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By John R. Lewis

DURING the past few years there has been considerable interest in the sizing and the preparation of the iron ore fed into blast furnaces. Furnacemen know that proper sizing of ore tends to increase the efficiency of the furnace. It has been shown by Joseph1 and his associates that there is a direct relationship between the porosity of an ore particle and the time required for its reduction in the blast furnace. This relationship may be stated as follows: All other factors remaining constant, the time for reduction of a given sample of ore is inversely proportional to its porosity. As a consequence, large pieces of very porous ore, say 3 or 4 in. in cross section, will be completely reduced by the time they reach the hot zone just above the tuyeres, while large pieces of dense, nonporous ore may reach the hot zone with their centers unreduced. This means that for the latter complete reduction will be accomplished by the so-called "direct method;" i.e., where carbon reacts directly with the ore. Some recent work by Philbrook2 seems to contradict this rule. He found that of two unlike ores he studied, the one with the lower porosity reduced more readily. He explained his results as "possibly due to an apparently greater tendency of the `A' ore (lower porosity) to crack during preliminary dehydration and during reduction." This brings his results in line with the rule stated above. It is not the author's intention to enter into a discussion of the merits of "direct" versus "indirect" reduction. It is enough to say that, in general, indirect reduction is desirable. For the greatest efficiency, Gruner's theorem3 requires that all reduction in the blast furnace be indirect. Joseph seems to believe this also, because in his recent article on Some Comparisons between Iron Ore, Sinter and Nodules as Blast Furnace Feed' he concludes that: "In general, the carbon in blast-furnace coke is used most efficiently when the largest amount of the carbon charged reaches the tuyeres." However, P. V. Martin,' in an excellent paper, has shown that some direct reduction may actually increase the efficiency of the furnace; that is, increase its rate of production while maintaining maximum fuel economy. For nonporous ores there is more opportunity to have an excess of direct reduction unless the factors that make for indirect reduction are favored; for instance; the proper sizing of the ore particles. Another factor that has an important bearing on the reduction rate, as it is affected by particle size, is the flow of heat into the particle. The ore particle

Jan 1, 1947

By J. D. T. Capocchi, M. B. Mourao

The rate of reaction between iron oxides and carbonaceous materials, agglomerated as pellets, was studied experimentally by measuring the weight loss as a function of time. The effects of temperature, carbon type, inert gas flow rate, pellet size and additions (sodium. carbonate and Portland cement) were determined. It was shown that the value of the apparent activation energy can display large deviations under different experimental conditions; in the present work it was found to be 226.6 kJ/mol. The reaction with coke is slower than with charcoal, and the rate increases as the flow of inert gas in the reaction vessel decreases. Comparison of the rates for pellets of different sizes has shown that for small pellets the initial rate is faster but that it slows down at high conversions owing to the penetration of inert gas into the pellet. Additions of sodium carbonate and Portland cement increase the rate; sodium. carbonate promotes the catalysis of the Boudouard reaction, which is the slowest of the partial reactions. The increase in the rate with Portland cement is attributed to the release of water vapour

Jun 18, 1905

By K. Y. Lee, J. M. Park, C. W. Park

Laboratory-scale experiments were carried out to investigate the effect of ladle slag composition on the decreasing behaviour of aluminum content in steel, i.e., reoxidation of molten steel in contact with slag, using a vertical tube furnace. The steel composition and the slag system chosen were for ultra low carbon and CaO-Al2O3-FeO-MnO-MgO based to simulate ULC steel grades. It has been observed that the reoxidation rate shows a good relationship with (T. Fe) content in slag. In case of (T. Fe) content higher than 1.5 weight per cent, the reoxidation rate increases linearly with increasing (T. Fe) content. For a given (T. Fe) content, it decreases with the increasing (CaO)/(Al2O3) ratio of the slag. However, in the case of (T. Fe) content lower than 1.5 weight percent, no particular relationships are observed between the reoxidation rate and (T. Fe) content or the (CaO)/(Al2O3) ratio of the slag. These results were used to propose for an aim a slag composition for the ULC steel grades in a steelmaking plant. Keywords: slag deoxidation, slag killing, slag composition control, IF steel, ULC steel grade

Jan 1, 2004

By John Chipman

IN the manufacture of rimming steel-which constitutes the bulk of the world's production of mild steel-the factors that determine the quality of the product are very closely associated with the pouring and solidification of the steel in the ingot mold. The behavior of the metal in the mold is, on the one hand, the resultant of the complex processes through which the liquid metal has passed, and, on the other, it is an indication of the probable behavior of the ingot during subsequent rolling and finishing operations. A detailed study of the mechanism of solidifica-tion of rimming ingots ought to yield information that will be useful iii controlling the structure of the ingot and the quality of the ultimate product. The first step in such a study is to determine the rate at which the solid shell of the ingot forms from the liquid metal in the mold. A knowledge of the rate of solidification will make it possible to correlate observations of rimming action and gas evolution with studies of the structure, porosity, and segregation within the ingot. Thus, if the metal in the mold is observed to fall, let us say one minute after pouring, the portion of the structure associated with this fall will lie located in the part of the ingot that is solidifying at that particular moment. The knowledge that the ingot solidifies to a depth of ¾ in. in the first minute enables us to locate in the ingot the structural features corresponding to the observed fall. Conversely, the blowhole condition associated with a rising or growing ingot will be found in the part of the ingot that is solidifying at the time the phenomenon occurs. The time required for the complete solidification of an ingot has long been a matter of speculation. It is of considerable practical importance in connection with charging and heating in the soaking pits. Too rapid handling of the ingot through heating and rolling processes has been thought to be associated-with excessive pipe and other internal defects, so that a further object of this investigation was to attempt to estimate the time required for complete solidification, or the minimum practical time within which the subsequent operations can be performed with the minimum hazard.

Jan 1, 1937

By Renato G. Bautista

The chemistry of the separation of metals from each other and from the other undesirable components involve multiple simultaneous chemical reactions. In the case of leaching, the heterogeneous chemical reactions between the solid and the liquid phase may be limited to a few reactions. In the homogeneous liquid phase, the number of simultaneous chemical reactions could be double or triple that of the number of heterogeneous reactions:. The rate of dissolution becomes very dependent on the changing concentrations of the significant chemical species taking part in the multiple reactions in both the heterogenous and homogeneous phase. The rate expression developed for the process must take into account the mechanism of chemical reactions in order to best represent the actual process. This paper also examine the role of mass transfer with chemical reaction in the develpoment of the rate equations for dissolution, liquid-liquid extraction, membrane separation, precipitation, and electrodeposition.

Jan 1, 1996

By Renato G. Bautista

"The chemistry of the separation of metals from each other and from the other undesirable components involve multiple simultaneous chemical reactions. In the case of leaching, the heterogeneous chemical reactions between the solid and the liquid phase may be limited to a few reactions. In the homogeneous liquid phase, the number of simultaneous chemical reactions could be double or triple that of the number of heterogeneous reactions. The rate of dissolution becomes very dependent on the changing concentrations of the significant chemical species taking part in the multiple reactions in both the heterogenous and homogeneous phase. The rate expression developed for the process must take into account the mechanism of chemical reactions in order to best represent the actual process. This paper also examine the role of mass transfer with chemical reaction in the develpoment of the rate equations for dissolution, liquid-liquid extraction, membrane separation, precipitation, and electrodeposition.IntroductionThe understanding and the elucidation of the mechanism of the rate phenomena for a specific chemical reaction system is of prime importance in the development of a successful chemical process. The development of successful emerging technologies for metals separation will depend on the accurate interpretation of the intrinsic chemical reaction kinetics and the rate of mass transfer of the desired metal species during its separation from the undesirable chemical species. This is the case whether the process application is for separation, concentration, and /or purification.The chemical processes that will be examined in this presentation will include leaching, solvent extraction, membrane separation, precipitation, and electrodeposition."

Jan 1, 1996

By N. J. Themelis

In the last two decades, the Outokumpu flash smelting process has become the dominant new technology for copper smelting and has? also been applied to the smelting of other metal sulfides. The application of oxygen enrichment and improvements in concentrate burner and furnace design have resulted in ever increasing smelting rates per unit volume of the reaction shaft. This paper examines the. rate phenomena taking place in the reaction shaft of the Outokumpu furnace and compares information obtained from a mathematical model of heat and mass transfer rates to results obtained in pi1ot tests conducted at Pori, Finland, and to actual performance of a number of flash smelters around the world. 2?

Jan 1, 1985

By Charles F. Coleman

Kinetics studies and other rate measurements are reviewed in the amine extraction of uranium and of some other related and associated metal ions. Equilibration' is relatively fast in the uranium sulfate systems most important to uranium-hydrometallurgy. Significantly slow; equilibration-has ' been encountered' in some other systems. Most of the recorded rate information, both qualitative and quantitative; has come from exploratory and, process-development development work, while some kinetics studies have been directed specifically toward elucidation of, extraction mechanisms. In contrast to some other extraction systems, relatively little attention has been given to the kinetics of uranium extraction by amines. This is because investigators have not been troubled by slow extractions. Instead, when rate limitations have been of concern in amine extraction (Amex) process developments, they have been mainly from slow phase disengagement rather than from slow equilibration. Nevertheless, taking uranium together with several other elements that are closely related to it or associated with it in typical processes, a considerable body of rate information has been recorded.

Jan 1, 1979

By Jun Li

Rate processes of silver cyanidation were studied with the objective of understanding the reaction mechanism. The research was divided into three sections: anodic dissolution of silver in cyanide solutions, cathodic reduction of oxygen on silver surfaces and the direct leaching of silver in oxygenated cyanide solutions. The charge transfer steps plus the diffusion of reactants from bulk solutions to the silver surface were identified as rate-limiting and the rates of both anodic and cathodic reactions can be calculated using the Butler-Volmer equation and Fick's first law. Based on mixed potential theory and the results of electrochemical studies, a comparison of the rate obtained from direct leaching with that predicted from the calculation is made. Calculated results agree well with the experimental data.

Jan 1, 1992

The kinetics of adsorption of gold di-cyanide onto activated carbon has been investigated extensively over the past two decades. These studies have demonstrated that both film and intra-particle mass transfer affect the kinetics. The dominant mechanism of intra-particle mass transfer has not yet been identified. In the work described, surface diffusion and pore diffusion are considered as possible rate-determining mechanisms of intra-particle mass transfer. Mathematical models are described that incorporate film mass transfer and the respective intra-particle mass transfer mechanism with equilibrium described by a Freundlich isotherm. Rate constants of film mass transfer and pore or surface diffusivities were estimated by the fitting of the respective models to experimental carbon adsorption data. The estimated pore diffusivities, after they had been corrected for the porosity and tortuosity of the carbon, were found in most instances to be higher than the molecular diffusivity of dilute gold di-cyanide in aqueous solution. This situation is not physically viable. The surface diffusion mechanism acting in parallel with the pore-diffusion mechanism is thus responsible for the intra-particle transportation of most of the gold.

Jan 1, 1996

By Frederick N. Rhines, Robert F. Mehl

IT has been shown elsewhere1 that the data on the rates of diffusion in solid metals are fragmentary and in many cases unacceptable. As a result, relatively little is known concerning the factors determining rates of diffusion and the variations in these rates with temperature. The first form of Fick's law (equation 1 below), ‡ in which the diffusion coefficient D is assumed invariant with composition, has been recognized for many years as only an approximation. The differential equation representing the second form of Fick's law (equation 4 below) has only recently been integrated by Matano,2 and unfortunately only in cases where a full diffusion-penetration curve (concentration-distance curve) has been obtained can the Matano solution be applied. The proper analysis of diffusion data is thus confined to the data of Grube and Zedele and of Zedele.§ These data are essentially for one temperature alone and do not furnish any information on the variation of the activation heat of diffusion, Q, with concentration: no information exists on the variation of Q with concentration within a singles olid solution field. 11 Much of the argument concerning the properties of metals that determine D and Q has been drawn from data in which variations of the quantities with concentration are unknown, for these data have been taken from experiments that could not furnish this information. Speculation concerning the properties of metals that may be effective in determining D and Q on the basis of data in which the chosen D and Q values are averages over wide concentration ranges of values at particular concentrations, ranges often of 100 per cent, is likely not to be fruitful.

Jan 1, 1938

By Frederick Rhines

IT has been shown elsewhere1 that the data on the rates of diffusion in solid metals are fragmentary and in many cases unacceptable. As a result, relatively little is known concerning the factors determining rates of diffusion and the variations in these rates with temperature. The first form of Fick's law (equation 1 below), ? in which the diffusion coefficient D is assumed invariant with composition, has been recognized for many years as only an approximation. The differential equation representing the second form of Fick's law (equation 4 below) has only recently been integrated by Matano,2 and unfortunately only in cases where a full diffusion-penetration curve (concentration-distance curve) has been obtained can the Matano solution be applied. The proper analysis of diffusion data is thus confined to the data of Grube and Jedele and of Jedele.§ These data are essentially for one temperature alone and do not furnish any information on the variation of the activa-tion heat of diffusion, Q, with concentration: no information exists on the variation of Q with concentration within a singles olid solution field. Much of the argument concerning the properties of metals that deter-mine D and Q has been drawn from data in which variations of the quan-tities with concentration are unknown, for these data- have been taken from experiments that could not furnish this information. Speculation concerning the properties of metals that may be effective in determining D and Q on the basis of data in which the chosen D and Q values are averages over wide concentration ranges of values at particular concen-trations, ranges often of 100 per cent, is likely not to be fruitful.

Jan 1, 1938

By Lars Thomassen, Ernest Kirkendall, Clair Upthegrove

THE amount of research done in the last few years on the subject of diffusion in solid metals is significant of the importance of this problem. To review the literature dealing with diffusion is unnecessary here. Desch1 in 1912 reviewed the work that had been done on diffusion in solids and gave a bibliography of the literature published before that time. Mehl's paper in 19362 is an excellent review of diffusion in metals and contains a large bibliography. Of importance also for its review and bibliography is an article by A. I. Krynitsky.3 While considerable material has appeared in the literature on diffusion in brass, the amount of information is not great compared to that pertaining to some of the other alloys. Most of the information published is of a qualitative nature; that which is quantitative varies considerably. Thus the quantitative determination of the rates of diffusion of copper and zinc in alpha brass by a new method appeared worth while. In the present investigation the rate of diffusion of zinc in approximately the same composition alpha brass has been determined at three temperatures. PROCEDURE The method used consisted of plating copper on a beta brass, heating it to allow diffusion to take place, and measuring the concentration of copper by determining the lattice constant of the alloy. This method is unique in that it uses a beta brass of such a composition that at the temperature at which diffusion takes place the beta brass is saturated with copper. Thus, while the beta brass supplies the zinc, no diffusion takes

Jan 1, 1938

By Ernest Kirkendall

THE amount of research done in the last few years on the subject of diffusion in solid metals is significant of the importance of this problem. To review the literature dealing with diffusion is unnecessary here. Desch1 in 1912 reviewed the work that had been done on diffusion in solids and gave a bibliography of the literature published before that time. Mehl's paper in 1936 2 is an excellent review of diffusion in metals and contains a large bibliography. Of importance also for its review and bibliography is an article by A. I. Krynitsky.3 While considerable material has appeared in the literature on diffusion in brass, the amount of information is not great compared to that pertain-ing to some of the other alloys. Most of the information published is of a qualitative nature; that which is quantitative varies considerably. Thus the quantitative determination of the rates of diffusion of copper and zinc in alpha brass by a new method appeared worth while. In the present investigation the rate of diffusion of zinc in approxi-mately the same composition alpha brass has been determined at three temperatures.

Jan 1, 1938

By L. E. Eary

Many of the major international gold mining companies provide data on rates of greenhouse gas (GHG) emissions as part of their environmental reporting commitments. These data are evaluated by an index defined as the annual GHG emission rate in metric tons, divided by the annual amount of gold produced in grams, and referred to as GHGgold. This paper examines ranges of GHGgold values for a cross section of gold mines as a function of mining method (openpit, underground and combined operation) and ore-processing method (mill, heap leach and combined methods) for reported ranges of operational data, including annual total tons mined, ore processed and gold grade. The evaluation shows that ranges and distributions of rates of GHG emission are approximately similar across different mining methods and ore-processing methods. The data presented in this paper provide the context needed to make comparisons of GHG emissions reported in companies’ annual reports to the ranges reported for the overall gold mining industry.

Jan 1, 2009

By T. E. Leontis, F. N. Rhines

THE oxide scale that forms upon magnesium at elevated temperatures is nonprotective in the sense that the rate of oxidation is constant and thus does not decrease with the growth of the scale as it does with other common metals. This generality was first stated by Pilling and Bedworth1 and has been verified by Suzuki2 and by Scheil.3 Pilling and Bedworth argued that the nonprotective characteristic could be predicted from the fact that magnesium oxide occupies less space than does the metal from which it springs, wherefore the scale is not expected to cover the metal so completely as to exclude all direct access to the atmosphere. Linear oxidation is thought by Scheil to be common to all cases where the reaction occurs at the oxide-metal interface. According to Suzuki,2 the product of high-temperature oxidation in the air is MgO contaminated with no more than traces of a nitride. When the metal is allowed to burn freely a fume composed of cubic crystals of Mg04 is given off. Delavault5 observed that excrescences form upon liquid magnesium and alloys in the course of oxidation. Beyond this it is known that the use of atmospheres containing small quantities of sulphur dioxide6 or carbon dioxide serve to retard the oxidation of solid magnesium and that beryllium7and calcium8 minimize the oxidation of molten magnesium exposed to the air. Many studies have been devoted to the nature and rates of "protective" oxidation, as exemplified by the cases of copper and iron, wherein the rate is characteristically parabolic. The theory of parabolic oxidation is well developed.9 Linear oxidation, on the other hand, has received but little attention and the theories proposed by Pilling and Bedworth and by Scheil have yet to withstand careful examination. There exists no comprehensive survey of the high-temperature oxidation of magnesium (or of any other metal that exhibits linear oxidation) over a broad range of temperature, under a variety of atmospheric conditions and covering a large group of alloys. It has been the purpose of the present investigation to provide such a survey, with the object of gaining a fuller understanding of linear oxidation, especially as applied to magnesium. EXPERIMENTAL PROCEDURE AND RESULTS The experimental studies undertaken were of two kinds: (I) measurement of the rate of oxidation as influenced by the

Jan 1, 1946

By W. A. Anderson, F. N. Rhines, W. A. Johnson

THE rate of the high-temperature oxidation of pure copper has been measured repeatedly by numerous investigators. It appears to be generally agreed: (I) that at constant temperature, after the initial stages of oxidation have been passed and the scale has attained a substantial depth, the film thickness increases in proportion to the square root of the time of oxidation; and (2) that for any given period of oxidation the logarithm of the square of the film thickness is proportional to the reciprocal of the absolute temperature of oxidation.' These relationships are explained upon the basis that the rate of diffusion of copper to the external surface of the film is the controlling factor in establishing the rate of growth. Extensive studies have been devoted also to the mechanism and rates of the early stages of oxidation. There is thus available a reasonably well established theory of the oxidation of pure copper upon which to construct an explanation of the more complex oxidation of copper alloys. Few general principles have as yet emerged from the chaos of observations that have been reported in the field of the oxidation of alloys.2 It is evident, however, that the copper alloys may be divided into two main groups, whose oxidation characteristics are distinguish able. The first group, composed of the alloys with the noble metals, forms substantially pure copper oxide scales; the alloying element is concentrated within the residual metal, and sometimes particles of almost pure noble metal are found in the scales completely surrounded by copper oxide. In the second group, composed of the alloys of copper with the baser metals, the alloying element appears as an oxide in the scale, often in greater concentration than in the alloy itself and sometimes to the exclusion of copper oxide. The oxide scales of the latter class have been found to be made up of one, two, and sometimes more distinguishable layers of which the innermost is often metallic in character, composed of particles of the oxide of the alloying element embedded in essentially pure copper and known as the subscale or zone of internal oxidation. The need for a thorough quantitative study of these modes of oxidation is evident. Since it is apparent that several mechanisms must be cooperating to produce the complex oxide scales found on copper alloys, the analysis of the process into its several simple operations should prove instructive. Fortunately, it is possible experimentally to produce internal oxidation in the absence of an external scale; this permits the isolation and intensive study of one of the steps in the oxidation process. In the present research the rates of internal oxidation of an extensive series of dilute solid solution alloys of copper have been measured and a theory has been developed to predict the observed

Jan 1, 1941

THE problem of reaction rates in the open-hearth process is essentially that of trying to form a fairly clear picture of the "chemical mechanisms" in the bath. Quantitative data on reaction rates would perhaps not be of much practical importance even if they were available; however, what few approximate data there are can be used in combination with data given in Chapters 16 and 17 to sketch a picture of the "chemical mechanics" of the open-hearth process that is consistent with essentially all the present available evidence. The result may later be found incorrect in many details but even so it will illustrate certain useful methods for obtaining a clearer understanding of the process. Consistent with the treatment in Chapter 15, but in simpler terms, we may say that chemical reactions in general involve the following elements or steps: 1. The reacting molecules are mixed together in space in such fashion as to favor collisions among them. 2. Units of what is usually an intermediate molecular arrangement called an activated complex are formed at a certain rate, depending on temperature and concentrations. 3. These activated complex units decompose into the reaction products (this step usually assumed to be so rapid as never to limit the over-all process). 4. In any of these steps, heat energy may have to flow into, or away from, the reaction zone to permit the reaction to proceed. 5. The products of reaction will usually have to move out of the way to permit further reaction. The temperature factor enters mainly through step 2, and its effect is very marked. (What is called temperature is really the mean energy content of all the molecules of the substance involved; at any one temperature a certain proportion of the moleculea will have much higher energy content than the mean value.) Various reaction rates measured at around room tem-

Jan 1, 1951

THE problem of reaction rates in the open-hearth process is essentially that of trying to form a fairly clear picture of the "chemical mechanisms" in the bath. Quantitative data on reaction rates would perhaps not be of much practical importance even if they were available; however, what few approximate data there are can be used in combination with data given in Chapters 16 and 17 to sketch a picture of the "chemical mechanics" of the open-hearth process that is consistent with essentially all the present available evidence. The result may later be found incorrect in many details but even so it will illustrate certain useful methods for obtaining a clearer understanding of the process. Consistent with the treatment in Chapter 15, but in simpler terms, we may say that chemical reactions in general involve the following elements or steps : 1. The reacting molecules are mixed together in space in such fashion as to favor collisions among them. 2. Units of what is usually an intermediate molecular arrangement called an activated complex are formed at a certain rate, depending on temperature and concentrations. 3. .These activated complex units decompose into the reaction products (this step usually assumed to be so rapid as never to limit the over-all process). 4. In any of these steps, heat energy may have to flow into, or away from, the reaction zone to permit the reaction to proceed. 5. The products of reaction will usually have to move out of the way to permit further reaction. The temperature factor enters mainly through step 2, and its effect is very marked. (What is called temperature is really the mean energy content of all the molecules of the substance involved; at any one temperature a certain proportion of the molecules will have much higher energy content than the mean value.) Various reaction rates measured at around room tem-

Jan 1, 1964

By Pascale St-Germain, Michael Li, Lionel J. J. Catalan

The oxygen flux into water-covered reactive sulphidic tailings is required for evaluating the long-term performance and predicting the quality of engineered shallow water covers. This information can also serve as an input to the design of water covers for reactive tailings decommissioning. This paper describes some dissolved oxygen (DO) profiles recently measured in the field across the tailings/water interface and oxygen fluxes derived from these profiles. These fluxes are compared with previously reported flux values from similar field measurements. Techniques and pitfalls for measuring DO profiles and calculating oxygen fluxes are also discussed.

Jan 1, 2000