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By R. R. Joseph, K. A. Gschneidner

The solid solubility of magnesium in the close-packed modifications of lanthanum, cerium, praseodymium, neodymium, gadolinium, dysprosium, and lutetium was determined from approximately 250°C to the eutectoid temperature by the X-ray parametric technique. The maximum solubility at the eutectoid temperature was found to be 9.4 at. pet in La, 8.2 in Ce, 9.2 in Pr, 8.2 in Nd, 14.1 in Gd, 13.5 in Dy, and 11.5 in Lu. The solubility when compared at a homologous temperature was found to increase in a smooth manner with decreasing size factor from lanthanum to lutetium. It was found that the apparent atomic radius of magnesium when dissolved in the lanthanide solvent was constant and could be accounted for by consideration of several models dealing with departures from Vegard's law. The eutectoid temperatures for the lanthanide-rich La-Mg, Ce-Mg, and Nd-Mg systems were found to be 544", 505°, and 551°c, respectively. A study of the solid solubility of magnesium in the lanthanide metals was initiated because the valency and electron egativity difference are essentially constant and favorable for solid-solution formation, and thus one could examine the effect of size on terminal solid solutions. The size factors based on metal radii range from 14.6 pet for lanthanum to 7.5 pet for lutetium. Since the electronegativity difference is small, 0.06 unit or less, application of the Hume-~othery' and Darken and Gurry2 criteria for solid-solution formation indicates that the solubility of magnesium would be expected to be small for lanthanum (between 5 and 10 at. pet) and to increase as we proceed along the lanthanide series. A search of the literature revealed no data on the solubility of magnesium in the lanthanide metals except for the solubility of magnesium in cerium at 450oCA typical phase diagram for the lanthanide-rich end of the lanthanide-magnesium phase diagram is shown in Fig. 1. EXPERIMENTAL PROCEDURES Preparation of Alloys. The lanthanide metals used in the preparation of alloys for this investigation were prepared from the corresponding fluoride by metallothermic reduction techniques previously described by Daane.4 The chemical analyses of the metals used are listed in Table I.

Jan 1, 1965

By H. Kazemi, G. W. Thomas, M. S. Seth

The double-porosity model of Warren and Root7 for examining pressure drawdown and buildup phenomena in naturally fractured reservoirs has been extended to intetpret interference test results. Both analytical and numerical solutions are presented. The practicality of some of the assumptions in the Warren-Root model was also investigated. The standard procedure for interpreting interference tests in naturally fractured reservoirs beretofore employed an equivalent homogeneous reservoir model. A comparison of our results with the equivalent homogeneous model indicates the latter is inadequate for early time responses. For late time responses, however, the simpler equivalent homogeneous model yields favorable results. Finally, the effects of well spacing and the magnitude of the interporosity flow parameter are briefly cited. INTRODUCTION Interference tests can be used to provide reservoir information not obtainable from conventional pressure drawdown and buildup tests. The technique involves measuring the response in one or more wells arising from a pressure perturbation introduced into another well. It has been. successfully applied to single-layer, homogeneous, unfractured, isotropic and anisotropic formations to arrive at values of well storage capacity and a measure of directional permeability.l The techniques of interference testing usually can be extended to heterogeneous systems, provided the permeability contrast between any existing rock layers is not excessive.9 In such cases, the practical interference effects in an observation well of an interconnecting heterogeneous reservoir can be predicted using an equivalent homogeneous model. The calculated properties are then average values. Russell and Prats2 have demonstrated the utility of this approach for a single-phase, two-layer system. For naturally fractured reservoirs, some different approaches usually are necessary. The major departure from homogeneous or nearly homogeneous reservoir treatment is to characterize the fractured system as an entity having "double-porosity"; namely, we suppose the existence of both primary and secondary porosity, where the former is contained within a systematic array of identical rectangular matrix blocks and the latter is contained within an orthogonal system of continuous, uniform fractures (see Fig. 1). It is sufficient to assume that the permeability of the rock matrix is so small that movement of reservoir fluids to the producing wells is entirely through the fracture network. This assumption has been validated by Barenblatt3 and .employed by others?-7 Warren and Root7 used the double-porosity model to develop an interpretation of pressure drawdown and pressure buildup tests in naturally fractured

Jan 1, 1970

By Arthur L. Hall

The purpose of this symposium is to challenge industry to better air classification, and as a first step toward fulfillment, to spotlight three fairly recent, aerodynamically designed, highly efficient air classifiers. This discussion does not intend to imply that present practice is bad. Actually, when present air separators are used for the jobs for which they were originally designed, they give high production and uniform operation, with a minimum of maintenance. The customers of nonmetallic mineral pigment producers, however, are making increasing demands for finer products, such as 99.9 pct -20µ, which appears to be beyond the economic capabilities of standard air separators industrially used over the last 10 to 30 years. Here is an actual example. A 10-ft diam pebble mill is in closed circuit with a conventional 12-ft diam centrifugal air separator, grinding 20-mesh wollastonite to a series of fine grades up to 99.97 pct - U.S. No. 325 mesh (44µ). Fig. 1 shows variations in fineness of mill discharge (or air separator feed), recycle for regrinding (or air separator tails), and product as measured by a wet rotating sieve test. For example, when the mill is turning out a product 80 pct -325, the mill discharge or separator feed is 30 pct -325, and the coarse tailings or recycle is only 5 pct -325. Hence 25 pct of the 30 pct available is accepted as product. This is efficient separation, and the ratio of recycle to feed is only about 2: 1. How- ever, to make a product testing 99.97 pct -325 the separator feed is 62 pct -325 and the coarse tailing 60 pct -325. In this case the recycle ratio is about 13: 1 and the economic limit to produce fineness has been substantially reached with this given equipment and process arrangement.

Jan 10, 1957

By C. O. Lee, Z. W. Bartlett, R. H. Feierabend

The Grand Isle sulfur mine is located in the Gulf of Mexico, approximately seven miles off the coast of Grand Isle, Jefferson Parish, La. The deposit is on acreage covered by oil, gas, and mineral leases originally issued in favor of Humble Oil & Refining Co. by the State of Louisiana which were continued, maintained, and redesignated by the U.S. Department of the Interior after passage of the Outer Continental Shelf Lands Act. The sulfur deposit was discovered in 1949 when Humble Oil & Refining Co. penetrated more than 200 ft of sulfur-bearing limestone in a zone between 1813 and 2075 ft below sea level. In 1954, Humble drilled ten more sulfur prospect holes, eight of which encountered sulfur ore. On September 19, 1956, Freeport Sulphur Co. acquired from Humble Oil & Refining Co, the sulfur rights underlying the tracts, and the actual design of the installation began the same month. The first structural contract was awarded in December 1957 and offshore erection began in June 1958. The initial phase of construction has been completed and production by the Frasch process commenced in April 1960. The estimated total cost of the project is $30 million, of which $8 million is the extra cost incurred by the necessity of offshore operations. More than $22 million was expended before production was started. GEOLOGY OF DEPOSIT Grand Isle is the third largest sulfur deposit in the U.S. The orebody embraces several hundred acres, but its outer limits are yet to be defined to the northeast, east, and south. Most Gulf Coast sulfur deposits occur in a caprock mantle of calcite (referred to as limestone), anhydrite, and occasionally gypsum, which covers the apex of an intrusive mass of salt. Commercial quantities of sulfur are usually confined to the calcite or limestone member. Most often such limestone is completely enclosed by dense anhydrite below and impervious sediments above, which effectively form a closed reservoir. The depth of the Grand Isle orebody ranges from 1800 ft to 2500 ft below sea level. Within the present boundary, the sulfur-bearing limestone varies in thickness from 220 ft to 425 ft, while the sulfur content varies an average of about 15 pct in the leanest hole to an average of about 30 pct in the richest. Rock containing less than 5 pct sulfur is not classed as ore, and holes assaying less than 20,-000 long tons per acre of sulfur in place are not considered commercial offshore. The sulfur enrich-

Jan 1, 1961

By Robert G. Nisle

The classic theory of pressure build-up in shut-in oil wells as developed by Horner and van Everdingen is based on two-dimensional radial symmetry in the well-reservoir system. Such symmetry does not exist in the case of a well which parfiially penetrates the producing formation. As a result of this lack of symmetry the use of the classic theory in such cases become questionable. In this paper the mathematical theory has been extended to include the case of partially penetrating wells. Numerical solutions illustrating the up-dication of the equations are presented. The effect of partial penetration on pressure build-up is shown by a comparison of synthetic pressure build-up curves derived from the numerical solution of the equation for partially penetrating wells for various degrees of penetration. It is shown that partial penetration is detectable from the characteristic shape of the pressure build-up curve and that formation productivity may be calculated from the pressure buildup data in a manner identical to that described by the classic theory. INTRO DUCTION The use of pressure build-up data on shut-in oil wells is a well-established technique for the measurement of reservoir productivity. The work of Homer' and van Everdingen' is well known. Since the publication of their pioneering work, others"' have elaborated and extended the technique. These authors have dealt exclusively with the case of wells that completely penetrate he producing formation. Two-dimensional radial symmetry is achieved, thereby, and the problem is greatly simplified. This ideal situation is seldom encountered in practice. But, in spite of this, the technique is often employed anyway. The question, therefore, arises: how much confidence can be placed in the results of such calculations when the data are taken on wells that only partially penetrate the producing formation? It is the purpose of this work to answer this question. Only the single-phase fluid case will be considered. van Everdigen' has presented a rigorous solution of the two-dimensional case, but because of mathematical complexity, this solution has not proved to be particularly useful. Horner' utilized Kelvin's point source solution in two dimensions and showed that it is a sufficiently good approximation for oil reservoir studies. The geometry of the well and the producing formation is illustrated in Fig. l. Geometrically the formation may be described as an infinite slab. The infinite slab is defined as the solid (the porous medium in this case) bounded by two parallel planes. Thus, the slab extends to very great distances in both the positive and negative directions of two of the coordinate axes, but is finite in

By J. E. Warren, J. H. Hartsock

An asymptotic solution to the equation that describes the flow of a slightly compressible fluid in an infinite porous medium has been used to estimate the interaction between two adjacent wells producing from a common reservoir. A direct method for approximating the interference time defined by Stevens and Thodosl has been suggested. An alternative definition for the time of interference, based on the minimum pressure change in the interference region, has been proposed; also, a direct method of determination has been prescribed. Examples have been employed to illustrate the use of both methods.

By W. H. Yarroll Discussion by W. A. Griffith

W. A. Griffith (Head, Research Department, Phelps Dodge Corp., Morenci, Ariz.) - It is gratifying to see the increasingly common use of classical statistical procedures by metallurgical researchers. Mr. Yarroll has given excellent illustrations of the utility of multiple correlation analysis of complex metallurgical data. Our experience in applying these procedures to historical plant operating data has differed, however, from that which he suggests. The uninitiated frequently assume that the volumi-

Jan 1, 1969

By B. A. Wilcox, A. H. Clauer

DURING the course of an investigation on the high-temperature creep behavior of TD Nickel* (Ni + 2) vol pct ThO2), it was observed that the creep fractures were similar in appearance to low-temperature ductile fibrous fractures and creep ruptures by cavitation. Microfractographs of fibrous ruptures are typically characterized by a dimpled appearance, with second-phase particles frequently found near the bottom of the dimples.'-4 These somewhat resemble creep ruptures by cavitation, in that fracture occurs by void formation, with the subsequent growth and final merging of the voids to form a complete fracture.' It is the purpose of this communication to describe the creep fracture of TD nickel and suggest a mechanism for the rupturing process. The discussion is relevant to material crept to fracture in vacuo at a constant stress of 18,000 psi, over the temperature range 900" to ll00°C. The material used in this investigation was 1/2-in.-diam bar stock supplied by Du Pont, contain- ing 2.3 vol pct Tho2. The final fabrication treatment consisted of -95 pct reduction by swaging followed by a 1-hr anneal at 1000°C. Transmission and replica electron microscopy revealed that the material had a fibered structure with a transverse grain size of -1 µ and a longitudinal grain size of 10 to 15 µ. Selected-area diffraction indicated that the fiber axis was parallel to (00l), in agreement with the results of Inman et a1.6 The thoria particle size varied from 80 to 1000Å, with an average size of 400Å, and the mean particle spacing was about 1200Å. The remarkable structural stability7 was confirmed by annealing for 6 hr at 1300°C (about ' 0.9 the absolute melting point). Transmission electron microscopy revealed that the only structural change was a slight decrease in dislocation density. Furthermore, recrystallization or grain growth during creep has not been observed. All specimens were annealed in vacuo at 1300°C for 3 hr prior to creep testing. The following times to rupture were obtained for vacuum creep tests at a constant stress of 18,000 psi: 900°C, 854 hr; 930°C,

Jan 1, 1965

By Elmer W. Pehrson

Minerals have played a prominent role in the affairs of man and nations since time immemorial but with the advent of the industrial revolution, expanding use of the products of the mineral kingdom became synonymous with the material progress of mankind. Individuals and business groups have recognized this fact so have been aggressive in searching for and utilizing mineral resources, with notable success. Indeed, their achievements are primarily responsible for the present Machine Age. On the other hand, until recently the body politic has failed to grasp fully the essentiality of minerals although, at times, access to mineral supplies has been an important factor in the political maneuvers of nations. This chapter is concerned primarily with the broader political and economic relationships of mineral resources to the world economy, and with the internal and external actions of nations in the field of minerals. Many factors that condition the mineral economy of regions and the world as a whole, influence the internal and external affairs of individual nations. The more important of these are: 1. The nature of man's dependence on minerals. 2. The problems resulting from the unique characteristics of mineral occurrence. 3. Geopolitical concepts. 4. Minerals and world power. Actions of individual nations affecting their mineral economy seek two basic objectives : 1. Attainment and maintenance of prosperity. 2. Military security. Other objectives may be cited but on careful analysis they become integral parts or extreme phases of the two points noted above. For example, the twentieth century aggressions of the USSR, Germany, Italy, and Japan might be considered as direct bids for world power but they also can be interpreted as exaggerated or mistaken efforts toward military security and peacetime prosperity. Similarly, trade barriers, nationalization of industries, foreign exchange manipulations, taxation, monopolistic prac-

Jan 1, 1959

By W. C. Phalen

The production of salt in the United States divides itself at the outset into two distinct classes…

Jan 1, 1915

[Executive J. V. W. REYNDERS, Chairman WILLIAM H. BASSETT E. DEGOLYER I-I. C. BELLINGER RICHARD PETERS, JR. Finance GEORGE OTIS SMITH, Chairman H. A. GUESS F. JULIUS FOHS Admissions GEORGE D. BARRON, Chairman DAVID LEVINGER P. A. MOSMAN H. K. MASTERS J. A, SINGMASTER Alternates F. G. BREYER C. W. HAMILTON F. E. PIERCE]

Jan 1, 1928

By E. T. Turkdogan

Jan 1, 1962

By Richard Miller

RECENT studies of creep have made it apparent that plastic deforma-tion may occur in metals under stresses less than the elastic limit as deter-mined from short-time tests. In summarizing conclusions drawn from creep tests by various investigators, Tapsell1 said: "It is evident that if a material has a true elastic range, the elastic limit must represent the maximum stress for no creep." The presence of a. definite elastic limit, represented in single crystals by a critical or threshold shearing stress, is claimed by Schmid2, Elam3 and others who have investigated the plastic deformation of single crystals. However, this "law of critical shearing stress" was deter-mined2 from short-time tests, and the measurement of the deformation was made with apparatus primarily designed to observe large amounts of plastic deformation, not to detect elastic changes. Experimental data recently obtained with highly sensitive instru-ments by A. W. Hanson4 on zinc and by Podaschowsky5 on rock salt indicate that the elastic range in single crystals is considerably narrower than formerly was supposed. Moreover, a theoretical possibility of permanent deformation, under the influence of even the smallest shear stress in single crystals above a certain temperature (Td), has been developed by G. I. Taylor6. This evidence seemed to warrant an examination of the elastic limit in large single crystals by means of creep tests. The first metal chosen for examination was zinc.

Jan 1, 1936

By W. C. Maurer

A study of the mechanics of shear failure of rock under pressure has been made. The transition from brittle to ductile failure occurs when the friction along the fracture surfaces exceeds the shear strength of the rock. A machine has been developed for measuring both the shear strength of rock and the friction along rock fracture surfaces. In this shear machine, the fractures are forced along definite planes; as a result, the rock is stronger than in compression tests where the fractures choose the weakest paths through the specimens. Friction is composed of several forces: (1) the forces to slide irregulurities on surfaces over each other; (2) forces to shear some of these irregularities; (3) molecular attractions across the fractures; and (4) forces required to break bonds resulting from melting and welding at the tips of irregularities on the surfaces. Friction along rock fracture surfaces is not proportional to contact pressure as usually assumed; instead, it increases as the contact pressure raised to the 0.4 to 0.8 power. INTRODUCTION It is difficult to produce tensile stresses under the high compressive stresses present in the earth; therefore, in deep drilling and geological faulting, shear failure predominates. This shear failure mechanism is complicated because rock is a heterogeneous material containing pore spaces, microfractures, elastic discontinuities and other imperfections. A study of shear failure of rock under pressure has been made to obtain a better understanding of this complex mechanism. A machine has been developed and used to measure the shear strength of rock and friction along sheared surfaces. This machine has certain advantages over the compression test — shear properties can be measured under low normal stresses and shear stress and normal stress can be varied independently. The first part of this paper is a description of shear failure of rock under pressure. The role of shear strength and friction along fracture surfaces in the shear failure mechanism will be discussed. The second part consists of a description of the shear machine and a discussion of the shear strength and friction data obtained using this machine. It will be shown that shear strength depends upon the size of the stressed zone, and that friction does not increase linearly with contact pressure as usually assumed. Attempts are made to relate some of the new concepts to tectonic failure and to dril ling. SHEAR FAILURE IN ROCK TRIAXIAL TESTS The shear failure mechanism is illustrated by the triaxial test shown in Fig. 1. In this test, a cylindrical rock specimen is subjected to a confining pressure, PC, and an axial pressure, pa. These external pressures produce normal a and shear T stresses on inclined planes within the specimen equal to1 where 0 is the angle between the specimen axis and a normal to the inclined plane. Fig. 2 shows how triaxial specimens deform as the axial pressure is increased. The pressure is

Jan 1, 1966

The income of the Institute is derived from dues, subscriptions to MINING AND METALLURGY and sale of publications. These sources are fortunately supplemented by the interest from invested funds now amounting to over $500,000, a considerable portion constituting endowments for especial purposes. Aside from the medal funds the principal endowments are the James Douglas Fund for support of the Library, the Rocky Mountain Fund and the Seeley W. Mudd Memorial Fund. The income from the two last named is available for the support of research and a variety of other purposes. It is allocated by the Board of Directors upon recommendation of standing committees in each case. An active effort is being made to increase the endowments of the Institute, it being felt that unusual opportunities exist for research and public and professional service through the organization.

Jan 1, 1936

By A. G. Rozner

TRANSVERSE rupture tests have been commonly used in mechanical investigations of brittle materials. The specimens are simple, easy to prepare, and loading presents no difficulty. Owing to the complexity of stress distribution in bending1 one can determine stresses rigorously only for the elastic range. The bend-test results, however, are at times converted into tensile-strength data, determined as maximum fiber stress. The assumption is made that for small plastic deformations the linear stress-strain relation applies. This problem was experimentally investigated by Bach3 who tested cast iron in bending and in tension and found that the maximum fiber strength obtained in bending exceeded the experimental tensile strength by a factor depending on the geometry of the tested piece. The factor varied from 1.57 for a rectangular cross section to 2.12 for a circular cross section of the tested beam. Since this work was carried out 60 years ago, the cast iron used could be expected to have been highly brittle, thus the extent of plastic deformation prior to fracture very small. We have therefore carried out a number of tests on magnesium-modified cast iron with an average elongation of -5 pct. It was hoped that the data obtained from the tests would serve as a guideline for comparing data obtained in tension and bending for brittle materials. Mechanical properties were measured at room temperature on an Instron tensile machine at a crosshead speed of 0.05 in. per min. The three-point bend test employed cylindrical bars 0.20 in. in diameter with a 1.0-in. span. For the tensile test, cylindrical tensile specimens with a gage length of 0.85 in. and a diameter of 0.160 in. were used. Results are summarized in Table I. From Table I one can see that fracture strength

Jan 1, 1965

By L. F. Stutzman, George Thodos

A new graphical method, which is a modification of that proposed by Buckley and Leverett', is presented for the determination of the displacing fluid saturation at breakthrough for frontal drive mechanisms. This method is applicable to all types of fluids, which may be either soluble or insoluble in the oil at reservoir and injection conditions. This adaptation has unique advantages in handling problems in which either liquids or gases are the displacing fluids. INTRODUCTION In the displacement of oil from a reservoir with water or gas injected into the formation or by the expansion of a gas cap, the determination of breakthrough or flood advance is important to define the initial and subordinate phases of the operation. Thus, the determination of the displacing fluid saturation at breakthrough is fundamental to the establishment of over-all reservoir production. Methods for analyzing this saturation and for calculating production rates have been previously reported1,'*".". All of these methods utilize the rate equation for linear flow developed by Buckley and Leverett1. xs = QT - Qn/A? (?fu/?Su) .....(1) Sp where f, represents the volumetric fraction of displacing fluid in the total flowing fluid within the reservoir as is defined by: fo = 1/1+ ku/kd µn/µn .......(2) Since the time, ?, necessary for the flood front to travel distance ?X is unknown, Eq. 1 cannot be solved directly for the determination of the breakthrough point. Therefore, it becomes necessary to solve Eq. 1 simultaneously with an equation representing a fluid bal-ance on the reservoir behind the flood front. To develop such a fluid balance equation, it has been assumed that the fluid composition is uniform in the reservoir behind the flood front. Based upon this assumption, the follow-ing equation can be derived from a material balance on the displacing fluid: x = (?X) s Dx ? x=0 [ Snx - Sn1 ] dx = QT - Qn/A? It is readily observed that the displacing fluid satura-tion behind the flood front, Snx, may be determined through the simultaneous application of Eqs. 1 and 3. Although the approach may vary, this objective re-mains the same for all of the previously mentioned graphical or analytical methods. After Sox is determined, it is then possible to calculate the gas-oil and/or water-oil ratios and the rates during the initial and subordinate phases of production, and thereby define the production history of the reservoir. In this presentation only the de-termination of Snx is considered, and the reader is re-ferred to the several texts in reservoir engineering2,4,5 for a complete discussion on the methods for establish-ing the production history of a reservoir. PROPOSED METHOD FOR DETERMINING Snx Since at any time the quantity, QT - Qn/A? is a constant, Eq. 1 may be expressed in differential form as follows: dxsn = QT - Qn/A? d (? fn/? Sn) sn .....(4) Eq. 4 may be substituted directly into Eq. 3 to obtain: ? fn/? Sn ? [ Snz - Sn] QT - Qn/A? d ( ? fn/? Sn) = QT - Qn/A? ...............(5) Eq. 5 simplifies to the expression: ? fn/? Sn ? [ Snz - Sn] QT - Qn/A? d ( ? fn/? Sn) = 1 ....(6)

Jan 1, 1958

By L. Obert, D. E. Stephenson

The objectives of this investigation were to develop a laboratory procedure in which core discing could be produced under known (and variable) stress conditions, and to study the discing characteristics of several fypes of rock. Discing of rock cores refers to the formation of discs or wafers of relatively uniform thickness which fracture or rupture on surfaces approximately *Fracture is a type of failure in which there is a complete loss of cohesion and fresh surfaces are created. Rupture is a type of failure in which there Is only a partial loss of cohesion. normal to the axis to the core (see Fig. 1). Usually the surfaces of the discs are concave-convex with the concave side toward the collar of the hole. The surface of the fractured discs are like those created by a tension failure (or possibly a shear failure with virtually no normal compressive stress). This phenomenon has been observed by a number of investigators1-5 in the course of diamond drilling in underground mines, especially in areas suspected of being under high stress. The state of stress in the core required to produce discing is not exactly known. Tranter and craggs6 theoretically investigated the stress distribution in an infinite cylinder, subjected to hydrostatic pressure, minus p, from z = 0 to z = 8 and unloaded from z = 0 to z = 8, Fig. 2. The exact solution to this problem shows that a tensile stress develops in the loaded region near z = 0 with the greatest tensile stress on the axis of the cylinder. A tensile stress also developed on the surface of the cylinder at a point just outside of the loaded zone. Jaeger and Cook3 experimentally investigated the discing mechanism by biaxially loading cores in a pressure jacket sealed at the ends by O-rings. According to the Tranter and Craggs theory it would be expected that failure should occur at the pressure discontinuity at the O-rings. The experimental results showed that if the specimen was unjacketed it broke at random points within the pressurized zone and at a pressure somewhat greater than the tensile strength of the specimen, presumably due to the development of a

Jan 1, 1965

By H. O. McLeod, J. M. Campbell

Data analysis of pentane and hexane adsorption from natural gas in a fixed bed of silica gel shows that constant length mass transfer zones form, the curvature of the adsorption isotherm controls the growth of the mass transfer zone and surface diffusion of molecules inside the silica gel particle controls the mass transfer rate. Curvature of the hexane isothem is more than the curvature of the pentane isotherm. Because of this curvature the hexane adsorption zones reached a constant length. In contrast, the pentane adsorption zones were always increasing in length during each run. A procedure was developed to obtain correct mass transfer coefficients using effluent curve slopes. These transfer roefficients increase with the amount of hydrocarbon adsorbed on the silica gel particle. The characteristic shape of the hexane effluent curves also show that molecular diffusion inside the silica gel particle controls the adsorption rate of pentane and hexane. INTRODUCTION The purpose of this study was to determine the mechanisms that control the dynamic adsorption of hydrocarbons from a natural gas onto silica gel. Before one can deal effectively with multicomponent adsorption, the transfer mechanisms by which a single hydrocarbon component is adsorbed from the gas stream must be defined. Two principal investigations of this system have been published ' and indicate that diffusion through the gas around the particle controls the adsorption rate. Some of the experimental observations in each study either do not support this transfer mechanism or are inconsistent with the mathematical model used in analysis. In this study surface diffusion of molecules inside the particle controls the mass transfer rate of pentane and hexane. This mechanism is indicated by the effluent curve shape for a constant length transfer zone and by the variation of the mass transfer coefficient with concentration of the adsorbed hydrocarbon. THEORY AND DEFINITIONS — MATHEMATICAL MODELS Mathematical solutions for the isothermal adsorption of a trace component from a carrier gas are derived from three relationships: the mass balance or continuity equation, the equilibrium relationship between the gas and solid phases, and a mass transfer rate equation. The transfer rate is proportional to the adsorbate concentration gradient within either the gas or solid phase. Mathematical solutions of these equations usually give the adsorbate concentration as a function of time and distance from the bed inlet. That part of the bed in which the adsorbate concentration changes from a maximum to a minimum value is called the transfer zone. This transfer zone is directly related to a plot of the effluent concentration vs time which has a characteristic S-shape. This general shape is determined by the continuity equation and occurs in many processes of diffusional transfer.

Jan 1, 1967

By V. H. Whihelm

Since 1935 California has enjoyed a remarkable cycle of discovery, which has placed the state in a very satisfactory position in regard to oil reserves. Most ol the geophysical plays have been drilled and it is possible that new discoveries must be made by the application of careful geologic and stratigraphic studies. During 1940 only one new field was discovered, which, although not of major importance, may lead to additional discoveries. During the year, 113 wildcats were drilled. New discoveries, extensions and a reappraisal of discoveries made in 1939 will not approximate over 50,000,000 bbl., as against an estimated withdrawal during the year of 224,000,000 barrels. Demand in terms of crude for 1940 was 632,000 bbl. per day as against 626,000 bbl. per day for 1939. Demand for gasoline was the same as in 1939, but the demand lor fuel oil increased 3.8 per cent. Compared with 1939, Japanese shipments decreased from 75,786 bbl, per day to 61,000 bbl. per day, but the balance of Pacific foreign shipments increased from 59,409 bbl. per day to 61,304. Total with-drawals from storage during the year will approximate 7,000,000 bbl., almost all of which is fuel oil. Drilling activity was slightly greater than in 1939 and accounted for 890 new producing wells as against 851 for 1939 (Table 3). Production averaged 611,900 bbl. per day as compared with 614.,842 bbl. per day for 1939. The productive acreage figure of the state was increased by 4000 through discoveries and extensions. New Discoveries Los Angeles Basin District Del Vdle Field.—Northwest of Newhall, where the first oil well in California was drilled, R. E. Havenstrite completed his Lincoln No. I well, flowing 390 bbl. of 50" gravity oil together with 7000 M CU. ft. of gas. Later the well was recompleted, after cutting off the gas, for 950 bbl. of 34" gravity oil. The type of structure from which this production is coming is a plunging anticline, complicated by faulting. The Lincoln No. I well uncovered approximately 180 ft. of net sand. This field contains a gas cap and its indicated productive area approximates 500 acres. An intensive wildcat drilling campaign is expected during this coming year in the district in the vicinity of the Del Valle field. Extensions and Deeper Sand Developments Los Ange1es Basin District Athens Field.—On the northwest plunge of the Athens structure, the Thorley Oil Co. completed its No. 12-1 well, flowing 250 bbl. of 3 2" gravity oil from a depth of 8097 ft. The area in which the well is located is complicated by faulting and it is impossible at this date to determine the importance of this deep-zone discovery.

Jan 1, 1941