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By Jongmin Jeong, Jaehong Shin, Joo Hyun Park, Chul-Woo Nam, Kyung-Ho Park

Because sulfur and phosphorus are very harmful in steel products, there are increasing requirements for refining these elements from ferroalloys industries. Hence, in the present study, simultaneous desulfurization (de-S) and reducing dephosphorization (Rde-P) from silicomanganese (SiMn) alloy were investigated using metal-slag equilibration method under highly reducing condition at 1773 K. Experiments were carried out by equilibration between SiMn alloy and MnO-based slag in graphite crucible under p(O2) = 10−18 atm. Slag composition was designed by changing basicity (CaO/SiO2) and MnO content at fixed Al2O3 (=20%) and MgO (=5%) contents. De-S ratio increased with increasing basicity until C/S = 1.5 whereas Rde-P ratio was not significantly affected by slag basicity. This was because thermodynamic driving force of de-S reaction was greater than that of Rde-P reaction under present experimental conditions. The de-S and Rde-P ratios commonly increased with decreasing oxygen partial pressure.

Mar 1, 2017

By S. E. Olsen, K. Tang

Slag-metal and slag-metal-gas heterogeneous equilibria involving MnO-containing slags have been simulated using recently developed Mn-based alloy and IRSID oxide thermochemical databases. A large number of experimental equilibrium data have been used to verify the calculation results. The experimental slag-metal and slag-metal-gas equilibria in MnO-SiO2binary, MnO-SiO2-CaO and MnO-SiO2-Al2O3ternary, MnO-SiO2-CaO-Al2O3quaternary andMnO-SiO2-CaO-Al2O3-MgO higher-order system can be reproduced within experimental uncertainties. The influence of temperature, CO partial pressure and slag chemistry on the Mn-and Si-distribution equilibria have been quantitatively evaluated. This leads to a sound basis for optimizing the manganese ferroalloy production processes. Key words: MnO-containing slag, manganese ferroalloy, equilibrium simulation, thermochemical database

Jan 1, 2004

By Shahab Alizadeh, Ahmad Khodadadi Darban, Mehdi Mohseni, Mahmoud Abdollahy

This study probed the selective separation of lanthanum and yttrium in a nitrate medium in the presence of aluminum and calcium impurities using di-(2-ethylhexyl) phosphoric acid (D2EHPA). The factors studied in a central composite design (CCD) included extractant concentration, pH, concentration ratio of total impurities to rare earth elements, and interaction of these three factors. The extraction mechanism and types of extracted metal-containing species were delineated by the slope analysis method. The obtained thermodynamic data showed that lanthanum and yttrium extraction by the D2EHPA extractant was exothermic. The extraction of both rare earth elements was accompanied by an entropy reduction. The negative magnitude of ΔS in yttrium extraction reaction suggests stronger D2EHPA-Y(III) complexation relative to La(III). As entropy decreased and enthalpy increased, the extraction process became unspontaneous. Using the proposed flowsheet, lanthanum and yttrium products with > 90% purity were obtained.

Aug 10, 2021

By Chikabumi Yamauchi, Mitsuru Tanahashi, Toshiharu Fujisawa

"Thermodynamic properties of impurities in molten silicon are of prime importance in developing economical production methods of solar grade silicon. In the present research work, thermodynamic properties of boron, the most difficult element to remove from molten silicon, were measured by chemical equilibration techniques at 1723 and 1773 K. Activity coefficients and self-interaction parameters of boron in molten silicon were determined by equilibrating the melt with solid BN under controlled nitrogen partial pressures. Interaction parameters between boron and nitrogen in molten silicon were also determined by equilibrating the molten Si-B alloys with solid Si3N4• Based on the data obtained, the stability diagram of the Si-B-N system was established.IntroductionPhotovoltaic power generation using a silicon solar cell is expected to be the most promising energy source, because it is inexhaustible, cleaner and more safety than conventional energy sources, such as thermal or atomic power generation. At present, expensive off-grade silicon for semiconductor (SEG-Si) is used for a solar cell production. However, if a large-scale photovoltaic energy conversion using silicon solar cell comes into wide use in the near future, silicon will be sure to be in short supply for the cell. Therefore, a development of a new large scale process for solar grade silicon (SOG-Si) production is definitely necessary, which can remove contained impurities from silicon.Among the impurities contained in silicon, boron is one of the most difficult ones to remove by a zone melting or an unidirectional solidification, because its segregation coefficient in silicon is close to unity (0.8). In addition, boron behaves as a p-type silicon semiconductor dopant and, therefore, its content in SOG-Si must be severely controlled. Although some attempts to remove boron by various metallurgical methods have been carried out [I -4], quantitative analysis has not been made due to lack in the information on the thermodynamic properties of boron in molten silicon. From this view point, the activity of boron in molten silicon was determined in the present study by chemical equilibration techniques at 1723 and 1773 K."

Jan 1, 1998

By Jan Vrestal, Josef Tomiska, Pavel Broz

"Thermodynamic investigations on fcc solid ternary Fe-Ni-Cr alloys have been performed by means of the computer-aided Knudsen cell mass spectrometry. Ternary T.AP.-series (Thermodynamically adapted power series) are used for the algebraic representation of the thermodynamic excess properties. At 1650 K the molar excess Gibbs energy GE is negative over the whole field of stable fcc phase. The molar heat of mixing HE is exothermic in the predominant part of the fcc phase field. Only between the section with a constant ratio of mole fraction Xcr/XNi = 0.64 and the fcc phase field boundary the HE values are slightly endothermic. The results of this work can be used successfully for phase diagram calculations.IntroductionThermodynamic investigations on multicomponent alloy systems such as the Fe-Ni-Cr ternary system including the three binary boundary systems are very time-wasting and usually beset with considerable experimental difficulties. Additionally, the required experimental equipment is very expansive and the obtained results are not always satistying. Therefore it is understandable that many phase diagram calculations are based only on few experimental values of the molar excess free Gibbs energy GE. Consequently, Kundrat and Elliott [1] as well as Hillert and Qiu [2] used in their reassessments of the phase diagram of the Fe-Ni-Cr system thermodynamic data mainly assumed and/or optimized by means of various reasoning.Lee [3] reported recently, a revision of the used thermodynamic description of the Fe-Ni liquid phase is necessary to obtain a better agreement with the experimental data on the bcc/liquid or fcc/liquid tie lines and liquidus temperatures in the Fe-rich region of the Fe-Ni-Cr ternary system than in the previous assessments. This is 'in full agreement with mass spectrometric investigations of Fe-Ni alloys in the liquid and in the fcc solid phase, published earlier [4,5]. Indeed, phase diagram calculations based upon the molar excess free Gibbs energies GE obtained in these studies yield liquidus and solidus lines in excellent agreement with experimental phase diagram data [5]. Nevertheless, these experimental data have not been considered later on any more, not even in the revision by Lee [3]."

Jan 1, 1996

By Leiting Shen

The thermodynamics of tungsten ore decomposition in mineral acid and alkaline solutions were studied. The published thermodynamic data of tungsten minerals were collected and assessed. The Gibbs energies of CaWO4 (−1538.43 kJ/mol), FeWO4 (−1053.91 kJ/mol), MnWO4 (−1206.08 kJ/mol), H2WO4 (−1003.92 kJ/ mol), and Na2WO4 (−1455.58 kJ/mol, aq) at 25 °C were adopted in the calculation using HSC software. The results show that CaWO4 is decomposed more readily in Na2CO3 solution than in NaOH,while FeWO4 andMnWO4 aremore reactive inNaOH solutions. Froma thermodynamic point of view, tungsten ore decomposes easily in acid solutions despite most ΔGo T increasing slightly with temperature. Oxidizing Fe2+ to Fe3+ in acidic solutions facilitates decomposition of FeWO4, and the reaction of CaWO4 in H2SO4 solution occurs more easily than in other mineral acids, due to the formation of sparsely soluble CaSO4. The results fit well with the experimental data and industrial experience previously reported in the literature.

By Jiayan Li, Yi Tan, Yao Liu, Yaqiong Li, Shenrui Wu

"A metallurgical grade silicon (MG-Si) refining concept process was presented. Under vacuum conditions, silicon was selectively oxidized by high purity silicon dioxide to form gaseous silicon monoxide while impurities with low vapor pressure in MG-Si were rejected in residue; Then high purity silicon was obtained from the disproportionation of condensed silicon monoxide; and by-produced silicon dioxide was recycled for the oxidation step. Thermodynamics on boron rejection during the oxidation were studied in this work. In the temperature range of 1200-1800K, the saturated vapor pressure of boron, and the Gibbs free energy changes, the equilibrium partial pressures of silicon monoxide and boron oxides of potential reactions were calculated. And the effect of boron activity in MG-Si was also discussed. The results indicated that boron in MG-Si can be rejected during the oxidation and it showed the potential for the further development of the new refining process.IntroductionAs global energy consumption growing dramatically, higher prices of energy and global warming problem have attracted more and more attention [1]. As a clean and renewable energy industry, the photovoltaic (PV) industry converts solar energy to electricity using solar cell device and has a growth rate of about 30% in recent years. It has caused a shortage of silicon feedstock due to that about 90% of solar cells are made of crystalline silicon. And high energy consumption during the production of silicon material, i.e. solar grade silicon (SoG-Si), is main obstacle for its mass production."

Jan 1, 2012

By J. H. E. Jeffes, K. T. Jacob

The activity coefficients of oxygen in liquid Pb-Sn alloys have been measured between 550 and 1100°C by use of solid oxide galvanic cells: Pt, Ni-NiO | Zr02 Solid electrolyte | O (Pb + Sn), Cermet, Pt; and Pt, Fe-FeO | Zr02 Solid electrolyte | 0(Pb + Sn), Cermet, Pt. Alcock and Richardson's quasi-chemical equation, with the coordination number of atoms set to 2, is found to predict successfully the activity coefficients of oxygen in these alloys. The relative partial molar enthalpy and entropy of oxygen at 1 atom per cent in the alloys have been calculated from the variation of the activity coefficient with temperature. The addition of Sn to an unsaturated solution of O in Pb is shown to decrease significantly both the partial molar enthalpy and entropy of O. As the measurements were restricted to a narrow range between 750 and 1100°C in Pb-rich alloys, however, the pronounced variation of the partial molar enthalpy of O with temperature at constant alloy composition predicted by the quasi-chemical model could not be verified.

Dec 1, 1971

By Zhang-Guang Gao, Ming-Mei Zhu, Rui-Rui Zhao, Chao Jiang

This paper focuses on the CaO-SiO2-FeO-MgO-MnO-P2O5 slag system that represents the major components of dephosphorization slag in BOF. Phosphorus distribution between 2CaOSiO2-3CaOP2O5 Solid Solution and Liquid Slag were analyzed by FactSage. The effects of slag content, basicity on the distribution ratio of P between the solid solution phase and the liquid phase (LP) and the percentage content of P in solid solution phase and liquid phase have been discussed. The results show that, with the increase of basicity, LP (wt%) decreases until the basicity reaches 1.9, then it turns to increase. LP (wt%) increases gradually with the increasing amount of FeO or P2O5.

Mar 1, 2017

J. T. LITTLETON, JR., ? Corning, N. Y. (written discussion?).-This. discussion will add little that has not been brought out but will show how the problems encountered in the Corning Glass Works were overcome. The chief points of consideration in any equipment are, first, the work the equipment is called upon to do; second, the installation; and, third, the man who will use it. These three points should determine the type of apparatus adopted. If only rough measurements, merely a little better than the eye, are desired, the cost of the instruments should be considered; but if accurate temperature control is necessary, the cost of the equipment deserves only small consideration. There is no question that the real problem for any factory is the installation, making sure that the elements really give the temperatures desired; also, the instruments must be so designed that any man can use them.

Jan 12, 1919

By Qiang Zhong, Qian Li, Yongbin Yang, Tao Jiang

Thermogravimetric analysis (TGA) has been used to research the pyrolysis and combustion processes of coal used in rotary kiln of iron ore oxide pellet. Furthermore, the effects of air flow and oxygen concentration on the combustion behavior of coal were examined with TGA. The results showed that two individual stages can be distinguished for the pyrolysis of coal, the water evaporation stage and the de-volatilization stage. And the information on ignition and burnout characteristics can be obtained from the combustion process analyzed by TGA. Large air flow almost has no effect to the combustion process except that it enhances combustion intensity. However, the combustion process is further accelerated under oxygen-enriched conditions. With all experimental results, it could provide an attractive approach of analyzing coal for the rotary kiln process.

Jan 1, 2016

By M. J. Makhula, R. M. S. Falcon, S. O. Bada, L. M. Falcon

"SynopsisThe combustion and co-combustion behaviour of macadamia nut shell, high-ash coal, and anthracite, along with their blends was studied using thermogravimetry. The reactivities of all samples were analysed in air, oxygen, and CO2 atmospheres and at different heating rates from 10 to 40°C/min. Macadamia shell was found to have a lower ash content, 0.36%, than coal with 27.49% ash. The calorific values were similar, 19.64 MJ/kg and 19.44 MJ/kg respectively. The differential thermogravimetric results indicate that as the heating rates increase the ignition, peak, and burnout temperatures increase significantly, leading to high combustion rates. The interaction between the fuels was evaluated using the weighted average model, and the results indicated that there is more synergetic interaction between 20% macadamia plus 80% coal under oxygen than in air and CO2 atmospheres. The results of the investigation provide the combustion and co-combustion characteristics of various samples and their blends and indicate their combustion compatibilities. IntroductionThe global macadamia nut industry is developing at a very rapid rate. South Africa is currently the world’s third largest producer, with a production of about 35 000 t as of 2012 (Department of Agriculture, Forestry and Fisheries, 2013), compared to 840 t produced in 1996. The greatest numbers of the macadamia nut farms in South Africa can be found in Mpumalanga, Limpopo, and KwaZulu-Natal provinces, with Mpumalanga as the largest producing area. There are many factors influencing the increased demand for macadamia nuts, the most important factor perhaps being their nutritional value (California Dried Fruit and Nuts, 2011; MPC, 2014) and their suitability as a feedstock for manufacturing cosmetics, bakery products, nut paste, chocolates, sauces, and ice-cream. As a fuel, macadamia shell has a high heating value ‘as-fired’ of about 20.71 MJ/kg (Vhathvarothai et al., 2013), which could in turn be used in drying the nust, and the shell could also be milled and applied as a fertilizer."

Jan 1, 2015

By T. Yegulalp, R. Farrauto, A. Belova, M. Castaldi

Calcium oxide, with its ability to capture and store carbon dioxide, is emerging to become an important tool in carbon management. Calcium oxide can be used reversibly to capture carbon dioxide in situ and then be regenerated to produce a pure stream of carbon dioxide ready for sequestration; the Zero Emission Coal Alliance technology utilizes this property of calcium oxide to generate emissions-free electric power from coal. The reaction of calcium oxide with carbon dioxide resulting in thermodynamically stable carbonate is well understood; however, the efficiency of this reaction is limited by the diffusion of gases through bulk calcium oxide and through a layer of carbonate formed on the surface. In addition, the regeneration of calcium oxide is an endothermic reaction and is favored at high temperatures. The purpose of this paper is twofold: first, to address the diffusion limitation, a thin layer of calcium oxide, supported on a high surface area material, is studied thermogravimetrically to demonstrate the physical adsorption of carbon dioxide on calcium oxide. The adsorption is to take place at temperatures lower than required to form calcium carbonate.

Jan 1, 2007

By Ypma PJM

The Westmoreland uranium deposits occur on the northern flank of the Murphy Tectonic Ridge in the upper member of the Westmoreland Conglom- erate. Uranium mineralization is spatially associated with the contact of the overlying basaltic Siegal Volcanics and the margins of in- trusive dolerite dykes which are geochemically similar to the Siegal Volcanics. Thermoluminescence (TL) measurements on 800 samples from within the orebodies and surr- ounding host rock (up to 8 kilometres away from the deposits) have indicated that all of the Westmoreland Conglomerate has suffered major radiation damagg attributable to at least 10 ppm uranium over 10 years. The underlying rhyolitic Mid Proterozoic Cliffdale Volcanics have distinctive TL glow curves indicative of radiation sensitization caused by high uranium contents. These vol- canics are part of the Mid Proterozoic volcanic event known to be enriched in uranium. The Westmoreland Conglomerate has been derived by erosion of the uranium-rich Cliffdale Volcanics and associated Nicholson Granite Complex which makes it likely that the Westmoreland Conglom- erate had a high inherent uranium content.

Jan 1, 1984

By D J. McDougall

Due to changes in the solid-state conditions of minerals in the rocks surrounding hydrothermal, contact meta-somatic or metamorphosed ore deposits, positive or negative thermoluminescent anomalies may be found in their vicinity. Several types of equipment which can be used for both quantitative and semi-quantitative measurements of the emission are discussed and compared. Methods of selecting, preparing and testing samples to ensure reproducible results are outlined, along with the kind of data which can be obtained from different types of equipment. The normal thermoluminescence of rock-forming min~ erals in the common rock types is noted, and variations in the solid-state conditions in the wall rocks which will cause marked increases or decreases of true thermoluminescence are outlined, as well as the thermolum-nescence-like emissions which are present in the vicinity of ore deposits. Introduction T HERMOLUMINESCENCE occurs when certain crystalline materials are heated to temperatures ranging between 180' and 400°C. The light emission can be ascribed to the release of electrons metastably trapped within the crystal lattice, with peak emissions taking place at temperatures which are more or less specific for a particular set of traps; the area under

Jan 1, 1965

By Paul F. Gnirk, Ralph A. Wagner, Joe L. Ratigan

This thermomechanical analysis used the finite element method to investigate the behavior of crushed salt backfill in a waste disposal room situated in a salt dome repository. The first of two objectives was to determine the transient temperature rise and degree of thermomechanical consolidation that occur in the backfill as a function of drillhole depths. The second objective involved the evaluation of closure due to salt creep of unlined emplacement drillholes and the determination of pressure on steel sleeve liners in the drillholes should liners become necessary for canister retrieval. The retrievability period was considered to extend for 25 years after waste emplacement. The canisters were assumed to contain ten-year old high level waste with a thermal output of 4.3 kW at the time of emplacement.

Jan 1, 1981

By A. Sissing

Paper written on project work carried out in partial fulfilment of M.Sc. (Chemical Engineering) degree Thermophilic bioleaching, conducted at temperatures in excess of 65°C, provides considerable benefit over mesophilic bioleaching, particularly through extending the extent of leaching of base metal minerals such as chalcopyrite. Thermophilic bioleaching is facilitated through a group of micro-organisms known as the Archae, well adapted to extreme environment. In order to maximize the space time utilization of the stirred tank reactor in the thermophilic bioleaching process, it is desirable to maximize the loading of the finely divided mineral phase present while not adversely affecting the microbial performance. In this paper, the effect of the loading of the solid particulate phase on the bioleaching performance of Sulfolobus metallicus was studied in a stirred tank reactor. Emphasis was placed on the effect of the concentration of the finely divided solid phase (35 ? 75 µm). A model system comprised of 3% (w/v) pyrite in the presence of varying quantities of quartzite in the range 0 to 24% (w/v) was used to obtain the different solids concentrations. The bioleaching experiments revealed similar bioleaching performance in the presence of 3 to 18% (w/v) total solids. Above 18% (w/v) total solids (15% quartzite loading), bioleaching was impaired progressively with increasing solids concentration. At the highest solids loading studied of 27% (w/v), bioleaching was still observed. In terms of mass transfer, oxygen transfer potential was not significantly influenced in the bioleaching process over the range of solids investigated.

Jan 1, 2003

By Y. J. Yu, C. D. Zhang, Y. S. Zhao, W. G. Liang, Y. D. Geng, J. L. Bi

"In this study, the coefficient of thermal expansion (CTE) and thermal conductivity (TC) of shale in two perpendicular directions, vertical and parallel to the bedding of the rock, are firstly measured by experiment. The experimental results show that the CTE of the shale in the vertical direction is 1.69 times as much as that in the parallel direction, while the TC in the parallel direction is 1.83 times larger than that of the vertical direction. Based on the no initial strain assumptions, numerical simulations for the thermal cracking in shale are carried out with the obtained coefficients. Using finite element method and thermal-mechanical coupling theory, two fracture mechanical parameters, KI and J-integral of the shale are also analyzed for the shale thermal fracturing. The simulation results show that both KI and J-integral reach the maximum when the fracturing angle equals to 0° in the shale, namely parallel to the bedding direciton. It is also found that the two fracture parameters decrease with the fracturing angle increasing. Additionally, the thermal fracturing effect of the shale is evaluated under a given scenario. The study is significant for shale oil or gas recovery by in situ pyrolyzing method.INTRODUCTIONOil shale is regarded as a kind of unconventional resource that can contribute to production of shale oil and hydrocarbon gases (Rahm & Dianne, 2011). As is known that there is a large deposit of oil shale in China, and present technology for exploiting oil shale still concentrates on open-pit mining, obtaining shale oil by retorting shale on the ground (Li, Tang, Xue, Zheng, & Du, 2014; Qian, Yin, 2008). However, this technology has a bad effect on the environment and leads to severe resource waste for utilizing oil shale. Exploiting oil shale by in-situ method for ‘green mining’ is widely necessary in China (Kang, Wang, Cao, Liang, Chang, & Liu, 2013; Waters, Dean, Downie, Kerrihard, Austbo, & McPherson, 2009; Zoback, Kohli, Das, & McClure, 2012). One of effective method to exploit shale oil is heating oil shale in-situ underground. For instance, the in-situ conversion process (ICP technique) from Shell Company etc. used a direct heating method, and convectional heating oil shale underground by injecting superheated steam from Mining Technology Institute, Taiyuan University of Technology and constructing horizontal fracture in vertical wellbore from Chevron Company use indirect heating method (Chaudhary, Ehlig, & Wattenbarger, 2011; Hazra, Lee, Economides, & Moridis, 2013; Zhao et al., 2010). The convectional heating method contains complicated procedures with phase transition in double-media of fracture-matrix of oil shale subjected to multi-physical fields coupling including stress, fluid and temperature (Zhao et al., 2010). The characteristics of thermodynamics, solid mechanics and seepage of oil shale have been investigated separately (Hopkins, Rosen, & Hill,1998; Kang, Zhao, & Yang, 2008; Yang, Zhao, Kang, 2010; Zhao, Yang, Feng, Liang, & Kang, 2008; Zhao, Cao, Zhao, Lin, & Wang, 2008). However, it is quite difficult to solve constrained problem of each physical parameter in multi-physical fields coupling for oil shale pyrolysis."

Jan 1, 2015

By M. Q. W. Jones

This paper presents a compilation of physical properties of rocks from the Bushveld Complex. The database consists of more than 900 measurements each of thermal conductivity and density. The data are well distributed from localities around the Complex and most rock types are well represented. Thermal conductivity and density are shown to vary widely in the ranges 1.8-4.2 W m-1K-1and 2600-4200 kg m-3respectively. Although only 190 heat capacity measurements are available, this parameter is quite uniform for most rock types present, 800-900 J kg-1K-1, except for chromitite, which has a lower average, 750 J kg-1K-1. Rocks encountered in deep platinum mines are particularly well characterized and this has important implications for prediction of mine refrigeration requirements. The heat flux into a semi-infinite region with properties typical of the Bushveld Complex as a function of time is substantially lower than an equivalent model for the Witwatersrand Basin.

Jan 1, 2015

By D. P. Patil, B. K. Parekh

Water is the mainstay for beneficiation of fine size coal and minerals; however, it is also the least desirable constituent in the final product. The basic concept of the novel process described in this paper is based on the differential surface heat conduction/ absorption capacity of individual particles, which differs for different species of minerals. When a mixture of fine material is exposed to a radiant energy source, the various solids present in the mixture will absorb heat energy depending on their heat-conducting properties and there will be a difference in the surface temperature of the particles. When this differentially heated solid mixture is placed on a moving belt, which is coated with a low temperature melting resin, the hotter component of the mixture will stick to the belt and relatively cooler particles will stay free on the belt and fall off at the end of the belt run. Experiments were conducted with pyrite, coal, and quartz of 6 × 18 mesh particle size. The goal of the test program was to find the optimum conditions at which there exists a required temperature difference between minerals and coal particles by controlling the operating system variables. Preliminary tests results showed that there is a potential for separating mineral matter from coal using the thermo-adhesive separation technique.

Jan 6, 2022