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By H. O. HOPMAN

(Canal Zone Meeting, November, 1910.) I. INTRODUCTION. THE substance of this paper was prepared for the Seventh International Congress of Applied Chemistry, held in London, May, 1909, under the title, Some Developments in Blast-Roasting. In the absence of the author, a -short abstract of the paper was read, and the abstract only will appear in the proceedings of the congress. The present paper has been partly rewritten and considerably enlarged by information gained since the original was prepared ; also some illustrations have been added. Blast-roasting' is a generic term for the process of forcing air through finely-divided. metallic sulphide with the object of roasting and agglomerating in a single operation. At first the process was confined to a galena-concentrate ; lime, limestone, or gypsum was added, to serve both as a diluent to keep separate the particles of galena that they might be thoroughly oxidized, and as a flux that the partly-roasted ore might be agglomerated by the formation of some slag. Later it was extended to treat other metallic sulphides. The leading processes were the Huntington-Heberlein and the Savelsberg of Europe, and the Carmichael-Bradford of Australia. In the United States and Canada, the Huntington-Heberlein process has found application in some instances with galena-concentrates, for which it was originally intended; but this class of ore is not often treated alone, hence the process has had to be modified to suit conditions. The Savelsberg process has been transplanted to this country in about its original form. The Carmichael-Bradford is not used at present. The changes called for in the Huntington-Heberlein process to adapt it to the class of lead-bearing ores usually smelted have been the 1 A. S. Dwight, Engineering and Mining Journal, vol. lxxxv., No. 13, p. 649 (Mar. 28, 1908).

Jun 1, 1910

By T. R. A. Davey

The fundamental principles by which bismuth may be removed from lead by pyrometallurgical processes are enumerated. Qualitative discussion of the phase diagrams concerned is followed by presentation of quantitative diagrams. Brief mention is made of the practical aspects. Data presented show how chemical lead (<0.005 pct Bi) may be produced by the Jollivet, Dittmer, and Kroll-Betterton processes. BISMUTH is an element whose properties are very similar to those of lead, and its minerals are associated to a greater or lesser extent with nearly all the major lead ore deposits of the world. In consequence, the lead produced contains bismuth unless a special debismuthizing process is practiced. There does not appear to be any published comprehensive review of the effect of bismuth as an impurity on the properties of lead, and there is some uncertainty as to the beneficial or detrimental effects of small amounts of bismuth in lead used for particular applications. Standard specifications of most countries stipulate a maximum bismuth content of 0.005 pct for chemical lead. With one exception, this specification is met only by lead producers whose ores are relatively bismuth-free, or whose refineries are electrolytic. In lead for certain applications a higher bismuth content is preferred by some fabricators.&apos; In contrast to the refining for silver, copper, and antimony, the refining for bismuth does not usually result in a large overalil economic gain from the sale of byproduct. Thus, debismuthizing is customarily practiced only if market conditions demand a lead with a bismuth content lower than that produced by classical refining; i.e., softening, desilverizing, and zinc refining. Until this century, debismuthizing was carried out only a:; an incidental result of desilverizing, as later described. This century has seen the development of the Betts electrolytic process—the only successful one of many electrolytic processes proposed and patented —and a number of precipitation processes based on the pioneering work of Kroll,&apos; although only one of these, the Kroll-Better ton process,&apos; is in wide commercial use today. It is proposed in this paper to deal only with the pyrometallurgical processes, excluding those based on aqueous electrolysis. Historical Background Prior to 1833 silver (and incidentally bismuth) could not be removed from lead. To recover silver from rich bullion, the only course available to lead refineries was to cupel the bullion, forming a slag of litharge. The first slag tappings or skimmings, on reduction, yielded soft lead of very low silver and bismuth contents. Intermediate skimmings yielded a lead of somewhat higher silver and bismuth contents, which could if desired be recupelled. The last skimmings yielded a litharge very high in bismuth, which could by successive oxidation and reduction cycles be separated into high purity bismuth, and lead returns. This oxidation reduction process, with modern operating techniques, can still be used today to produce a portion of a lead refinery&apos;s output of very low bismuth content, as discussed later. In 1833 Pattinsone discovered that lead bullion could be purified of silver and bismuth by fractional crystallization, the primary lead crystals formed by partial freezing being purer than the melt. Repeated processing in pans produced a lead containing as little as 0.02 pct Bi. The simple explanation of this

Jan 1, 1957

By Ernest M. Spokes

For bituminous and lignite coals the economic picture continued to improve as it has each year since the low of 1961, with production at 480 mil- lion tons in 1964 compared with 1963&apos;s 459 million tons. The anthracite industry produced 16.3 million tons in 1964 and 18.3 million tons in 1963. The industry is looking toward a further expansion; among the new developments will be a mining wheel producing 3 million tons of lignite per year in South Dakota. It is expected that electric power generation will continue to provide the market for most of the increase in consumption, with exports second in importance in the expansion. Improvements in methods of mining and transporting coal underground and in strip mines, and the cooperation of carriers in finding ways to reduce transportation costs to distant markets, have made possible these expansions. Research continues to reduce costs of mining, transportation, steam generation of electric power and production of steam for space heating and manufacturing processes, to retain some markets and expand others. Other research seeks to expand markets by developing fuel from coal which will be more attractive than competing fuels, by reducing sulfur and other sources of air pollution. Public relations efforts of the industry are bearing fruit in a greater acceptance of coal as a modern fuel.

Jan 2, 1965

By F. W. Jessen, C. C. Patton

Adsorbed films were formed on polished stainless steel specimens from dilute benzene solutions of two crude oil distillation residua. Although the two residua were extremely dissimilar in composition, contact angle measurements showed that the two films increased the wettability of the steel specimens to oil by equal amounts. Furthermore, the wettability of the films was essentially unaffected by the desorption techniques used. Paraffin deposits were formed from heptane-wax solutions on the same stainless steel specimens. These deposits definitely adhered to the surface. Presence of an adsorbed crude oil film on the metal surface increased its free surface energy and resulted in increased deposition of paraffin. The addition to the heptane - wax solution of small amounts of the same distillation residua that were used to form the adsorbed films resulted in decreased cohesive strength in the deposits formed, which resulted in decreased deposition. The presence of a crude oil fraction both in the solution and as a preadsorbed film eliminated the adherence of a deposit of any kind. A mechanism of deposition is proposed which explains the results obtained. INTRODUCTION The natural formation of any predominantly organic accumulation in oilwell tubing, surface flow lines or other production and storage facilities is called a paraffin deposit. These deposits restrict the production of crude oil, causing a substantial increase in production costs because of decreased flow capacity, expense for periodic deposit removal and unproductive downtime. The conditions under which such deposits form, their physical characteristics and the nature and severity of the problem created are extremely varied. Over the past several years, much progress has been made in developing and utilizing methods to remove accumulated paraffin deposition. However, like so many other problems, the basic stumbling block appears to be a lack of understanding of the fundamental mechanism involved in the formation of such deposits. Crude petroleum is known to contain considerable quantities of polar, surface active substances which Doddl has shown to be present at the oil-water interface. Denekas, Mattax and Davis2 observed that the wettability of reservoir rocks was drastically altered by exposure to crude oil fractions; and Zisman, et a1.3 showed that the nature of the compounds adsorbed on a surface would determine its wettability characteristics. Cole and Jessen4 and Ehrig5showed that surface wettability can have a profound effect on the magnitude of paraffin deposition, and Parks6 demonstrated chat the presence of certain adsorbed films on a metal surface would reduce the adherence of paraffin to that surface. Zisman7 has since advanced the theory that the conditions for adhesion are the same as for wetting. Therefore, it was felt that there was adequate evidence to support the supposition that adsorption of compounds from a crude oil might play an important part in paraffin deposition. ADSORPTION-WETTABILITY EXPERIMENTS Initial experiments were conducted to determine the effects of adsorption from solution of crude oil residua on the wettability of a polished stainless steel surface. Distillation residua with initial atmospheric boiling points of 700F were used in preference to the whole crudes in order to concentrate on the molecular weight range of interest, and to eliminate the possibility of composition change due to evaporation of the light ends. Also, these high boiling materials would be expected to be adsorbed from the whole oil in preference to similar compounds of lower molecular weight.

Jan 1, 1966

By S. R. B. Cooke, H. S. Choi, I. Iwasaki

In a previous article1 the function of various fatty acids as collectors for iron ores was reported for the two alternate processes; (a) the flotation of iron-oxide minerals, and (b) the flotation of calcium-activated siliceous gangue. The selectivity of separation was shown to be markedly dependent not only on such common parameters as pH and the levels of collector and activator addition, but also on the structure and the degree of unsaturation of the acids used. The iron ores employed consisted primarily of hematite, goethite, and quartz and as the effectiveness of any one acid on the separation depends on the individual response of each constituent mineral toward the given collector, a comprehensive knowledge of the floatability of the individual minerals is desirable for the interpretation of the results obtained. The mechanism by which a collector ion becomes attached to a mineral-solution interface has been a subject of much investigation. From quantitative studies of the properties of the electrical double layer on mercury2 and on several solid surfaces3,4,5,6 , the adsorption of some flotation reagents at the mineral-solution interface is beginning to be understood. For example, it has been demonstrated from streaming potential measurements made on quartz5 and corundum6 that the interfacial electrical condition is strongly dependent on the pH. Thisoccurs presumably through the following electrolytic reaction at the interface, and in the presence of a flotation collector, controls the floatability of the solids. A concurrent investigation of the flotation behavior of goethite and of quartz carried out at the School of Mines and Metallurgy7 has shown a positive correlation with the electrokinetic behavior of these minerals. The purpose of the present investigation was to collect general information on the floatability of hematite, and to investigate the function of various 18-carbon aliphatic acids on the floatability of hematite, goethite, and of activated quartz. Electrophoretic mobility measurements, simplified flotation tests using a modified Hallimond tube, and contact angle and frothability measurements were employed. The results are of direct application in the interpretation of the batch flotation results on natural ores as

Jan 1, 1961

By E. H. T. Whitten

Fundamental principles of trend surface analysis are briefly reviewed. Recent analyses of several granite masses illustrate the method of estimating the quantitative regional composition and also variation trends. Mineralogi-cal, bulk chemical, and other quantitative variates can be employed. Such results should improve gravimetric surveys (etc.) relying on correction terms based upon estimated rock composition. For the first time realistic estimates of the mean composition of rock bodies can be made with the aid of trend components. Deviation maps hold promise for delimitation of disseminated mineralized areas. Deviations comprise residual "anomalies" after removal of trend components. In petrogenetic work such deviations have been shown to reflect local influences (e.g., contamination of magma by assimilation of xenoliths or country rocks of the envelope). Similarly, mineralization should be reflected as deviations standing out from background trends. Actual examples are given. Present results largely involved projection of data onto a horizontal plane, but if sufficient data are available use of three spatial coordinates increases accuracy for prediction in "unexposed" areas. Regression analysis shows that statistical correlations between variates for regionally distributed specimens are often strong (particularly with percentage data). Hence, in preliminary surveys more easily determined variates may sometimes be employed to gain first estimates of the distribution of components more economically significant. The sampling plan is of paramount importance. Unless a suitable sampling plan is devised and adhered to rigorously during collection of the samples, all subsequent analysis is liable to strong bias and to yield spurious estimates of the truth. For a wide variety of purposes it is becoming necessary to assess the quantitative composition and variability of rock masses and mineralized zones of various types. In petrology and petrography this is something of a break with tradition, because virtually all descriptions heretofore have been qualitative. Although vast amounts of qualitative data have been compiled, little is known about the quantitative behavior of rock components. However, if variability of rocks could be understood and expressed with sufficient accuracy, there would be considerable advantage to both economic and petrogenetic problems. For example, if, on the basis of a limited series of observations, the three-dimensional geometry of a disseminated orebody (or ore-bearing formation) could be predicted accurately, it would be possible to extrapolate with confidence the structure into unexposed areas. The following example based upon the geometry of an igneous cone sheet illustrates the point. The significant rock-unit gives outcrops at a number of points on the exposed surface ABCD (Fig. 1A). Study of n exposures may enable a geologist to predict that the rock-unit is circular in form and thus indicate where the unit can be expected in unexposed terrain. Such observations are made at sites with u, v coordinates, but, if subsurface information is available at sites with uvw coordinates, it will eventually become possible to predict accurately the three-dimensional form of the rock mass. Geologic rock masses or mineral deposits are not generally as regular and symmetrical in geometric form as the body illustrated in Fig. 1A. However, even where the broad limits of a major rock mass are known, a more acute problem arises in attempting to obtain detailed quantitative estimates of its internal variability; it is difficult to predict the variability of a mass from a limited number of observa-

Jan 1, 1961

By W. A. Wood, H. M. Bendler

Cylindrical fatigue specimens of OFHC* copper were subjected to alternating torsion while under axial tension. The superimposed tension strongly influenced the fatigue life of the specimens as well as causing characteristic changes in the structure of the fissures that form and develop throughout the life of the specimen. A further effect of the superimposed tension is a continuous extension of the specimen throughout its life in a manner formally similar to creep at elevated temperatures. RECENTLY, studies of the structural changes leading to fracture of metals by fatigue have been made by a technique which reveals, in section, the lattice distortion arising from slip movements inside the metal and the disturbances built up by these slip movements at the metal surface.1&apos;2 According to this approach, fatigue develops as follows: a) fine slip movements concentrate in bands, producing little strain-hardening and thus permitting abnormal totals of plastic strain before fracture and, therefore, abnormal amounts of lattice distortion along each slip band; b) both forward and backward slip movements occur in each band which, according to their distribution across the band, may build up surface disturbances that include sharp notches; c) these notches early in the life of a specimen penetrate the distorted slip zones and transform them into deep, fine fissures; d) the fissures on continued cycling locally saturate the metal and cause local collapse in the form of a microcrack. Thus, the significant consequence of fatigue or cyclic

Jan 1, 1962

By Kenneth F. Whinery, John M. Campbell

Basically, the Buckley-Leverett theory involves two systems which are similar in nature but are differentiated by time. These systems may be described by the fractional flow and frontal advance equations which essentially characterize the mechanics of oil movement while being expelled from the reservoir. The fractional flow equation originally developed by Leverettl may be expressed in the more usable form The development of this equation is based on Darcy&apos;s law describing fluid flow through porous media and applies to the flow at only one point (it is a point function). For simplification, the fractional flow equation is written in the above form because the capillary forces always increase the fractional flow of the displacing phase regardless of the direction of flow or the displacing phase. If, for simplicity, the effects due to gravity and capillary pressure differences are neglected, the fraction of the displacing fluid, f, at any point in the flowing stream is related to the properties of the system by 1 Thus, it is seen that in the absence of capillary and gravitational effects, fd for a given sand and fluids varies only with saturation and pressure. The magnitude of the viscosity ratio, —a has an effective range (range of about 30) in the system where gas is displacing oil and a much smaller range for water displacing oil. In order to make the fractional flow equation more versatile, it is necessary to connect the fractional flow at a given point and saturation with time. This problem was approached by Buckley and Leverett" who developed the frontal advance equation, Eq. 3 states that the rate of advance of a plane that has a fixed saturation, Sd, is proportional to the change in composition of the flow stream caused by a small change in the saturation of the displacing fluid. It is, essentially, a transformation of a material balance equation representing the net rate of accumulation of the displacing phase within a homogeneous sand block. This accumulation is proportional to the difference between the rate at which the displacing fluid enters the sand and that at which it leaves. Eq. 3 describes the velocity with which a plane of constant displacing phase saturation advances through a porous system. Buckley and Leverett," Babson,&apos; Kern," Welge, and others have adequately discussed the basic mechanism and application of the fractional flow and frontal advance equations. APPLICATIONS OF THE FRONTAL ADVANCE THEORY TO PETROLEUM RECOVERY Two general applications of the Buckley-Leverett frontal advance theory involve the system in which the oil is being displaced by an expanding gas cap overlying the oil zone and that in which the oil is being displaced by water. Displacement by Gas in the Presence of an Immobile Water Saturation A system in which gas is the displacing phase may be thought of as having two forces effecting the displacement process. These forces are the gravitational force and that force exerted by the displacing gas. The gravitational effects control the displacing efficiency of the gas. The gravitational effect will be less at higher rates of flow, thereby reducing the effectiveness of the displacement of the oil by the gas. The more efficient displacements occur at flow rates which are less than the gravity free fall rate. Capillary forces can be neglected without materially changing the magnitude of the gas saturation. The Mile Six pool is used herein to illustrate the calculating procedures in evaluating gas drive-gravity drainage field perfomlance. These calculations represent the determination of the gas-oil contact when the distribution of the hydrocarbon pore volume is considered. Two methods

By Cyril Wells, Paul E. Busby, Donald P. Hart

EARLY workers in the field have established that the diffusion of nitrogen follows normal diffusion laws. Concentration-penetration data from layer analyses of reasonably pure iron specimens nitrided in an atmosphere of CO-NH, are given in the literature,&apos; and were utilized to calculate diffusion constants for nitrogen. The diffusion of nitrogen in y-iron may be represented approximately by the equation D - 1.07x10-&apos; e-:".&apos;m&apos;"&apos;r The diflusion coefficients, D, given by this relation represent mean values, since carburization occurred simultaneously with nitriding. The rate of diffusion in a-iron has been determined from calculations based on data obtained by measuring the internal friction of samples at each of several frequencies and temperatures.&apos; The expression for the diffusion of nitrogen in a-iron derived from these experiments is D= 1.4x10-1 e-it tudent Increasing carbon content decreases the diffusion of nitrogen in a-iron.3 Oxygen, either dissolved or combined, has been shown&apos; to exert a marked influence on the diffusion of nitrogen from a nitriding atmosphere. D values increase rapidly with increasing amount of dissolved oxide in the metal, but diffusion is completely inhibited if preliminary oxidation has produced the slightest trace of iron oxide on the surface. Diffusion coefficients have also been calculated from permeability and solubility data,&apos; but these values are of questionable accuracy since the boundary conditions assumed may not actually exist. Experimental Method The method selected for determining the diffusion coefficient of nitrogen in a-iron in the present investigation was the so-called fractional saturation method. This method consists of heating the specimen in an atmosphere of H2-NH8 mixtures of known composition for a predetermined time. Following this treatment, the specimen is analyzed for nitrogen; and the diffusion coefficient is calculated from a known relationship of the fractional saturation, time of diffusion, and dimensions of the specimen. This relation is based on a solution of Fick&apos;s second law and assumes that the surface of the specimen immediately reaches a given concentration which remains constant during the diffusion anneal. Tabular solutions are available4-5 and provide the relationship between fractional saturation and the quantity \/Dt /a, where D is the diffusion coefficient in cm2 per sec, t is the time of the diffusion anneal in seconds, and a, in the present experiments, is the half-thickness of the slab specimen in cm. The method is adequately discussed elsewhere.9-10 Material The material for this study consisted of 3/32 in. thick (0.24 cm) carbonyl iron plate. The major impurities in this iron are oxygen and carbon, which are readily removed by long time high temperature treatment in an atmosphere of purified hydrogen. In order to reduce the diffusion anneal time for saturation runs, some of this material was rolled to a thickness of 0.015 in. (0.038 cm) prior to the hydrogen treatment. Hydrogen treatments were carried out in a hydrogen-purified Armco iron tube heated in a global

Jan 1, 1957

[Chairman ZAY JEFFRIES, Vice-chairman S. SKOWRONSKI, Chairman WILLIAM M, CORSE, Secretary Executive Committee J. R. FREEMAN, JR., Local Section G. E. JOHNSON R. S. ARCHER, Non-ferrous Data Sheets P. D. MERICA EDGAR C. BAIN, Journal Committee L. W. SPRING SAM TOUR, Papers Committee F. L. WOLF H. C. JENNISON, Membership Committee Local Section Committee J. R. FREEMAN, JR., Chairman R. J. ANDERSON, Cincinnati R L. DOWDELL, Minneapolis R. S. WILLIAMS, Boston G. H. CLAMER, Philadelphia W. A. SCHEUCH, Chicago R. F, Woon, New York Papers Committee S. SKOWRONSKI, Chairman F. H. DIx, JR.-Aluminum E. R. DARBY-Bronze C. S. WITH ERELL-Copper H. A. BEDWORTH-Brass W. K. FRANK-BRONZE F. W. HARRIS-Copper R. L. SUHL-Nickel H. M. ST. JOHN--Foundry Metallurgy R. S. DEAN-Theoretical Metallurgy]

Jan 1, 1928

By P. C. Hodges

WHILE there is very little romance connected with the operation of a stone quarry, yet to those who have participated in the growth and development of a business that has been a pioneer in its field and that FIG. 1.-LOCATION OF PROPERTY OF MARBLE CLIFF QUARRIES COMPANY. has been in continual operation two-thirds of a century there is bound to be a background of experience, which if properly capitalized, brings progress as well as satisfaction in its accomplishment.

Jan 1, 1936

By G. Thodos, W. F. Stevens

The point-source function introduced by Horner&apos; us a solution to the general unsteady-state equation for the flow of fluids through porous media has been utilized to calculate pressure profiles for adjacent wells as a function of time. By trial and error, the time at which the pressure waves meet to cause interference can then be calculated. For this calculation, the time of interference is arbitrarily defined as that time when both pressure waves exhibit a pressure decrease of 25 psi ar the same point within the formation. To illustrate the method, an example involving two adjacent wells producing at different rates has been worked out and is presented in detail. INTRODUCTION The initiation of production of a new well is usually accompanied by pressure drawdown measurements in order to establish the extent and characteristics of the formation. The interpretation of such pressure drawdown data is based on mathematical developments involving a single well in an infinite reservoir. If more than one well is present in a reservoir, the possibility of interaction between wells exists. Therefore, care must be taken in interpreting the pressure drawdown data. It becomes important to be able to determine when this interaction, or interference, becomes significant. This paper presents a method for the prediction of the approximate time of interference between two such adjacent wells. The basic differential equation describing the pressure distribution existing during unsteady-state flow of a slightly compressible fluid has been solved by Hor-ner.&apos; for a constant production rate from a circular homogeneous reservoir of infinite extent. The solution utilizes the point-source function to define the pressure at various points within the formation as a function of time. The resulting expression is: q = production rate, STB/D ,;= formation volume factor, dimension-less µ = fluid viscosity, cp k = formation permeability. md H = formation thickness, ft C - fluid compressibility, psi&apos; F = formation porosity, dimensionless R = distance from centerline of well, ft T = production time, hours Ei(—u) = Ei-function of U Eq. 1 may be used to calculate the pressure profiles generated during production from a single well in an infinite reservoir.

By L. L. Seigle

Free energies, heats, and entropies of mixing of solid Fe-Au alloys have been measured by the galvanic cell method between 800° and 900°C. A positive deviation from Raoult&apos;s law and a large excess entropy of mixing were observed, both attributable to lattice distortion caused by the disparity in component atom sizes. Since the terminal solid solutortiontions are not regular, thermodynamic properties computed from the location of the mis-cibility gap do not agree well with measured quantities. The electromotive force data suggest some changes in the existing Fe-Au phase diagram. ALTHOUGH a considerable amount of information has been accumulated about the thermodynamic properties of metal solid solutions which exhibit negative deviation from Raoult&apos;s law, particularly those in which ordering occurs, relatively few experimental measurements have been made on solutions with positive deviation. This is due to the infrequency of broad homogeneous regions suitable for experimental measurement in solutions of this type, since any marked positive deviations from ideality lead to restricted solubility and the formation of miscibility gaps. Thermodynamic data reported in the literature for such systems have usually been calculated from the location of the miscibility gap boundaries under the assumption that the entropies of mixing are ideal, i.e., the terminal solutions are regular.&apos; One of the few binary systems with both positive deviation and a wide homogeneous range in the solid is the Ni-Au system. A recent investigation of solid Ni-Au alloys&apos; revealed that the entropies of mixing were much larger than ideal and consequently thermal data computed from the phase boundaries assuming regular solutions were seriously in error. Theoretical considerations put forward by Zener indicated that high entropy values should generally be associated with systems possessing a miscibility gap in the solid, when this is due to differences in the size of component atoms. These facts suggest that the regular solution assumption is a poor approximation for many solid solutions with positive deviation and that reliable thermodynamic data generally cannot be obtained by conventional methods from the location of miscibility gap boundaries. The Fe-Au system, Fig. 1, resembles the Ni-Au system in certain respects. The presence of a miscibility gap in the solid indicates a large positive deviation from ideality, but there is nevertheless an extensive single phase region suitable for experimental measurement. The following investigation of solid Fe-Au alloys was carried out in order to obtain additional data on the thermodynamic properties of metal solid solutions with positive deviation from Raoult&apos;s law and to further compare thermodynamic data computed from miscibility gap boundaries with those measured experimentally. Experimental Method The thermodynamic properties were derived from measurements of the potential developed between pure solid iron and Fe-Au alloys in a high temperature galvanic cell. The experimental apparatus and technique were the same as those used for the Ni-Au alloys and described in a previous report.&apos; Cell electrodes were 1/16 in. diam rods swaged from chill-cast ingots and annealed for one week at 850°C. The alloys were prepared by melting fine gold granules under argon with pure iron obtained from the National Research Co. The cell electrolyte was

Jan 1, 1957

By B. D. Lichter

In a previous paper, Oelsen, Schuermann, and Hey-nertl pointed out the possibility of obtaining complete thermodynamic functions for alloy systems from calorimetric measurements alone. Specifically, if the heat content of a heterogeneous, multicomponent system is known as a function of temperature and composition, then it is possible to derive the heats, entropies, and free energies of formation of liquid phases and of solid intermediate phases of fixed composition. The authors present equations and graphical techniques applicable to eutectic systems and systems with intermediate phases without solid solubility at lower temperatures. eijering has considered possible extension of the treatment to systems with complete solid-state miscibility at lower temperatures; however, experimental difficulties practically restrict the method to systems with very limited miscibility in the solid state. The purpose of this note is to present an alternative derivation of the heats and entropies of formation of liquid phases and of solid intermediate phases from heat-content measurements alone. Fig. 1 shows three types of phase diagram to which the analysis may be applied. If the heat content is determined as a function of composition x, at temperature T, we have quite generally and the heat of mixing of the liquid is obtained directly from heat-content measurements. If the temperature T lies in a two-phase region (solid-liquid) then

Jan 1, 1967

By Herbert H. Kellogg

The chemistry of sulfide roasting is analyzed to show those aspects of performance which Thecan be predicted from considerations of thermodynamic equilibrium. It is concluded that equilibrium calculations can serve as a yardstick for prediction of roaster-gas composition and sulfate formation in the calcine for fluid-bed roasting practice. A method of calculation which combines the equilibrium and stoichiometric factors is outlined, and illustrated by an example from the roasting of Cu-Fe sulfides. ON first examination the roasting of sulfides would not seem to be a process to which equilibrium calculations could be applied to yield results of practical value. The burning of sulfides is an ex-tremely spontaneous reaction, excess air is always used to obtain rapid reaction, and in most traditional roaster designs (hearth roasting) the temperature and gas composition vary widely from point to point in the roaster. These are all conditions which promote a non-equilibrium state in the roasting process. However, the introduction of the fluid-bed roaster1 has brought to roasting practice new conditions of operation, so that equilibrium calculations can be used to predict certain limited aspects of practical operation. The fluid bed is characterized by uniformity of temperature, gas composition, and calcine composition from point to point throughout the bed. These relatively uniform properties of the bed make the meaningful calculation of the equilibrium state of certain reactions in roasting possible. It is the purpose of this paper to analyze roasting from an equilibrium viewpoint, to show where the method may be expected to yield valuable information, where it fails, and to outline methods of calculation. Main Roasting Reaction The reaction MS (s) + 3/2 0, = MO (s) + SO, [I] might well be called the main roasting reaction. It adequately accounts for the well known facts that metal sulfide and air are the main reactants, and metal oxide and SO, the main products. Deviations from this simple stoichiometry will be discussed under side reactions. For all metal sulfides, Reaction 1 is strongly exothermic and the equilibrium position is far to the right. Since the reaction is exothermic, the equilibrium shifts in the right-to-left direction as the temperature is raised. However, at all practical roaster temperatures (between 500" and 1200°C), the amount of this shift is small, and the equilibrium position remains far to the right. The main roasting reaction is essentially irreversible, and the application of equilibrium considerations to this reaction will not be! a fruitful field of investigation. A knowledge of the rate of this reaction. although not the proper subject of this paper, is of great importance to the roasting process. Analysis of the factors which influence this rate shows that: 1) The rate will increase rapidly with increased temperature. 2) The rate will be proportional to the partial pressure of oxygen at the surface of the reacting particle. Because of diffusion effects, the partial pressure of oxygen at the particle surface may be considerably less than in the bulk of the roaster gas. For this reason, intimate contact between gas and solid and high relative velocity between gas and solid, such as can be obtained in a fluid bed or flash roaster, will markedly increase the rate of reaction. 3) The rate will be proportional to the surface area of metal sulfide. Therefore, smaller particle size will permit a more rapid rate per unit of weight. To achieve practical rates of roasting the partial pressure of oxygen in the roaster gases must be maintained at a finite level at all times. Even where the gas-solid contact is very good, as in the fluid-bed roaster, the oxygen content of the gas must not be allowed to drop below some limiting value (perhaps 1 pct), or the rate of the main roasting reaction will become too small for practical operation. Side Reactions in the Gas Phase The gas phase during roasting of metallic sulfides contains the elements oxygen, sulfur, nitrogen, by-

Jan 1, 1957

By Robert B. Fulton

The use of industrial minerals by the chemical industry as raw materials for manufacturing and in processing spans a wide assortment of minerals. This chapter aims to supplement rather than duplicate the commodity chapters. Its objective, to describe the uses of industrial minerals in the manufacture of chemicals, is attained by considering minerals used by the chemical industry in terms of the chemical element required and by giving particular emphasis to market factors. The mineral aspect, which is covered in the commodity chapters, is subordinated and attention is focused on the chemical and market aspects. Condensing this broad subject into a few pages permits treating only the most important elements derived from industrial minerals. The elements derived from petroleum, hydrogen and carbon, which quantitatively dominate as raw materials for the chemical industry, are omitted, as are the metallic elements and the minerals covered in other "use" chapters such as phosphorous, potash, and nitrogen for fertilizers and titanium dioxide for pigments. After eliminating on this basis, our definition leaves six elements of major importance: boron, bromine, chlorine, fluorine, sodium, and sulfur. These elements are treated individually under separate headings. Salt brines have particular importance as raw material sources for the chemical industry as shown in Table 1 "Salt Brine Derivatives" (Anon., 1967), which charts the chemical compounds derived from four types of brines: (1) Owens Lake type brines which are sources of boron and sodium compounds; (2) Midland type brines from which bromine, iodine, and chlorides of calcium, magnesium, potassium, and sodium are derived; (3) Searles Lake type yielding boron, bromine, lithium, magnesium, potassium, and sodium compounds; and (4) Silver Peak type produced mainly for lithium. Table 2 (Jones, 1973) affords an overview of the chief industrial minerals, the chemical products derived from them, and end uses of the products.

Jan 1, 1975

By H. Linder, W. H. Dennen

The graphitic carbon content of soils may be used to detect and delimit subsurface graphitic zones. Spectrographic measurement of carbon in C horizon soils from several areas in the northeastern United States shows good correlation with known graphitic bodies. Bodies of graphite and sulfides are readily located by electromagnetic prospecting methods, but these methods cannot generally discriminate between them. Usual practice, therefore, requires follow-up work on electrically anomalous areas by trenching, drilling, or soil sampling in order to determine the mineralogical nature of the conductor. The efficiency and cost of such follow-up is consequently an important factor in prospecting. The presence of buried sulfide deposits is often reflected in concentrations of metals in the superincumbent soil. Simple chemical tests for such metal concentrations have been developed and applied with considerable success. Bodies of graphite or mixtures of graphite and sulfides are, however, very common and a means whereby buried graphite could be detected by soil testing should provide valuable additional information in the search for ore sulfide and graphite deposits. Graphite is a notably stable substance and should persist in soil above graphite-rich horizons. Microscopic examination of soil samples high in carbon, however, failed to reveal any recognizable graphite fragments indicating a grain size in the clay range. Presumably such small particles would have some mobility in a soil by a translocation mechanism similar to that proposed for the movement of clay particles in a soil profile. Experimental data supports this idea since the boundary between background and anomalous soils carbon values is quite sharp, but the anomalous zone is slightly broader than the graphitic source rock. A simple spectrochemical technique for the determination of carbon in geological materials has been described by Dennen,1 and may be directly applied to soils. A modification of this technique which employs an arcing chamber through which nitrogen is passed is recommended to decrease contributions from atmospheric carbon dioxide. Tests indicate that soils over graphitic zones may be strongly enriched in carbon. The spectrochemical determination of carbon depends upon the formation of the cyanogen molecule (CN) from carbon in a sample and atmospheric nitrogen, under the high temperatures associated with a dc arc. Samples for analysis are dried, lumps broken, and screened. A small portion of the -100 mesh fraction is packed into a copper electrode and excited as the cathode of a dc arc. The band spectra of cyanogen are recorded photographically and the density of the bandhead CN 3883A is measured. The limit of detection of the method is about 0.01 pct C and its coefficient of variation is about 15 pct. Soils, of course, contain carbon in other forms than graphite, and the amount of interference from such sources was examined. The C horizon of several soils from Massachusetts, Maine, and Pennsylvania were found to have a carbon content of 0.3 to 0.5 pct by weight. This content is chiefly due to the presence of carbonates and vegetable matter in the sample and may be readily eliminated, or at least

Jan 1, 1961

By R. A. Wattenbarger, H. J. Ramey

The trend in gas well testing has been to rely more on the early-time flow data of drawdown and buildup tests than on stabilized flow tests. The stabilized testing methods often are not adequate for complicated modern gas reservoirs because many of these reservoirs have extremely low permeabilities and the transient flow period of a well test can last for days or weeks. It has become common to augment the flow capacity of gas wells by hydraulically fracturing their producing formations. In deep reservoirs the induced fractures are generally vertical and tend to follow a single plane of weakness. The presence of a vertical fracture at the wellbore complicates the transient flow behavior of a low permeability gas well. The flow is further complicated when turbulence occurs near the wellbore. Russell and Truittl published transient drawdown solutions for vertically-fractured liquid wells. They developed methods of drawdown and buildup testing utilizing these solutions, which were based on numerical simulation. Clark2 applied the basic Russell-Truitt solutions to analyze fractured water injection wells by falloff tests. Field examples were given to substantiate the method of analysis. The Russell-Truitt solutions and well testing methods can be extended to gas well flow. Millheim and Cichowicz3 presented the drawdown equations for *Now with Scientific Software Corp., Denver. ideal gas flow, including the effects of formation damage and turbulence. Two actual field cases were presented, both of which exhibited extensive fractures and turbulent flow. For the pressure range of these well tests, the use of ideal gas equations was acceptable. These field cases were significant in being the first published data showing the occurrence of turbulence in fractured gas wells. We, also, observed such cases in practice. Our purpose here is to extend the theory of fractured gas well testing to the flow of real gases. To determine the effects of wellbore storage and turbulence on well test interpretation, we developed a finite-difference model to simulate well test conditions. Since gas wells usually are widely spaced and have high compressibility, the emphasis has been put on the early transient behavior before the effects of the outer boundary are noticeable at the wellbore. The Mathematical Model The geometry of our mathematical model is similar to that used by Prats.4 The well is centered in a circular uniform reservoir. A vertical fracture of infinite flow capacity penetrates the formation and passes through the wellbore. The wellbore itself is not important. Fig. 1 shows a sketch of the problem. Fig. 2 shows the idealized model. The equation for the flow of real gas in a porous medium with uniform porosity, permeability and thickness is5-7

Jan 1, 1970

Jan 1, 1970

By E. B. Johnson

Cleveland-Cliffs lron Co., which operates Marquette lron Mining Co.&apos;s Republic mine, conducted a test whereby 35,000 tons of self-fluxed pellets were produced in the grate-kiln system from specular hematite flotation concentrates. A brief description of the pelletizing plant is presented along with pertinent operating details. Date is included which compare operating conditions and the chemical and physical properties of the green and fired pellets for the self-fluxing pelletizing test with the normal acid pelletizing operation. The success of self-fluxed sinter in enhancing the operation of the blast furnace during the past few years has reasonably led to the assumption that the use of self-fluxed pellets might result in even greater furnace efficiencies. A great share of development work in agglomeration has been directed towards techniques related to the production of self-fluxed pellets, but only a limited tonnage of self-fluxed pellets had been produced on a commercial scale until this past year when The Cleveland-Cliffs Iron Co. produced 35,000 tons of such pellets by the grate kiln system at the Republic mine during the period May 21-June 5, 1962. REPUBLIC&apos;S GRATE-KILN PLANT The grate-kiln pelletizing process consists of four stages, namely: feed or balling circuit, traveling grate, rotary kiln and annular cooler (Fig. 1). The balling section is conventional and utilizes four 9x30-ft balling drums in closed circuit with 5x14-ft vibrating screens having 3/8-in. rod decks. The traveling grate is 12 ft wide by 126 ft long and has 14 windboxes — six in the drying section and eight in the preheat section. The rotary kiln is 15 ft ID shell and 114 ft long. The annular cooler is 40 ft in diameter and has 12 windboxes. The cooler is divided into two zones by a moveable curtain wall. The high temperature air from the first zone is used as secondary combustion air in the kiln. Normally the only heat supplied is through the burning of No. 6 oil in the single kiln burner. Hot gases pass counter to the pellet flow through the system. The exit gases from the kiln pass down draft through the preheat section through cyclones and are drawn through the drying bed prior to exiting via the stack. The temperatures are normally held within the following ranges: Kiln 2400-2445 °F Preheat 1850-1950°F Drying 480-520°F Exit gas 200°F Pellets 120°F The design capacity of the Republic mine grate-kiln system was 2500 Itpd. Sustained production in excess of 35% over design capacity has been achieved. No screening of the cooler product is practiced. PELLETIZING TEST CONDITIONS When a decision was made to proceed with a test at the Republic mine pelletizing plant to produce 35,000 tons of self-fluxed pellets, several potential failure factors had to be carefully considered. Research work on a batch and pilot plant scale indicated that the grate-kiln system at Republic would require some major changes in order to obtain optimum conditions. In many cases compromises were agreed upon as major equipment changes and revisions were not feasible. The pelletizing conditions which laboratory development tests revealed were required in order to insure successful production of self-fluxed pellets were: 1) Good mixing of limestone and concentrate and proper moisture control; 2) Higher gas flow rates in the preheat section than are normally used; 3) Higher preheat temperatures than normal; 4) Maximum kiln temperature 2350°F. There was just cause for concern about balling problems that might occur. Approximately 10% of dry pulverized limestone was to be added to the specular hematite concentrate just ahead of the Pekay mixers on the belt feeding the balling drum. Large scale

Jan 1, 1963