Search Documents

By J. H. Swisher

An experimental study has been made of the possible mechanisms for foam stability in the system CaO-SiO2-Cr2O3, where Cr2O3is the foaming agent. The degree of lowering of surface tension by Cr2O3 was determined at 1600 "C for high -silica melts. Measurements were also made of foam stability under standardized conditions. The results of the two sets of measurements then were correlated by applying the Gibbs and Marangoni theories of film elasticity. It was demonstrated that the Marangoni elasticity effect is probably the largest single contributor to foam stability, although the high uiscosity of' silicate melts makes some contribution in controlling the rate of drainage of liquid from bubble lamellae. ThE tendency of metallurgical slags to foam has frequently been observed during steel-refining operations. In the open-hearth furnace,this tendency is considered undesirable because it slows down the rate of heat transfer from the burners to the molten-metal bath. On the other hand, it is sometimes desirable to have a "foamy" slag in the basic oxygen converter.' A more effective blanket over the steel bath is made by a "foamy" slag, and loss in yield of metal due to splashing is minimized. In addition, a flush slag can be removed more easily in this condition. Since slag-foaming problems in the field have been attacked largely on an empirical basis, it appeared desirable to obtain a better basic understanding of the mechanism of foam stability. The experimental work was directed almost entirely toward the behavior of Cr2O3 as the foaming agent in CaO-SiO,-Cr2O3 melts. In the first stage of the investigation, the degree of lowering of surface tension by Cr2O3 was determined at 1600°C. The second stage consisted of measuring foam stabilities under standardized conditions. The two sets of experimental results then were correlated by applying various theories of foam stability. For convenience in interpreting the surface-tension and foam-stability results reported here, a portion of the CaO-SiO2-Cr2O3 phase diagram2 is reproduced in Fig. 1. EXPERIMENTAL 1) Surface-Tension Measurements. Very little information is available in the literature on the lowering of surface tension of slags by foaming agents. Kozakevitch 3 mentioned that the addition of 1.5 pct Cr2O3 lowered the surface tension of FeO slightly. In another system, some data on the lowering of surface tension of foaming slags by P2O5 were reported by Cooper and Kitchener.4 The technique used for the surface-tension measurements was the maximum bubble-pressure method,' using a single tube immersed to various depths in the melt. This method has been used extensively in high-temperature systems, such as in liquid metals, slags, and glasses.6,7 It has the advantage that the contact angle between the liquid and the tube material need not be known. The equation used for calculating surface-tension values from maximum bubble-pressure measurements is the Schroedinger equatioq5 which can be written as follows:

Jan 1, 1964

By K. L. Komarek

Based on theoretical and experimental evidence a discussion follows of the behavior of phosphorus -bearing iron ores in the R-N Direct Reduction Process and suggestions are made of methods of reducing the amount of phosphorus in the metallic end product. In ferrous metallurgy a direct reduction process is one in which iron ores are reduced to metallic iron with gaseous or solid reductants without the appearance of a liquid phase. A number of attractive features have induced several companies and government agencies to invest in the development of direct reduction processes. A summary of all direct reduction processes up to 1954 has been given by Barrett,' and Wiberg,2 and Willems3 have reviewed the most recent developments in this rapidly expanding field. Many difficulties have been encountered in direct reduction processes and the nature of these difficulties has varied from process to process. One problem common to almost all of them is the removal of phosphorus which is one of the reasons for the rather pessimistic outlook given by some government publications4'5 to direct reduction processes. In this paper an attempt is made to give a theoretical explanation of the variations in phosphorus removal observed in the R-NY Direct Reduction Process. However, many conclusions are general enough to be applicable to other processes. Most iron ores treated by the R-N process yield products lower in phosphorus than the original ore. A qualitative account of the factors has been given by Stewart, Reed, and Herasymenkoe but the erratic removal of phosphorus from some ores and the general importance of this problem make a more careful analysis of the theoretical aspects desirable. In the R-N process mixed ore or balled fines, ex-

Jan 1, 1963

By P. T. Carter, A. B. Murad, H. B. Bell

N. A. Gokcen (Michigan College of Mining and Technology, Houghton, Mich.)—The activities of silica, represented in Fig. 5 for the systems MnO-SiO2 and CaO-SiO2, are in disagreement with the established binary phase diagrams. At Ns102 = 0.50 in MnO-SiO2, and at Ns102, = 0.65 in CaO-SiO2, each binary system is saturated with respect to silica at 1550°C, and therefore as102, is unity in each case. The curves for as102 (FeO-SiO2) and as102, (MnO-SiO,) should nearly co-

Jan 1, 1953

By J. P. Morris

PREVIOUS investigations1,2 have shown that alloying elements in liquid iron influence the thermodynamic activity of sulphur and thereby affect the partition of sulphur between metal and slag in the desulphurization process. For example, the greater efficiency of desulphurization in the blast furnace as compared to the open hearth can be attributed in part to a higher level of sulphur activity in blast-furnace metal due to the higher concentration of carbon and silicon. In the present investigation, a short study was made of the influence of manganese on the activity of sulphur in liquid iron and iron-carbon alloys. In contrast to carbon and silicon, manganese was found to decrease the activity coefficient of sulphur; and in iron-carbon alloys it counteracts to some extent the influence of carbon. However, at manganese concentrations normally present in the blast furnace or open hearth, the effect of manganese is small. Since manganese sulphide has a limited solubility in iron, manganese can act, under certain conditions as a desulphurizing agent. Considerable data on the manganese-sulphur product in carbon-saturated melts were obtained in the investigation and have been included in this report. The experimental procedure was the same as that used in the earlier investigations on the effect of silicon' and carbon' on sulphur activity. Briefly, the method was as follows: The molten alloy, contained in a graphite or sintered alumina crucible, was brought to equilibrium at a constant temperature with a mixture of hydrogen and hydrogen sulphide of constant composition by bubbling the gas through the metal. Samples of' the melt were taken for analysis at regular intervals by suction through a 2 to 3 mm bore silica tube dipped into the metal. The experiments were run in a graphite spiral resistance furnace with melts weighing 50 to 60 g. The gas bubbling tubes were made of sintered alumina and were 5/16 in. OD, 1/16 in. ID, and 24 in. long. Equilibrium was assumed to have been attained when the sulphur content of the liquid metal reached a constant value. During an experiment there was a rapid loss of manganese from the melt by volatilization. To offset this loss, small additions of manganese were made periodically. The rate of manganese addition needed to maintain a constant manganese concentration was determined in preliminary tests. In all of the experiments, deposits of manganese sulphide formed above the melts in a cooler region of the furnace. Apparently, these deposits resulted from a reaction between manganese vapor and hydrogen sulphide in the gas. To prove that manganese sulphide did not volatilize from the melts to a measurable extent, an experiment was run in which helium was bubbled through liquid iron containing both manganese and sulphur. Although manganese volatilized rapidly in this test, there was no appreciable loss of sulphur. Volatilization of manganese sulphide from a melt would have led to an apparent equilibrium condition in which the sulphur content of the metal was lower than the true equilibrium value. The experimental results are shown in the first seven columns of Table I. The data in the last two columns were obtained from the previous work on the effect of carbon' and show what the results would have been in the absence of manganese but with temperature, gas composition, and carbon content of the metal remaining the same. Comparison of the last four columns show that, in the presence of manganese, the sulphur content of the metal increased at equilibrium and the activity coefficient of sulphur decreased. However, the results show that, for manganese concentrations below 3 pct, the effect of manganese is small. The values for activity coefficient of sulphur given in Table I were calculated from the following relations: S (in liquid metal) + H2 (gas) = H2S (gas) [l] K ph2s/?s X %S X phg = 0.00251 [2] where K is the equilibrium constant for the reaction, PH2S and ph2 are the partial pressures of hydrogen sulphide and hydrogen, respectively, and ?s is the activity coefficient of sulphur. The standard state for sulphur was taken to be a 1 pct solution of sulphur in pure iron. The numerical value for K at 1600°C was determined in the earlier work. For the purpose of showing graphically the results of the tests run at 1600°C, the activity coefficients of sulphur were recalculated so as to correspond to a manganese concentration in the metal of 2 pct in each case. In the calculation it was assumed that the increase in sulphur content of the metal at equilibrium caused by the presence of manganese

Jan 1, 1953

By D. J. Carney, C. W. Boquist, E. C. Rudolphy

Effect of variations in sinter feed composition on sinter strength, bulk density, re-ducibility, chemical composition, and microstructure were determined by sintering experimental samples on a production sintering machine. Increasing amounts of roll scale, ore fines, return fines, and blast furnace slag were most beneficial to feed permeability, sinter bulk density, and strength. Burnt lime additions improved feed permeability but were not beneficial to sinter strength or bulk density. Sinter reducibility was adversely affected by all additives. DEVELOPMENT of methods for evaluating sinter quality, which would in some way predict the behavior of the sinter during charging and smelting in the blast furnace, has been given considerable attention in recent years. In a previous investigation at South Works of the United States Steel Corp., standard sinter sampling and testing procedures were developed.1,2 By modifying the sinter sampling device, a method of sintering experimental mix sinter samples upon a production Dwight-Lloyd sintering machine was also developed. This technique afforded a rapid and controlled method of investigating the effects of the various raw materials and additives on sinter quality and was used in this present investigation. Since the beginning of the present study in 1953, the results of numerous sinter investigations have been published, most of which were concerned with production tests of iron ore sinter, both here and abroad. Three groups of investigators reported results of experimental sinter studies that were related to this investigation. Voice et al.3 studied the effects of controlled variables on sinter quality by producing and testing experimental Northants iron ore sinter using an experimental sintering unit. Mor-rissey and Powers' determined the relationship between iron ore sinter quality and the moisture and coke content using a small laboratory sintering system. Burlingame et al.5 studied the effects of "additives" upon iron ore sinter using a laboratory sintering apparatus and laboratory grade raw materials. At South Works, it was considered desirable to study the effects of sinter mix composition and additives upon the quality of a flue dust-base sinter produced on a production sintering unit. Extrapolation of controlled laboratory test data to sintering plant operation lacking such precise control is not altogether satisfactory. Therefore, the present study was conducted in a manner which approximated production conditions as closely as possible. The raw materials used were those commonly encoun- tered in the production of flue dust and flue dust ore-type sinters and these were varied within extremes encountered in this type of sinter production. Experimental Procedure The experimental sinters were produced from 100 lb mixtures of sinter feed. The principal raw materials and additives used, their particle size, and approximate chemical composition are listed in Table I. The mixing of the raw materials was accomplished by means of a miniature single shaft pug mill shown in Fig, 1. The use of the pug mill as a mixer was decidea upon after encountering difficulty in reproducing the mixing and chopping effect of the sinter plant pug mill with other types of available small mixers. The miniature pug mill was constructed, consisting of 31/2x2x1/4 in, blades spaced 3 in. apart along a 3 ft shaft. Preliminary tests were run with this small mixer to establish the proper rotation speed and the required number of passes through the pug mill to thoroughly mix and distribute all the raw materials in a manner approximating the production Pug mill- Although the effects of varying the mosture content were determined in one particular series of tests, the amount of moisture added was changed as the composition of the experimental mix was varied. The aim in making water additions was to achieve a permeability as high as possible for each particular

Jan 1, 1956

By E. T. Turkdogan, P. Grieveson, J. F. Beisler

Jan 1, 1963

By Renato G. Bautista, Theodore D. Tiemann

A kinetic study of the hydrogen reduction of taconite from the Wisconsin Gogebic range was made over the temperature range from 500° to 1000°C on eleven size fractions from 4 to 150 mesh. Two stages of reduction were observed, a rapid initial reaction followed by a slower reaction presumably taking place at an internal receding FexO-Fe interface. Calculated mean activation energies for the two reactions were 7800 and 14,600 cal per mole respectively. In recent years there has been an increased interest in the direct reduction of iron oxide ores to metallic iron by means of gaseous reducing agents such as hydrogen and carbon monoxide.1,2 These investigations have been motivated by the desire to develop a process that will by-pass the blast furnace in the production of steel. The majority of these processes have been developed to produce metallic iron by direct reduction from high-grade iron oxide ores.3"5 Very little work has been done on the low-grade siliceous iron oxide ores.6"8 The work reported here is directed principally towards the fundamental aspect of the reduction reactions of siliceous iron oxide ores, since the practical aspects of the gaseous reductant process were discussed previously. The ore used in the investigation was obtained originally from the United States Bureau of Mines10 trench sample of the Yale member of the Wisconsin Gogebic range iron formation. The Yale taconite has an average analysis of 28.2 pct Fe and approximately 50 pct SiO2. Chemically, these nonmagnetic taconites contain on the average about 53 pct silica and 30 pct Fe. An average analysis calculated fron the USBM10 figures for a composite of the five members (Norrie, Plymouth, Pence, Pabst, and ale) of the iron formation is given in Table I. Mineralogically, based on previous X-ray diffraction and other studies, the principal minerals are hematite (Fe2O3), geothite (Fe2O3.H2O), and quartz (SiO2). Minor amounts of iron containing silicates, siderite (FeCO3) and magnetite (FeO. Fe2O3) are present.10,11 The iron minerals and the quartz are finely disseminated requiring extremely fine grinding for liberation. For the experimental work, the ore sample was screened into a number of size fractions, the analyses and densities of which are given in Table II. EXPERIMENTAL PROCEDURE The reduction experiments were carried out in a 24 in. by 2 in. ID nichrome-wound vertical-tube furnace mounted on a stand. A 1 1/2 in. OD zirconium-oxide combustion tube was used inside the furnace to contain the atmosphere. To the top of this combustion tube was joined a pyrex ground-glass joint to which was attached a glass bulb with a small (1.0 mm) opening at the center, and with two outlets controlled with a stopcock on each side. A pyrex-glass joint with connections to three stopcock joints for introducing hydrogen, nitrogen, and mixtures of hydrogen and nitrogen gas was joined to the tapered bottom of the combustion tube. The sized ore fractions were contained in a 1 in. diameter by 1 1/2 in. 150-mesh nickel screen basket. The basket was suspended in the furnace from a balance by means of a supporting nickel wire which hung freely inside the combustion tube. The furnace temperature was controlled by a Leeds and Northrup Speedomax Type G controller, connected to a chromel-alumel thermocouple placed

Jan 1, 1962

By G. R. St. Pierre, A. J. Wilhelem

In connection with the reduction of hematite or magnetite to metallic iron, it appeared desirable to study the rate of reduction of each oxide to the next lower oxide under conditions which excluded all other condensed phases. For this purpose, pellets of Fe,O,, Fe,O,, and oFeOo were prepared. A gas train for the preparation of Ar-Hz-H20 mixtures was employed to establish a continuous flow of a controlled atmosphere over a pellet suspended on a balance. In this manner the following individual reduction steps could be studied: For example, pellets of hematite were reduced solely to magnetite by adjusting the gas atmosphere such that it was oxidizing to wustite. In other words, the reaction was complete when the hematite pellet had been totally converted to magnetite. The pellets were prepared from Baker Chemical ferric oxide. The ferric oxide powder was moistened and handrolled. Air sintering at 950°C produced Fe,0, pellets with a density of 3.65 g per cm3. The pellets ranged in size from 0.6 to 1.2 cm diam. The magnetite and

Jan 1, 1962

By K. C. Mills, E. T. Turkdogan

A number of investigators1 6 have noted the presence of a liquid miscibility gap in the Fe-Sn binary system. However, the first attempt to measure the

Jan 1, 1964

By Ford R. Bryan, Edward F. Runge

BECAUSE of the need for ductile heat resistant alloys of non-strategic composition, there has been metallurgical development of Fe-A1 alloys possessing improved ductility and hot strength, together with high oxidation resistance. Iron and alu- minum form solid solutions up to approximately 35 pct Al. Alloys in the 8 to 12 pct A1 range are characterized by excellent oxidation resistance, high electrical resistivity' and, when appropriately alloyed, have creep rupture strength equivalent to that of the austenitic stainless steels.' At higher aluminum levels, the magnetic properties are of considerable interest. Nachman and Buehler" have recently reported on the desirable magnetic characteristics of the 16 pct alloy.

Jan 1, 1957

By Donald J. Knight

HEAT Treatment at 1500' F of a mild steel containing 0.1 pct C, in an atmosphere which is oxidizing to both carbon and iron, results in the progressive oxidation of the metal surface with little or no change in the carbon content of the underlying metal. Further heat treatment of the scaled metal in either a neutral atmosphere or in a vacuum may or may not result in the decarburization of the metal depending upon the physical nature of the scale. It is apparent that if a continuous layer of oxide is present on the steel surface, the reaction OScale + Cmetal Cogas cannot progress since the SO formed gas would be unable to leave the oxide/metal interface. Thus, in order for the reaction to progress, the oxide must be cracked or porous. Vacuum heat treatment at 1500" F of samples with a thick continuous oxide scale showed no decarburization of the steel. However, when cracks were introduced mechanically into the scale prior to the vacuum heat treatment notable decarburization of the metal resulted and a structure as shown by Fig. 1 obtained, i.e., reduction of the crack walls to ferrite. With reference to the diagram of Fig. 2, it would appear that a mechanism of the following type takes place. Carbon atoms arriving at an oxide/metal/void interface, such as 'A', Fig. 2(a), can combine with oxygen atoms from the scale and leave the reaction site as Cogas thereby reducing the oxide to metal. On a greatly magnified scale, Fig. 2(b),this will appear as a ferrite projection along the crack wall. Carbon atoms entering this projection can react with oxygen atoms at point 'C', which is a new interface, and so on leading to a progressive growth of the ferrite along the crack wall and to the surface, Figs. 2 (c) and 1. It would appear that the only means by which thickening of the ferrite film can take place is by a diffusion of oxygen through the ferrite film to react with carbon at the newly formed ferrite/ void interface. Since the diffusion rate of carbon is reportedly much greater than that of oxygen, and since there is a low probability factor of oxygen and carbon atoms arriving simultaneously at the same site on the ferritehoid interface, there will be a tendency for more rapid lengthening than thickening of the ferrite layer, as is observed.

Jan 1, 1962

By S. Ramachandran, N. J. Grant, T. B. King

MANY investigations of the rate of the sulfur transfer reaction between carbon-saturated iron and blast furnace type slags have been made." It is evident that the reaction is complex, the rate being affected by the presence of elements dissolved in the metal that are readily oxidized and therefore capable of existing in the slag phase. Thus Goldman, Derge, and Philbrook- have shown that carbon, silicon, manganese, and aluminum, in order of increasing effectiveness, accelerate sulfur transfer from iron containing these elements to blast furnace type slags. Quantitative information is still, however, not available on the relation between what have been termed side reactions, such as silicon transfer and CO evolution, and the sulfur transfer reaction itself. In other words, the stoichiometry of the reaction has not been investigated. In the present investigation, the transfer of all reacting elements and the evolution of CO have been measured simultaneously in order to establish the mechanism of the reaction which occurs in practice. Information of this nature cannot be deduced from equilibrium studies. It should be pointed out that in kinetic studies of this type quantitative conclusions are applicable only to the system studied. This restriction should be borne in mind when attempts are made to compare results from different investigations. Apparatus The apparatus used enables slag and metal samples to be taken at frequent intervals and also provides a continuous record of the amount of gas evolved. A sketch of the apparatus is given in Fig. 1. It may be considered in three sections: 1) furnace section, 2) blank volume section, and 3) pressure measuring section. The furnace section is shown in detail in Fig. 2. It consists of two graphite crucibles, C and D, super-

Jan 1, 1957

By V. Koump, T. F. Perzak, R. G. Olsson

Jan 1, 1965

By B. M. Larsen

A discussion based on three commercial furnace tests and electrical analogue calculations is presented. It shows that while regenerator efficiency is mainly dependent on loading or relative amount of heat exchange surface plus the heat transfer coefficients as effected by flow velocity, the actual air preheat temperature can be high or low, largely independent of regenerator efficiency, mainly due to the diluting or unbalancing effects of cold air leakage into various parts of the furnace system. THERE are many signs of a renewal of interest in the heat regeneration aspect of the open hearth process, among them being the recent paper by Marsh,' the introduction of auxiliary checkers in the stacks of the Isley furnace design, and a number of recent installations of two-pass checkers in new and old furnaces. However, there are also signs of yielding to the usual temptation of oversimplifying a problem. Faced with the job of obtaining better draft on a furnace, for example, a good designer always recognizes that focusing attention on some one factor, such as height of the stack or capacity of the exhaust fan, does not make his problem any easier; rather he must look at the whole system, including such items as valve resistances, bends in the flues, and flow resistance in the waste heat boiler; then he must make his design in relation to the available draft so as to avoid any serious bottleneck in the system. Yet this example is really much simpler than the problem of air preheating, and again, the latter problem is not really made easier by concentrating on air temperature in uptakes and on the more obvious methods for making this air as hot as possible. Also to be considered are such things as the total amount of air needed theoretically for complete combustion at any selected fuel rate, together with that needed for oxygen absorbed into the bath and for burning the combustible gases given out from the bath, plus some excess air. Furthermore, how does this total air requirement relate to the regenerator efficiency at various loadings? How much of the total air equivalent in stack gases will come from preheated air passed through the whole length of the incoming regenerator and how much from air leakage into various zones of the whole furnace system? Does the effect of leakage air differ depending on whether it leaks into the ingoing regenerator, the furnace above floor level, the outgoing regenerator, or the stack zone? Over a number of years we have in this Laboratory experimented with methods for measuring hot gas temperatures; we have measured, approximately, the efficiency of a few regenerators on commercial furnaces and we have developed an electrical analogue' for calculations of regenerator efficiency. The whole problem is too complex to cover in one paper even with a more complete background of data than we possess, but we can attempt here to clarify certain aspects in a general way, hoping to assist specific plant studies on individual furnaces. Some of our earlier experience has been incorporated into chaps. 4, 19, 20, and 21 in the book "Basic Open Hearth Steelmaking,"" and on the assumption that this text is available to most readers, this discussion has been shortened by references to that book. The most recent design of a flowing-gas thermocouple which we are now using for measurement

Jan 1, 1955

By N. A. Gokcen, John Chipman

D. C. Hilty (Union Carbide and Carbon Research Laboratories, Niagara Falls, N. Y.)—This paper is a very nicely detailed analysis of a difficult problem. I would like to point out that the results that Mr. Crafts and I published a few years ago had no reference to activity, or anything else of a similar nature; our results were strictly empirical. It is quite gratifying that we now have a case where results involving activity coefficients and results derived from direct observations on actual steel melts are practically identical. When two different laboratories, working from two entirely different approaches, come out with results in such good agreement in their major significance, that is an achievement. It is something that was not possible 15 or 20 years ago. There is one question I would like to ask Dr. Chip-man. It has to do with a very minor point of disagreement in these results. When we reported the kink in the Si-O solubility curve I think you may recall that it came at the different temperature levels at about the order of 0.015 to 0.03 pct 0 and 0.03 to 0.07 pct Si—we also pointed out that we had difficulty in obtaining data at that level, although we finally did get some. I note in going through the data for the present paper, that there are no samples in those particular silicon and oxygen ranges. I wonder if that was purely accidental or was there a reason for it. D. E. Babcock (Republic Steel Corp., Youngstown, Ohio)—Mr. Hilty, do you have any explanation for that discrepancy between Dr. Chipman's curve and your own Mr. Hilty—Our explanation for it at that time was that for some reason our system probably was not in true equilibrium with SiO, that is, in equilibrium with the silica crucible at that level. We did observe, however, that that was the level at which both the metal and the slag became saturated with SiO,. On the average, in studying inclusion formation in small ingots permitted to solidify normally from the molten state, we observed pure silica inclusions at silicon contents over about 0.05 pct and FeO type inclusions at silicon

Jan 1, 1953

By N. A. Gokeen, M. Ohtani

EFFECT of elements on the solubility of carbon in liquid iron is useful in calculating and correlating a number of thermodynamic properties as shown elsewhere in detail.' Kitchener, Bockris, and spratt2, and later Turkdogan and Hancock3 have investigated the effect of sulfur on the solubility of carbon at various temperatures and concentrations. For any chosen sulfur concentration, the solubility of carbon reported by Kitchener et al. is considerably lower than that by Turkdogan and Hancock. It was therefore felt that a reinvestigation of this problem was necessary. EXPERIMENTAL METHOD An alloy of Fe-C-S .was prepared with electrolytic iron and ferrous sulfide melted by induction in a graphite crucible, 4 in. high 1 1/2 in. ID under a CO-atmosphere. The temperature, held at 1500" ± 5°C in all experiments, was measured with a Pt-Pt + 10 pct Rh thermocouple immersed into the melt. In order to assure saturation with carbon, the melt was stirred with a graphite rod. After approximately 1 hr at 1500 °C, a sample was obtained by sucking the melt into a silica tube, 4 mm ID. The sample was then analyzed for carbon and sulfur by usual methods. RESULTS The results are presented in Table I and plotted in Fig. 1 with the individual values of Turkdogan and Hancock.3 Scattering in the data is equivalent to 3 pct or less in carbon analysis. The broken line represents the empirical equation obtained by Kitchener et al. from their data. It is evident that the present data are in good agreement with those of the former investigators but in disagreement with the latter. The cause for this discrepancy cannot be readily offered since the experimental methods in the three investigations were nearly identical. Additional evidence corroborating the author's results may be presented in the following manner. The difference between the solubilities of carbon in the ternary Fe-C-X melt with a small concentration of any element X, and in the binary Fe-C melt is %?C = %CIII-%CII [1] where %?C is the change in solubility, and %CIII and %CII are the solubilities in the ternary and the binary systems respectively. The value of %Cii

Jan 1, 1961

By T. L. Joseph

A study is made of the amount of solution loss necessary to maintain the reducing power of the gas stream in the blast furnace. Curves are presented to show the effect of solution loss, moisture in the blast, and carbon dioxide from the flux on the nitrogen in the THE blast furnace process is based upon the counter flow of gases and solids. As CO, N, and H, flow upward from the combustion zones, oxygen is acquired from the descending charge. In the reduction of iron ore, a portion of CO is converted to CO, and similarly a portion of H, is converted to water vapor. The inert N,, from the air used in combustion, passes through the furnace with little change. Its concentration is, however, decreased by reactions such as direct reduction and solution loss which increase the volume of CO in the gas stream; Similarly the evolution of C02 from the limestone also dilutes the nitrogen. he purpose of this paper is to illustrate an idealized and simplified method of studying furnace processes by following changes in the gas phase between the tuyeres and the stock line. A more specific objective is to evaluate the effect of solution loss upon the CO/CO, ratio in that region of the furnace in which FeO is reduced to metallic iron. This last stage of reduction requires relatively high CO/CO, ratios to exceed the equilibrium requirements. Solution loss or the reaction of COZ with C to produce CO has a pronounced effect upon the ratio of the carbon gases and is necessary to maintain the reducing power of the gas stream if the consumption of coke is low. It will be explained later that indirect reduction followed by solution loss is stoichiometri-cally equivalent to direct reduction. Calculations will be made to show how the composition of the gas in the region of the mantle varies with coke consumption and with different amounts of solution loss. Such calculations show the condi- tions under which gasification of C with oxygen in the charge is needed to maintain the reducing power of the gas. Equilibrium conditions for FeO and the carbon gases will be used to establish a minimum CO/CO, ratio below which reduction will not proceed. The manner in which carbon is gasified in the furnace, at the tuyeres with oxygen in the air or above the tuyeres with oxygen from the charge, will be a basic feature of all calculations. It is hoped that greater interest in the use of top gas as a means of following furnace reactions will be aroused by the calculations and generalized curves which are presented. Bosh Gas Equations Subject to some alteration by the amount of moisture in the blast and by direct reduction, the gas leaving the combustion zones of a blast furnace has a definite composition. Because a relatively small amount of oxygen is acquired from the charge in the bosh and in the crucible, the products of combustion undergo little change until they enter the shaft. Bosh gas is, therefore, essentially the products of combustion of carbon in a deep fuel bed with air. The relative weights and volumes of reacting materials are expressed by the equation: 2~ + 0? + 3.76N, = 2C0 $ 3.76NZ [I] Air Bosh Gas -air = 79% N? = 3.76) 21% 02 Starting with a known mass of C consumed largely by air, Eq 1, but partly by water vapor, Eq 2, the volume and C + H2O = CO $ H? [21 composition of the bosh gas can be calculated and subsequent changes followed as reactions take place at various elevations in the furnace. As shown in

Jan 1, 1952

By D. J. Carney, E. Van Meter, J. J. Oravec

A study was made of combustion-air temperatures and factors affecting air temperatures in the open-hearth regenerative systems. Air-temperature surveys in the regenerative system revealed marked thermal gradients in the air above the checkers. The design of the fantail-uptake region plays a prominent part in increasing the heat recovery of the regenerative system. THE efficiency of the open-hearth regenerative system is one of the most important factors affecting open-hearth performance. Until recently, this factor has not received the attention in the literature given to many other items affecting performance, such as the type of charge, speed of charging, and the mechanical equipment of the open hearth. J. S. Marsh' emphasized the importance of the flame temperature and its dependence upon the combustion-air temperature. By means of measured air temperatures in open-hearth furnaces, data were presented which showed a remarkable degree of correlation between production rate and combustion-air temperature. This correlation was extremely good in view of the numerous factors, other than air temperature, which affect open-hearth production rates. In Marsh's work, a 100°F increase in air temperature reduced the heat time by approximately 45 min. Realizing the importance of combustion-air temperature, it is desirable to know which factors control the regenerative efficiency of the open-hearth furnace. B. M. Larsen recently discussed this subject.' The present paper illustrates a few of the more important items that affect regenerative efficiency and combustion-air temperature. In the latter part of 1951, a study of open-hearth combustion-air temperatures was begun at the South Works of the United States Steel Corp. In the initial work at open-hearth shop X, which produces low carbon steel products, temperatures were measured in the uptake in a manner similar to that used by Marsh' and the results obtained were very similar to the Bethlehem data. When it was decided to expand the study of combustion-air temperatures, open-hearth shop Y was selected because of the greater variety of furnace-design features, types of steel produced, and firing rates used. With the use of aspirating thermocouples, continuous gas analyzers, thermocouple and optical pyrometers, a study was made of: 1—effect of combustion-air temperature on open-hearth production rate, 2—thermal gradients present in various zones of the regenerative system, 3—effect of furnace-design variations on air temperature and heat recovery, 4-—effect of furnace-operating variables on heat recovery, and 5—variation in heat recovery with furnace age during the normal furnace campaign. Data collected on individual heats at 15 min intervals included air-flow rate, firing rate, checker temperature, combustion-air temperature, and furnace pressure. These data were collected on approximately 230 heats of steel. In addition, information was obtained at random on air infiltration and combustion-gas compositions. The data gathered have shown the desirability of closer control of open-hearth firing practices, a need for reducing air infiltration in the uptake zones, and a need for further study of design of checkers and of uptake-fantail areas. Equipment Air is practically a nonradiating medium. Consequently, in the measurement of air temperatures, the principle of heat conduction must be used rather than heat radiation. For this reason, aspirating-type thermocouple pyrometers normally are used to measure air temperatures. With these devices, air

Jan 1, 1956

By Tasuku Fuwa, John Chipman

Equilibrium data on the reactions of gases with carbon and oxygen dissolved in liquid iron are reviewed and correlated. A source of error in oxygen analysis of graphitic samples is exposed. New experimental data on the oxygen content of high -carbon iron in equilibrium with carbon monoxide indicate that the activity coefficient of oxygen is decreased by additions of carbon. The carbon-oxygen product decreases slightly with increasing carbon content. In recent years a number of investigations have been reported dealing with the equilibria between carbon and oxygen in liquid iron and gases containing carbon oxides. The laboratory study of these reactions dates back to 1931 with the publication of a paper by Vacher and Hamilton' on "The Carbon-Oxygen Equilibrium in Liquid Iron". The principal object of this study was to obtain data on the reaction shown by Eq. [3] below; their data and others by vacherZ permit evaluation of the other equilibrium constants as well. Subsequent studies have been reported by Matoba, Phragmen and Kalling and by Marshall and Chipman.5 The equilibria may be expressed by the following three equations: C + CO,= 2CO;Kl = Pc° [1] 0-+CO = CO,;K2=-P co, "0.PCO c + O = CO; K3 = In the equilibrium constants, ac and a0 are taken as equal to [% C] and [% 0] respectively in the infinitely dilute solution. At finite concentrations an activity coefficient is introduced such that ac =fc [%C], and so forth. It is to be noted that these equations represent only two independent relations, the third being derivable from any two. Richardson and Dennis have determined the conditions of equilibrium in reaction [I] at temperatures of 1560" to 1760°C. Their results have been confirmed by Rist and chipman7 who have shown how the data may be extended to cover the entire range of liquid compositions at temperatures from the eutectic up to 1760°C. An approximate confirmation has been reported by Fuwa and chipman.' These investigations also established the activity coefficient of carbon which was shown to increase rather rapidly with increasing concentration. For the very dilute solutions the value of Kl is expressed in the equation: log^i = - 7280/T+ 6.65 This equation leads to a value of Kl = 430 at 1540° C in excellent agreement with the average value of Marshall and Chipman.5 It is shown as line 1 in Fig. 1 together with the experimental observations. In the case of reaction [2] the direct experimental results can be supplemented by observations on the corresponding reaction with hydrogen, namely reaction [4]:

Jan 1, 1961

By J. M. Uys, T. B. King

WalSH, Chipman, King, and rant' have measured the water content (as hydrogen) of actual steel-making slags. An average water content of 290 ppm was found for basic open-hearth tapping slags and 114 ppm for acid open-hearth slags. Upon equilibration of these slags at 1550°C with a 25 pct H20-75 pct Nz atmosphere, the water content increased to about 410 and 300 ppm for the basic and acid slags, respectively. Walsh et al. concluded that an acid slag was thus relatively far removed from equilibrium, and that basic slags showed a closer approach to equilibrium, with the water vapor in the furnace atmosphere. Herasymenko2 contended that these conclusions were unjustified, as the oxygen pressure used in the equilibration experiments, ;bout 5 x X atm, was quite different from that found in the furnace. Consequently, during the experiments the slag composition would have changed due to oxidation of ferrous iron. As an extension of Walsh's work and to attempt to clarify this matter, the solubility of water in a basic open-hearth slag was measured as a function of oxygen pressure. Similar measurements were also made on synthetic silicates in the "Fe0"-Fe203-SiO, system. The experimental technique has been described previously by Walsh et a1.l and Uys and King.3 Samples of the basic open-hearth finishing slag, contained in 10-cc platinum crucibles, were equilibrated at 1550°C with atmospheres of different oxygen pressure but constant water-vapor pressure, Ph~o = 0.192 atm. Calculations, as well as measurements, indicate that this figure approximates the water pressure of the combustion gases in a steam-atomized, oil-fired open hearth. Oxygen pressures in the open hearth can vary from 10"2 atm in the combustion gases to between l0-' and 10" atm in the steel bath. The former figure depends on the combustion practice and the latter on the carbon content and temperature of the bath. The oxygen pressure of the slag should lie somewhere between these extremes and is expected to be closer to that of the steel bath than that of the combustion gases. Oxygen pressures were therefore varied between 10" and 6 x l0 atm. At the lowest pressure the slag "puffed up" when quenched (indicating possible loss of water) so experiments were not conducted at lower oxygen pressures. The results are shown in Fig. 1, which includes the water content of the slag "as sampled". The results show that the water content of the slag increased appreciably on equilibration with water vapor at 0.192 atm pressure and that the water solubility apparently decreases with increased oxygen pressure. The solubilities found are comparable to those of the Li20-Ca0-Si02 system.3 Work with synthetic slags in the "Fe0"-Fe203-SiOz system was performed at 1500" C, with Ph20 = 0.192 atrn and for oxygen pressures varying between 10"2 and 10-lo atm. Samples for chemical analysis were prepared as described by Larson.4 The results are shown in Fig. 2. Some low-silica melts tested at low oxygen pressures "puffed up" when quenched and analyzed less than 100 ppm water; these results are not included in Fig. 2. The melts containing 40 mol pct silica also showed a tendency to "puff up" during the quench, when they were tested at the lowest oxygen pressure. These results indicate that, at constant silica content, the solubility of water decreases somewhat with increased oxygen pressure. The effect is, however, small considering the wide range of oxygen pressures studied. Also, at constant oxygen pressure (above about lom5 atm) the solubility increases

Jan 1, 1963