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By Xiaolong Lin, Yuanbo Zhang, Guanghui Li, Zhizhong Li, Zhiwei Peng, Tao Jiang, Yan Zhang, Yutian Ma

Pyrometallurgical processes for recovering platinum group metals (PGMs) from spent catalyst have been the focus of current research for many years. They suffer from high energy consumption, large trapping agent consumption and huge slag production. Because of versatility of PGMs-containing spent catalysts, comprehensive recovery of valuable metals from these catalysts from an experimental point of view remains a challenge. In this study, thermodynamic analysis of pyrometallurgical smelting process in the presence of various additives for ef ficient recovery of PGMs was performed. It showed that addition of sodium salts would promote the migration and separation of the precious metals from carrier of the spent catalyst. By replacing calcium oxide with sodium carbonate and sodium borate, the smelting temperature could be reduced by more than 200 °C, which agreed well with the experimental findings.

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 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 Zhan Jing

Keywords: thermodynamic, Ni-Co alloy powders, composition, fibrous The mathematics model of Ni(II)-Co(II)-C2O42?-NH3?H2O-H2O of thermodynamic equilibrium system has been developed theoretically according to the law of conservation of mass and the law of simultaneous equilibrium, and the logarithm concentration-pH (log[Me2+]T-pH) diagrams of this system have been made. The effect of ligand and pH value was studied. Two issues in coprecipitation route to synthesize fibrous nickel-cobalt alloy precursor powder, com-position and morphology which are a first priority, are addressed based on thermodynamic analysis and experiments. The results show that suitable pH value range of coprecipitation of nickel ions and cobalt ions in theory can be obtained to maintain fibrous, excellent compositonal homogeneity and stoichiometry in coprecipitation products. Experimental demonstration is also carried out.

Jan 1, 2005

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 Kun Wang, Xinhui Li, Huaqing Xie, Qingbo Yu, Qin Qin

"Three typical model compounds of bio-oil (ethanol, acetone and phenol) were studied in the steam reforming process for hydrogen production. In the thermodynamic analysis, the three componds showed the similar trends. The hydrogen yields increased with the increase of steam/carbon (S/C) ratios, and the temperatures of the maximum hydrogen yields moved afterward to low temperature zone. However, the hydrogen contents were just about 70%. For improving hydrogen yield, a new system for steam reforming of bio-oil with site CO2 capture was put forward. This system required the catalst with the larger granularity having greater mechanical strength and higher abrasion resistance. So, six Ni-base catalysts loaded on Al2O3 particles prepared were used and among them, Mg-Ni/Co catalyst showed the best catalytic performance. For the simulated bio-oil (the mixture of the compounds), the hydrogen yield can attain 63% with Mg-Ni/Co catalyst with the good stability and regeneration ability.IntroductionCurrently the interest in the use of hydrogen as a clean energy carrier is increasing, and the main way for producing hydrogen is steam reforming of fossil fuels, containing steam reforming of nature gas, naphtha and coal. But this way caused substantial amounts of CO2 emitted, and these sources of hydrogen which are non-renewable energy will eventually be used up [1, 2]. As a kind of renewable energy, biomass is recognized as an attractive alternative to fossil fuels, because of its neutral CO2 emissions [3]. There are mainly two thermochemical processes using biomass to produce hydrogen, gasification and flash pyrolysis followed by steam reforming (SR) of the biooil produced in the flash pryolysis process [4]. The latter was known as one of the most promising and economically viable methods for hydrogen production [5]. In the last decades, the biomass flash pyrolysis technology was adequately developed and fairly mature [6]. But the steam reforming of bio-oil is still at the research stage and yet has been leading to more and more concerns by the researchers. In their research, the catalysts were widely studied and yet mainly were powdery[7-10], and the reactors manily were fixed bed reactors[11-13], readly causing the carbon deposition and the catalyst deactivation, against the continuous running. In this paper, a new systerm was put forward and could realize continuous production of hydrogen, yet needed catalysts with the larger granularity having greater mechanical strength and higher abrasion resistance, as well as powdery CO2 sorbents which mainly calcium oxide based ones.In this paper, the thermodynamic analysis of the steam reforming processes of three typical bio-oil model compounds (ethanol, acetone, phenol) was performed, and the effect of S/C ratio and temperature on the hydrogen yield and the compositions of gaseous products were investigated. Then, a new systerm for steam reforming of bio-oil with site CO2 capture was put forward, and the catalysts with a certain granularity were prepared and studied."

Jan 1, 2014

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, Paula Vehmaanperä, Antti Häkkinen

The dissolution of iron oxides in mixtures of acids is fairly uncommon but can result in a more efficient dissolution process. The objective in this work was to investigate the dissolution of synthetic hematite powder in mixtures of oxalic and sulfuric acid. Experiments were done at different acid ratios and temperatures. An increase in temperature from 15 to 35 °C increased solubility, whereas an increase from 35 to 50 °C did not change the solubility but had a profound effect on the kinetics. An important finding was that oxalic acid advanced the dissolution process since increasing the amount of oxalic acid in the system resulted in faster kinetics and higher solubilities. The dissolution kinetics were well described with the Kabai model, which was the only studied model able to describe the whole reaction time. However, the solid specific constant a varied for the different acid ratios and this is argued to be a result of changes in the solid phase. The changes in the constant a were not in line with the original study of Kabai, which indicates that a cannot be the solid specific constant but it can be the constant connected to dissolving media describing the changes in the dissolution mechanism.

Sep 23, 2020

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.

The published liquidus data on the Pb-PbS system have been correlated on the basis of one-coefficient Margules equations. Thermodynamic properties of the components of this system have been obtained, and it has also been found that the calculated miscibility gap of this system exists over a very narrow range of temperature (1041 to 1058°C).

Jan 1, 1972

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 S. R. Steinacker, H. Schnideritsch, J. Antrekowitsch

Primary copper industry flue dust plays an increasingly important role in the creation of matte and slag. From a thermodynamic point of view, the chemically formed section of fine particles play a techno-logically interesting role in comparison to the mechanical carry-over. Here, the volatilization and the sub-sequent condensation in the off gas system lead to a characteristic distribution of the contained elements which are represented by various compounds of desired metals like zinc and lead. On the contrary, certain undesired components such as arsenic, bismuth and cadmium accumulate within the product as well. This paper describes existing models and theories concerning the formation of flue dust in the copper smelting process and presents a thorough investigation of the physico-chemical fundamentals by verifying assump-tions with thermodynamic calculations. By fully understanding the formation patterns at different stages and temperatures within the process, better knowledge for flue dust in the first step of the pyrometallurgi-cal copper smelting can be obtained - hence leading to new ideas and incentives for the following stages in the copper production cycle.

Jan 1, 2015

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 Eric Klaffenbach

Valorization of slag from metallurgical industrial processes becomes ever more important as this may help optimizing and reducing the use of natural resources such as rock and sand. In view of this objective, metallurgical processes have to be analyzed in order to modify the slag composition so that it will meet the expected requirements of potential users of these resources. This paper gives the results of a thermodynamic analysis of the flash smelting process to understand the impact of operational parameters on slag chemistry and elemental partitioning in the process. It is shown that an increase of the matte grade and temperature leads to higher deportment of Pb, Zn and As to the slag. With increasing matte grade the volatilization of these elements decreases. Furthermore, the results indicate an increasing solubility of Cu and S in slag at higher temperatures.

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

By Miao Tian

Large quantities of copper complex resources are produced globally and urgent to be cleanly processed. This article presents a thermodynamic analysis of mixed smelting process including low-grade polymetallic copper sulfide concentrates, high copper content sulfide concentrates, metallurgical by-products (copper removal slag from lead metallurgy), and copper powder from electronic waste. A top blown smelting reactor to simulate mixed smelting process is developed using a metallurgical process simulator, METSIM. Reactor parameters, heat loss and phase distributions are estimated from actual plant data. The proper proportion between complicated primary and secondary copper resources is determined by analyzing the influence of the feed rates of various resources, oxygen, silica flux and revert on the smelting performance. Autogenous smelting process is built by optimized matching materials of copper complex resources, in terms of the reactor temperature, copper content in matte and slag, and the percentage of magnetite in slag.

By A. D. Davis

Limestone-based material is effective for reducing arsenic concentrations below the current limit of 10 parts per billion for drinking water, typically resulting in final concentrations of about 4 to 6 ppb. However, in laboratory and field testing, further reductions to the 1 ppb range are difficult to achieve with limestone unless other material such as iron is added. The removal mechanism with untreated limestone appears to be the formation of a low-solubility precipitate of hydrated calcium arsenate, in the form of arsenate-apatite. Likely reactions and thermodynamic data indicate a theoretical removal limit of about 2 to 4 ppb for arsenic using raw limestone. Limestone also can reduce concentrations of cadmium and lead below 1 ppb in water, resulting in >99% removal efficiency. Thermodynamic constraints appear to be favorable for reactions involving the formation of otavite during cadmium removal and the formation of hydrocerussite during lead removal.

Feb 27, 2013

By L. B. Pankratz

Thermodynamic data on the elements, oxides, sulfides, halides, and selected hydrides, carbides, nitrides, carbonates, sulfates, silicates, and miscellaneous compounds were reviewed, evaluated, and compiled at the Bureau of Mines. Values for CP°, S°, H° -H°298, ?Hf°, and ?Gf° are given in tabular form. A brief thermodynamic background and a number of examples and applications are presented.

Jan 1, 1984

By Yunyan Wang

Diagrams of pc-pH for the complex ions concentration and pH value and -g- for activity coefficient and ionic strength ln±MnSOI4had been drew based on the thermodynamic principle of coordination chemistry and combined with Pitzer theory at 298.15K. The diagram of -g- indicated that -gincreased sharply from 0.0000 up to 1.2147 when I changed from 0.00 ln±MnSOIln4±MnSO4to 0.09; The increase of -gbecame slowly when I was more than 1.00 and less than 1.69; kept still when I ln±MnSOln4-g±MnSO4was more than 2.25 and less than 4.00. Diagrams of pc-pH illustrated that the minimum solubility of Mn(OH)2(s) increased with the increase of I, the pc increased from 6.5 to 5.5 when I increased from 0.00 to 4.00; The pH of the minimum solubility of Mn(OH)2(s) increased with the increase of I, the pH increased from 11.80 to 12.76 when I increased from 0.00 to 2.89, the pH kept still when I (I was less than 4.0) increased. There is single function relationship between the minimum solubility of Mn(OH)2(s) and relevant pH in different I.

Jan 1, 2010