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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 (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 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 J. Y. Hwang

Microwave heating is an attractive alternative to conventional heating methods because heat is generated directly within the microwave absorbing materials. It has potential to be utilized for selective heating and removal of specified components from a materials mixture. This investigation was undertaken to explore the potential of selective heating and burning of binders for foundry sand reclamation. Selected raw materials and binders used in foundry operations were tested to determine their receptivity to microwave heating. Time needed to reach 600°C and/or the maximum temperature achieved for samples irradiated by microwaves for twenty minutes under 800 W microwave power are reported. The microwave heating characteristics of the selected materials are summarized and discussed. The interactions between microwaves and the raw materials used in a foundry. such as silica sand. chromite sand and bentonite (clay) binder were studied. The results showed that chromite sand coupled well with microwave energy at ambient temperature while silica sand did not. This was expected because the major component of chromite sand. iron chromite (FeCr2O4). is a good microwave absorber. while quartz, which is the major component of silica sand, is a microwave transparent material at ambient temperature. Bentonite absorbs microwaves well because it contains a hydroxyl functional group and water molecules in its structure. It was found that the structure of bentonite was changed through microwave irradiation. Microwave heating characteristics of silica sand mixed with different amounts of bentonite binders were investigated. The presence of bentonite in the mixture improved the microwave heating of silica sand significantly. and bentonite was deactivated by the microwave processing.

Jan 1, 1995

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

Jan 1, 2003

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

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

Jan 1, 2003

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 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 F. J. Arriagada

Where gold is present in a finely disseminated form within sulfide particles, the porosity and surface area of the calcined material strongly influence leaching since they control the penetration of solution inside the gold-bearing grains. On the basis of a stability diagram for the Fe-O-S in the temperature range of 400 to 750aC, the expected sequence chemical transformations associated with the oxidation of pyrite is discus-sed. By using analytical techniques which include scanning electron microscopy, X-ray diffraction and BET gas adsorption, the chemical and structural changes experienced by auriferous pyrite-arsenopyrite concentrates and pure pyrite samples are studied under an oxidizing roasting atmosphere of com-position 80% N + 20% O2 in the temperature range of 450 to 750°C. The results indicate that as the roasting temperature increases, the surface area of the calcines decreases sharply after a maximum value attained at about 450-500°C. SEM micrographs show that the needle-shaped tips which characterize the surface of the oxide product become wider and the size of the pores between them is decreased when the roasting temperature is in-creased from 550 to 750°C. This effect suggests that the formation of a more "closed" hematite product at higher temperatures is due to sintering associated with a faster growth and crystallization of the oxide. A strong correlation is shown between increasing roasting temperature and increase in gold lost in cyanidation tailings, an effect which may be partly attributed to the loss in surface area of the calcines.

Jan 1, 1982

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 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

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 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 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 Richard D. Hagni

The techniques of reflected light microscopy and cathodoluminescence microscopy are uniquely suited to the study of the products from many important industrial problems. Ref1 ected 1 ight microscopy provides the means to rapidly identify the mineralogy of an industrial sample, determine the abundance of each phase, and examine the mineral intergrowths or textures. Cathodoluminescence microscopy is a relatively new instrument that provides the means to cause many minerals to cathodoluminescence under the microscopy. The cathodoluminescence of a mineral allows it to be readily distinguished from other phases that differ in cathodoluminescence but are similar in optical properties. Cathodoluminescence microscopy is especially useful to detect cathodoluminescence minerals that are present in only small quantities. Reflected 1ight microscopy and cathodoluminescence microscopy have been successfully applied in studies of beneficiation products, prediction of beneficiation and leaching problems, phosphatic iron ores and mill products, pyrometallurgical products, roasted refractory gold-bearing sulfides, ceramic build-ups, electric arc furnace and smelter dusts, and other industrial products.

Jan 1, 1993

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 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

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 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 V. A. Luganav

The behavior of arsenopyrite under heating has been studied by many scientists. It has been already established that under heating at more than 650°c and without air access the arsenopyrite dissociates with the formation of one atom arsenic. Under vacuum the dissociation process begins at 5500C with the formation of elemental arsenic. The residue of dissociation process contains pyrrhotite and throilite. In the presence of pyrite, arsenopyrite dissociates under lower temperature and with a higher velocity than without it. The industrial realization of fool scale processing of arsenic bearing raw materials is possible only by the use of standard equipment and oxygen containing blast. In this view the paper presents the results of the study on the effect of oxygen in the gaseous phase and its addition into the charge of pyrite in the process of arsenopyrite decomposition. Thermodynamic analyses showed that under thermal processing of arsenopyrite in the presence of pyrite and limited quantities of oxygen in the gaseous phase the formation of arsenic sulfides is possible according to the following reactions:

Jan 1, 2003