silver recovery in a cyanide solution was used for the study. The maximum adsorption capacity was 6.19 mmol/g for silver. This model properly adjusts the experimental results of the adsorption equilibrium with high correlation coefficients, which also favors the formation of a single layer of molecules adsorbed for the silver in the electrocoagulation- generated species. The thermodynamic parameters ΔG, ΔH, and ΔS were estimated, and it was found that the adsorption process is exothermic and spontaneous. For the kinetic study, the Lagergren second-order equation was used to study the adsorption speed. To characterize the solids coming from the electrocoagulation, X-ray diffraction (XRD), and scanning electron microscopy (SEM) with energy-dispersive X-ray spectroscopy (EDX) were used; the results of this study suggest that silver is present in aluminite, hydroniumjarosite, and alunogen.

Oct 30, 2021

By M. Nagamori, A. J. Plumpton

"Commercial HCl-leaching of magnesite and serpentine yields highly concentrated aqueous solutions containing 25 mass % to 33 mass % MgCl2. The partial molar enthalpies and heat capacities, the ionic activities of Mg2+ and Cl–, and the Raoultian activity of H2O have been assessed for the concentrated MgCl2-H2O solutions at temperatures of 348 to 373 K. These thermodynamic data are used to calculate the pH of aqueous MgCl2 solutions saturated with a Mg-bearing mineral such as magnesite, serpentine, brucite, forsterite, enstatite or talc. On the basis of these thermodynamic data, technico-economic aspects are discussed as to neutralization with pulverized MgCO3, water evaporation from the MgCl2 solutions, and ore composition including such minor constituents as CaCO3, FeCO3 and Fe3O4. IntroductionA major magnesium electrolytic reduction plant operates in Quebec, where another will begin its production in the year 2000. One uses imported magnesite ore as raw material, while the other will utilize local asbestos tailings (serpentine). Both processes produce a concentrated salt solution of 25 mass % to 33 mass % MgCl2 by leaching the ore with concentrated hydrochloric acid. Thus, the two processes differ mainly in the HCl-leach and related operations. After the HCl-leach of the ore, the serpentine process yields about 25 times more wet cake to filter and wash than the magnesite counterpart. A comparative cost-engineering study with respect to slurry filtration and cake washing has been published elsewhere (Blackburn and Nagamori, 1994). By contrast, the present study considers the thermodynamics and technicoeconomics of the HCl-leach itself for both ores."

Jan 1, 1999

By William E. Frazier

The presence of minute amounts of sulfur (10ppm) in nickel-base superalloys has been associated with reduced oxidation resistance and the premature spallation of protective coatings. Removal of sulfur by annealing these alloys in a hydrogen atmosphere has been successfully attempted by several researchers. This paper examines the fundamental thermodynamics and kinetics governing hydrogen desulfurization of elemental nickel. Limiting conditions for successful desulfurization are delineated. Assuming that the diffusion of sulfur is the rate limiting process of desulfurization, the effectiveness as well as time associated with hydrogen desulfurization is explored.

Jan 1, 1994

By R. C. Reed, L. T. Wu, H. C. Harada, K. Kawagish, R. T. Wu

Oxidation of pure metals is a chemical reaction in which the metal loses one or more electrons, such that the atom of the metal changes from the neutral state to a positively charge ion and reacts with oxygen to form an oxide of the metal. The oxide can form as a protective and adherent scale that slows down further oxidation, or may spall off repeatedly, exposing fresh metal surface to react with oxygen. In multi-component alloy systems such as typical high temperature NiCrAlY bond coats, more than one oxidation mechanism may take place at once and thus, complicates the study of oxidation. To better understand the competition between formations of oxides of different compositions, a thermodynamic assessment is carried out to study the oxidation mechanism of a Ni-27Cr-9Al (at %) ternary alloy. Based on the assessment, it is demonstrated that the layering of different oxides can be determined, with the most stable oxide (alumina) existing directly above the metal-oxide interface and the least stable oxide (nickel oxide) locating on the outer most layer. A comparison between the calculated results and previously published experimental observations shows excellent agreement.

Jan 1, 2010

By Shilai Yuan, Huimin Lu, Zhijiang Gao, Panpan Wang

"Solvent refining of silicon through using Si-Al melts is a valid method to remove the impurities from metallurgical grade silicon (MG-Si) melt. The thermodynamic behavior of impurities Fe, Al, Ca, Ti, Cu, C, B and P in MG-Si during the solidification of MG-Si was studied based on the available thermodynamic parameters and experimental data. The morphology of inclusions was investigated by Scanning Electron Microscope (SEM). The chemical composition of inclusions in MG-Si and Al-Si melt was analyzed by EPMA. It is found that the amount of white inclusion reduces and most impurities are solved into the Al-Si melts. After solidification of Si–Al alloy using induction heating and acid leaching, impurities can be effectively removed. The solidification of silicon from the Si–Al melt is found to be more effective for purification than general silicon solidification.IntroductionPhotovoltaic energy is one of promising energy resources in a sustainable society because of its inexhaustibility and cleanliness. Although the production and installation of solar cells have increased significantly during the last decade, the cost of solar cell installation is still high. Multicrystalline silicon has now become the main material in the photovoltaic market because of its low production cost and because of the relative high conversion efficiency of solar cells made from this material, which has been studied for a long time [1-3].Electronic grade (EG) silicon (99.9999999% Si) is commonly used as the raw material to produce SOG-Si (99.9999% Si). Silicon produced from the chemical routes restricts the development of solar cells due to environment threaten, high energy consumption and low productivity. Purification of metallurgical grade silicon (MG-Si) is a low cost, environment friendly method. Although several metallurgical processes such as directional solidification, vacuum refining and electron beam melting [4], have been developed, the cost reduction and refining efficiencies for manufacturing silicon is still have to be further optimized.In the purification process, it is difficult to remove boron and phosphorus by the conventional metal refining method. The refining efficiency depends on the segregation behavior of different elements in solid silicon and the liquid phase. The segregation ratios of all investigated impurities were found to be much smaller than the segregation coefficients between solid and liquid Al-Si melts [5]. For instance, the segregation coefficient of B in Si is 0.8 at the silicon melting point (1687K), whereas it is around 0.2 when silicon is solidified from Si-Al melt at 1273K. For phosphorus the segregation coefficient is 0.06 when silicon is solidified from Si-Al melt at 973K°C, which is much less than 0.35 for recrystallization from liquid silicon. Since the segregation coefficient of boron in silicon is 0.8, it cannot be removed by directional solidification."

Jan 1, 2014

By Sheng-ping He, Zhuo Chen, Qian Wang, Kun-peng Xu

During the continuous casting (CC) process of Ti-Stabilized Stainless Steel, the nozzle clogging or even the crusts composed of TiN, Al2O3, TixOy and the complex inclusions MgOAl2O3, Al2O3 is often occurred. The main objective of the present study is to research the reaction between refining slag or mold flux and Ti-Stabilized Stainless Steel by thermodynamic calculation. A suitable refining slag composition was sought to absorb Al2O3, Tix Oy inclusions, and the reactions between different mold flux and steel was calculated and compared. It was found that a suitable refining slag was difficult to adjust aluminum and titanium to meet requirement simultaneously. The target refined slag is composited of 3–8.7% SiO2, 56–59% CaO, 33–38% Al2O3 and 4% MgO with low melting point and high absorption capacity of inclusions for in the refining of the 321 stainless steel. SiO2, Fe2O3, Na2O and B2O3 of mold flux would react with titanium in the steel. The CaO–SiO2 based mold flux had a strong reactivity than CaO–SiO2–Al2O3 and CaO–Al2O3 based mold flux.

Mar 1, 2017

By Nourreddine Menad

Plastic materials have been associated with electric and electronic applications since the early days of the electrical industry. Plastics can amount to 30 percents of the scrap mass. Generally, they are treated with flame retardants such as halogenated ones and they can result in different toxic chemical compounds. These plastics can be used as combustibles in the recovery of copper and precious metals. However, during their combustion, halogenated flame retardants can produce dibenzo-p-dioxins and dibenzo-furans. The estimated thermodynamic data of several organic compounds resulting from combustion of electric and electronic scrap, have been used in conjunction with the program HSC to calculate the conditions for dioxin and furan formation. The results show that the formation of the dioxins is dependent on the quantities of carbon, hydrogen, chlorine and oxygen reacting in a given system, as well as on parameters such as temperature and pressure.

Jan 1, 1998

By Motohiro Horiguchi, Kazuo Ichii, Toshio Oishi

"As a fundamental study to prepare copper-based alloys with rare earths (RE: La, Gd, Nd, Ce and Y) without any inclusions, the solubility of rare earth in liquid copper was experimentally determined. Liquid copper alloys were equilibrated with carbon and rare earth carbide in a graphite crucible in an argon atmosphere at 1523-1873 K.Solubilities of rare earth in liquid copper were determined by approaching the equilibrium values from both the lower and the ·higher concentrations than those expected· in the preliminary experiments. They were expressed as a function of temperature. Carbon in Cu-RE alloy was also analyzed and thermodynamically discussed.IntroductionOver the past several years, the demand for highly conductive and high strength copper-based alloys, such as Cu-Cr, Cu-Zr and Cu-Cr-Zr for use in electronic materials has increased.1 -7 These alloying elements are very reactive and easily oxidized to form oxide inclusions during melting. To avoid the oxide inclusions, it may be effective to utilize the strong reducing power of carbon in conditions under which no carbides form.In this study, to provide fundamental data for producing Cu-RE( rare earth) alloys without any inclusions, the solubility of rare earth in liquid copper in equilibrium with .carbon .was determined and discussed on the basis of the experimental results and the thermodynamic data.ExperimentalSample preparation for equilibrium experimentsOxygen-free copper (99.99%), lanthanum (99.9%), gadolinium (99.9%), neodymium (99.9%), cerium (99.9%) and yttrium (99.9%), and their oxides were used as starting materials.Each rare earth carbide was prepared by mixing rare earth oxide with carbon, which is a little more than the stoichiometric composition, pressing it into a tablet form and sintering at about 2000.K for 20 ks in a vacuum furnace using a graphite crucible. Powder X-ray analysis showed that only the carbon and rare earth carbide (REC2) was present in each sample.Cu-RE mother alloys (5-20 mass % RE) were prepared beforehand by mixing metallic rare earth with oxygen-free copper, and melting in an electric arc furnace."

Jan 1, 2000