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By H. Y. Sohn

The purpose of this article is to analyze critically and quantitatively the effect of chemical equilibrium on the overall rates of fluid-solid reactions. It is shown through a mathematical analysis that a reaction with a small equilibrium constant (a positive standard free energy of reaction) is more likely to be rate-controlled by pore diffusion or mass transfer than a reaction with a large equilibrium constant. The overall reaction rate of the former also tends to be slow. Furthermore, the apparent activation energy of such a reaction approaches the standard enthalpy of reaction (M-f'), rather than the true activation energy of the chemical reaction. The Law of Additive Reaction Times developed by the author is shown to apply to equilibrium-limited fluid-solid reactions and to be useful in quantitatively analyzing the behavior of such reactions.

Jan 1, 2003

By H. Y. Sohn

The purpose of this article is to analyze critically and quantitatively the effect of chemical equilibrium on the overall rates of fluid-solid reactions. It is shown through a mathematical analysis that a reaction with a small equilibrium constant (a positive standard free energy of reaction) is more likely to be rate-controlled by pore diffusion or mass transfer than a reaction with a large equilibrium constant. The overall reaction rate of the former also tends to be slow. Furthermore, the apparent activation energy of such a reaction approaches the standard enthalpy of reaction (Mf'), rather than the true activation energy of the chemical reaction. The Law of Additive Reaction Times developed by the author is shown to apply to equilibrium-limited fluid-solid reactions and to be useful in quantitatively analyzing the behavior of such reactions.

Jan 1, 2003

By Dandan Jian, Christian Karcher

Information of liquid steel flow patterns inside the mold may be obtained from the velocity at the free surface (meniscus). This meniscus flow may be measured using the contactless electromagnetic technique termed Lorentz force velocimetry (LFV). It is based on the measurement of Lorentz forces acting on a magnet system when an electrically conducting metal melt interacts with the field lines stretched by the magnet system. Force sensor and the magnet system form a so-called Lorentz force flowmeter. In this paper we present a series of model experiments that demonstrate the feasibility of using two identical flowmeters that are arranged in a certain distance one behind the other. In this case, surface velocity may be determined by just cross-correlating the two force signals recorded by the two sensors. This technique is called time-of-flight LFV. A special prototype of a respective measuring device, called meniscus velocity sensor (MVS), has been developed to measure local free-surface velocity. In the present paper we describe experimental results of respective measurements in the model test stand LiMeSCo (liquid metal surface velocity correlation). To check the potential of the time-of-flight technique, in a first step we measure surface velocities during solid-body rotation of metallic substances. We observe that small modulations in the signals that are due to the natural unevenness of the solid body can be used to determine surface velocities. In a second step we apply the time-of-flight technique to liquid metal free-surface flow. Here we use the low-melting eutectic alloy GaInSn as a test melt. In this case we observe that the cross-correlations between the signals are much rarer and much weaker than in the solid-body experiments. We conclude that the presence of the localized magnetic fields, produced by the permanent magnets of the flowmeter, give rise to intense deformation of the free surface and the creation of surface waves. The field acts as a magnetic obstacle. We observe that the flow velocity is decreased right underneath the magnetic field and is accelerated in the side regions. This magnetic obstacle effect may restrict the determination of the local surface velocity in application.

Jan 1, 2012

By K. Ohmori, K. Takeya, S. Yoshizawa, A. Kawamoto, T. Ishikawa

"High performance Sm2Fe17N3 magnet powder is developed nitriding Sm2Fe17 alloy that 'is made using a reduction and diffusion method. Typical remanence, coercivity and maximum energy product of the fine powder are 1.40 T, 1.13 T and 323 kJ/m3, respectively. Decreasing samarium content, oxygen content and the amount of a-Fe are found to be the important factors to realize high-energy product.High performance injection molded Sm2Fe17N3 anisotropic magnet is also developed using the powder and an original binder system developed in order to mold at low temperature. Typical remanence, coercivity and maximum energy product obtained are 0.77 T, 0.78 T and 103 kJ/m3, respectively in the density of 4.77 Mg/m3The temperature coefficient of remanence is -0.07 %/K and that of coercivity is -0.54.%/K. The initial irreversible flux loss of the magnet that has a permeance of two is -5 % at 100 °C and the irreversible .flux loss of it is -4.4 % exposing it at 80 °C for 1000h.IntroductionSm2Fe17N3 alloy powder is expected to be very useful for a bonded magnet. The reasons are as follows. The magnetization is as large as the Nd2Fe14B alloy. Curie temperature is even higher than the alloy. The uni-axial anisotropy is comparatively higher than the alloy. Consequently it is possible to obtain high coercivity after just milling the powder and therefore possible to obtain high-energy product in a bonded magnet as it is realized in the SmCo5 bonded magnet. On the other hand, sintering is difficult because it will be decomposed into samarium nitride and a-Fe when heating it up to 500°C:"

Jan 1, 2000

By Du Sichen, S. Seetharaman, A. Jakobsson

"In the Present paper, the principles of oxygen potential measurements have been discussed along with the design details for oxygen sensors that are used in copper industry. A description of some of commercial probes is presented along with their salient features. The application of these sensors in flash smelting, converter and casting sections of copper production are discussed along with their implications on process optimization.I. IntroductionThe high temperature galvanic cells have come into prominence on account of their numerous applications in both fundamental as well as applied measurements. Since the inception of the oxygen-ion conducting electrolytes like ZrOrCaO·by Kiukkola and Wagner [1], the oxygen concentration cells have been extensively used in laboratories as well as in industries. In metal-production technology, these cells have been used to monitor the oxygen potentials in metallic, slag as well as gas phases and also to control and styr metallurgical processes. The pioneer among the various industrial users of such cells is the copper industry. To-day, high temperature solid electrolyte cells involving oxygen ion conducting electrolytes have become an integral part of copper pyro-refining and continuous casting. In the present paper some of the applications according to the industrial processes are described including the developments that are going on in the European scene."

Jan 1, 1997

By H. Y. Sohn, M. Y. Mohassab-Ahmed

"As part of research to develop a novel flash ironmaking process using reduction of iron ore concentrate by natural gas or hydrogen, sulfur and phosphorus distribution ratios between MgOsaturated slag and iron were determined in the temperature range 1550-1650°C under three different gas atmospheres: H2/H2O, H2/H2O/CO/CO2, and CO/CO2. The distribution coefficients of sulfur (Ls) were 4.0, 2.0, and 0.8, respectively, under these atmospheres. The distribution coefficients of phosphorus (Lp) were, respectively, 8, 17, and 20 under these atmospheres. In the flash process over -25 wt% P and S volatilize during ore concentrate downward flight in the reactor shaft in addition to avoiding coke. Therefore, iron produced by the flash ironmaking process would have much lower sulfur contents than the typical hot metal produced by the BF.IntroductionGiven the issues related to large carbon dioxide emissions and energy consumption in the existing ironmaking technologies, a novel flash ironmaking technology was conceived by Sohn [1-3] at the University of Utah. This technology is the first ironmaking process that will convert iron ore concentrate directly to metallic iron in-flight. This process will produce iron directly from concentrate without requiring pelletization or sintering and avoid the need for coke. In addition, this process concept takes full advantage of the fine particle size of concentrate with a large surface area, which permits rapid reduction by a gas. In this novel ironmaking process, potential reductants and fuels are H2, natural gas, and coal gas. Therefore, an iron-slag bath is expected to be at equilibrium with gas atmospheres of mainly H2/H2O or CO/CO2/H2/H2O, respectively, corresponding to the use of H2 or natural gas/coal gas. Since the effects of an H2O- containing atmosphere on slag properties have not been studied before, it is critical for the development of the novel flash process to determine these effects. In H2-H2O-CO-CO2 gas mixtures under ironmaking conditions, H20 was found to have the most pronounced effect on the slag chemistry [ 4, 5]. In addition, it was found in this laboratory that water in the gas atmosphere affected the distribution of Mn between slag and molten iron [6]. Most previous work used CO/CO2 gas mixture to control oxygen partial pressure (p02) [7, 8]. Others used only inert atmospheres [9], although Kor and Richardson [10] used a mixture of C02/H2 to control p02. For phosphorus, previous research focused on Ar [11], Ar-CO mixture [12], CO [13], CO/CO2 [14] or N2/CO [15]. Therefore, it was necessary to investigate the effect of water vapor content in H2-H2O-CO-CO2 mixtures on the equilibrium distribution of sulfur and phosphorus between CaO-MgOsatSiO2-Al2O3-FeO- MnO (0.2-0.8 wt%)-P2O5 (0.1-0.9 wt%) slag and molten iron as part of the development of the novel flash ironmaking technology."

Jan 1, 2014

By Junzo Hino

Most of the waste that contains a small portion of copper is landfilled. The recycling process of copper from the waste, such as shredder residue, should be developed in order to save mineral resources and prevent environmental pollution. Shredder residue, generated from disposed automobiles and electric appliances, consists of many types of plastics, glasses and metals. The combustion heat of plastics is efficiently used for smelting in the recycling process that consists of melting and reduction. Because the waste contains numerous components the knowledge of the distribution behaviors of the main components is necessary to develop the recycling process. The distribution behaviors in the recycling process are evaluated by using the thermodynamic calculation program, HSC Chemistry. The calculation results are compared with the practical operation data of the recycling process and discussed.

Jan 1, 2003

By A. W. Bryson, K. C. Lenthall

"With the growth in the use of cobalt in industry, interest in its extraction and recovery has increased. With this increased interest comes the need for a fundamental knowledge of the processes involved in the recovery of cobalt metal. This paper examines the effects of cobalt concentration, catholyte pH, operating temperature and current density on cobalt electrowinning with respect to the current efficiency, cell potential and nature of the cobalt deposit. It is found that the cobalt concentration and catholyte pH affect the current efficiency, while current density and temperature affect the cell potential and thus the specific power consumption. Pitting on the deposit is affected by the catholyte pH and the operating temperature. Furthermore, the effect of feed flow-rate on catholyte pH, and thus current efficiency, is investigated. A model to predict the cell performance, which includes the flux of hydrogen ions through the diaphragm, is proposed.IntroductionCobalt metal is a silvery transitional metal found between nickel and iron on the periodic table. Due to its resistance to corrosion and other properties under high temperatures and its good work-hardening characteristics, it is favoured in alloys used in high temperature applications. These include aerospace, aircraft and high speed tools. Other applications include its use as a colourant in glass and ceramics, a drying agent in paints, a nutrient for livestock, a catalyst in the petroleum industry and, in the medical field, in prosthetics and radiology.The main deposits of cobalt are found in Central Africa, specifically Zaire and Zambia, although deposits also occur in Morocco, Canada and Australia. The cobalt is generally associated with other transitional metals including nickel, iron and copper. It is generally extracted by hydrometallurgical means and recovered from solution by electrowinning or hydrogen reduction. Little data [1-2] exists in literature on the electrowinning of cobalt from aqueous solutions. This paper investigates the effects of various operating conditions on the current efficiency, cell potential and deposit nature under continuous operation."

Jan 1, 1997

By N. Kanari

Reactivity of MgO towards C12+air, C12+N2 and C12+CO gas mixtures was studied up to 1000 °C. Carbochlorination of MgO occurs at temperatures lower than that of its oxychlorination. Effects of gas flow rate, temperature and partial pressure of the carbochlorinating gas mixture on the reaction rate were investigated. The apparent activation energy of MgO carbochlorination is 49 kJ1 mol between 425°C and 600°C. At 550 °C, the apparent reaction orders with respect to C12+CO, C12 and CO, are 2.37, 1.47 and 0.89, respectively. At this temperature, the maximum reaction rate was obtained using a C12+CO gas mixture having a Cl2lCO molar ratio equal to about 0.6.

Jan 1, 1998

By James P. Bennett

EAF slag chemistry and its control have been recognized as important in producing quality steel at a low price for a number of decades. EAF steel producers make lime and dolomite additions to furnaces, controlling the CIS ratios and sulfur pickup from the steel. Existing phase diagram data at 1600°C for CaO, MgO, FeO, SiO2, and Al2O3 was used to write a computer model optimizing slag chemistry for slag foaming and reduced refractory wear. The model, its development, and its use in an industrial steelmaking environment will be discussed along with how the model can improve energy efficiency. The importance of EAF mass balance to account for critical materials like Si in scrap and refractory wear using the model will also be emphasized.

Jan 1, 2003

By J. G. Zafiratos

The leaching of a Greek low-grade manganese dioxide ore, not amenable to conventional mineral processing operations, was studied using a mixed culture of Thiobacillus sp. bacteria. The experiments were carried out in specially designed continuously aerated and stirred tank reactors arranged in two-tank series. The first tank of each series was loaded with an elemental sulfur culture suspension while the second was loaded with a manganese ore high density slurry. The bacterial culture had been previously adapted to grow on elemental sulfur and also in the presence of manganese ore and dissolved manganous ion. A two level full factorial design was constructed in order to study the effects of the ferric ion concentration in the leach solution, the "elemental sulfu weight to ore weight" ratio, the ore pulp density and the composition of the dispersed gas. The responses which were investigated included percentage manganese recovery, co-dissolution of iron and manganese dissolution rate. Parameters with constant values throughout the experiments were the leach solution pH, the nutrient medium composition, the dilution rate and the ore and sulfur grain sizes. It was found that the ferric ion concentration was the most significant factor and had a positive effect on the final percentage extraction of manganese from the ore and also on the rate of manganese solubilization from the ore. The effects of the other factors studied are discussed in detail.

Jan 1, 1997

By S. L. Pohlman

Physical characteristics of possible importance in the acid leaching of Chrysocolla have been evaluated. Surface area studies and pore size distribution indicate: 1) a large surface area (350 m /gm); 2) an average pore size of 13 or 16 Å , depending upon use of the adsorption, or desorption, branch of the Type IV isotherm in the evaluation; ) the presence of a significant fraction of pores of size less than 15 Å determined by the accumulation surface area method. The initial structure is micro- crystalline on the basis of x-ray powder patterns; the silica leach residue is amorphous and has only 24 m2 /gm surface area, and loses integrity when dry. However, readsorption of copper onto the wet leach residue gives a product with integrity and 100 m2 /gm surface area. Visual observation of the leach residues supports evidence of a non-protective diffusion mechanism of leaching which is well correlated by the shrinking core model previously presented.

Jan 1, 1976

By James P. Bennett

EAF slag chemistry and its control have been recognized as important in producing quality steel at a low price for a number of decades_ EAF steel producers make lime and dolomite additions to furnaces, controlling the CIS ratios and sulfur pickup from the steel. Existing phase diagram data at 1600°C for CaO, MgO, FeO, SiO2, and Al2O3 was used to write a computer model optimizing slag chemistry for slag foaming and reduced refractory wear. The model, its development, and its use in an industrial steelmaking environment will be discussed along with how the model can improve energy efficiency. The importance of EAF mass balance to account for critical materials like Si in scrap and refractory wear using the model will also be emphasized_

Jan 1, 2003

By Kenneth S. Coley, Michael Pomeroy, Elaine Chen

Recent work on modeling of BOF steelmaking is reviewed, highlighting the critical aspects of each approach. It is concluded that the most successful models should be based on a deep understanding of the mechanisms and kinetics of the critical reactions. The importance of the decarburization mechanism is discussed with particular reference to its role in droplet swelling or bloating which has a profound influence on the droplet residence time in the slag. Conditions which cause bloating are discussed and the rate determining step is proposed to be primarily nucleation of CO bubbles inside the metal droplet with some influence from growth by reaction at the bubble/metal interface. The discrepancy in the super-saturation ratio required for classical nucleation is discussed and an approach using a surface tension modifying parameter is illustrated. Finally, the role of CO nucleation in controlling the driving force for dephosphorization is discussed.

Jan 1, 2014

By Derek J. Fray

Electric arc furnace dusts, especially those containing zinc ferrite, are notoriously difficult to process to give valuable products and non-toxic residues. The ideal process would remove and recover the toxic non-ferrous metals as pure metals, of commercial value, and non-toxic residue which can be used as a raw material in the steel industry. From an examination of the thermodynamics of the oxides and chlorides of the various elements in the dust, it is apparent that the chlorides of the toxic non-ferrous elements are more stable than the oxides while the reverse applies to the ferrous elements. This offers the opportunity for a complete separation of the zinc, lead and cadmium from the iron oxide. Results are presented for the chlorination of electric arc furnace dusts under oxidising conditions and the subsequent treatment of the chlorides to recover the pure metals and chlorine which can be recycled back to the reactor.

Jan 1, 1994

By Tao Zeng, Jianchao Li, Chang Jie, Jieyu Zhang, Jifang Xu, Kuochih Chou

"The densities of the selected quaternary Ca0-5%Mg0-Alz03-Si02 slag with low silica were measured by the Archimedean method in a wide temperature range from l 723K to 1823K. Slag compositions were chosen based on five different levels of Si02 content between 0.00 pct and 11.40 pct. The MgO content was equaled to 5.00 pct. The mass ratio of CaO/Alz03 was varied from 0.67 to 2.14. The effects of temperature, Ca0/Alz03 ratio and optical basicity were studied. It is shown that density decrease approximately linearly with an increase in temperature. With the same Si02 content, the density decreases with increasing of CaO/Alz03 ratio and optical basicity. Based on the experimental data as the boundary of the homogenous phase region predicated by F ACTSAGE software, the mass triangle model is used to calculate the density of selected limited homogenous phase region. The results showed that the mass triangle model is working well.IntroductionIt is of great importance to measure density of slag melt not only to the theory research for melt, which that is directly amenable to the structure correlations of molten slags, but also to the industrial application. Many metallurgy phenomena such as inclusion formation in molten melt and its removing, slag foaming, slag-metal reaction are closely related to the density of slag. Density is also required to estimate other fundamental properties, like surface tension, viscosity, and thermal conductivity from thermal diffusivity so that a relatively complete picture in regard to the behavior of high-temperature molten oxides could be made."

Jan 1, 2013

At its Copper Cliff Smelter, Inco Limited processes a bulk copper-nickel concentrate in two Inco oxygen flash furnaces, The furnace matte is converted to low iron matte for further processing, and the molten converter slag is recycled to the flash furnaces. The flash furnace slag is discarded. Natural gas or coke supplies a minor proportion of the process heat requirements, thus limiting the flash furnace matte grade to the target 45% CuNiCo. Coke addition to the furnace offers a potential means of establishing a reducing barrier on the surface of the molten bath. Such a practice would be conducive to producing sulfur deficient (partially metallized) matte. At the same iron content, the iron activity of sulfur deficient matte is higher than that of regular matte. A supernatant coke barrier could, therefore, be expected to lead to higher nickel and cobalt recoveries, reduction or even elimination of magnetite furnace bottom build-up and increased sulfur elimination as S02 in the flash furnace. Preliminary experiments were conducted in a miniplant flash furnace to investigate the effect on process metallurgy of the suggested modified scheme. This paper presents the experimental results and discusses key aspects of the possible operation of the Inco flash furnace with a coke barrier separating the freeboard from the molten bath.

Jan 1, 2003

By Mojtaba Ahmadiantehrani

A previous study showed that up to 80% gold extraction could be obtained with 160 lbs/ton hypochlorite consumption at ambient temperature from a low grade Carlin-type carbonaceous ore. Crushing the ore to a finer size and agglomerating with cement decreases hypochlorite consumption by 60%; while, agglomeration and curing the cement-ore mixture with hypochlorite solution has no significant effect on total gold extraction. The high hypochlorite consumption is due to oxygen depletion as the solution percolates through the column, i.e., oxidation of gangue materials. These side reactions are reduced at sub-ambient temperatures resulting in a substantial further decrease in hypochlorite consumption. The optimum temperature range and additional reduction of hypochlorite consumption by introducing the reagent into the column at different elevations will be discussed.

Jan 1, 1992

By S. R. Reddy

Thennodynamic properties of several quaternary systems are calculated using our recently modified Margules equations. The modified Margules equations are expressed up to infinite order in the vicinity of solvent. Quaternary system of one solvent and three,solute partials are derived. First order interaction coefficients of binary, ternary and cross -interaction parameters of quaternary system are used to'evaluate the partial functions. In the original fonn of Margules equations,derived partial functions are convergent and same 'as Unified ,Interaction Parameter Fonnalism. But considering up to infinite order of the Margules coefficients, the functions are divergent, in order to overcome this restriction, Margules equations are modified to get consistent equations. Derived partial functions are thennodynamica Hy consistent with Maxwell and Gibbs Duhem relations. The derived logarithmic activity coefficient of the solvent and solutes are consistent with the ternary systems. The calculated data, ie., activity coefficient values of nitrogen and interaction coefficients are in good agreement with the data of Fe-Cr-V -N. Fe-Ni-V -N, Fe-Cr-Ta-N and Fe-Ni-Ta-N systems.

Jan 1, 1999

By I. Iwasaki

Platinum group elements (PGE) are often found in arsenide and sulfarsenide minerals as inclusions in copper-nickel bearing gabbroic rocks. Major losses of platinum in flotation have been attributed to the poor recoveries of the arsenic minerals. Flotation characteristics of a synthetic nickel arsenide and arsenopyrite were studied through rest potential and oxidation rate determinations, surface analyses, and micro-and batch-flotation tests. The use of nitrogen during grinding and flotation together with copper activation improved the PGE recoveries from Duluth Complex ores. The flotation behaviors of the sulfarsenide minerals are still unresolved. The role that electrochemical interactions play among arsenides, sulfarsenides, sulfides and grinding media on their f10atabilities is discussed.

Jan 1, 1988