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By J. F. Havard

The enterprises based upon the industrial minerals are diversified in geologic habit, mining systems, processing techniques and marketing methods. Nevertheless, in 1972 these enterprises faced many of the same frustrations and hopes and knotty problems and crucial decisions. Volume and profits were generally improved but were uneven in extent and effect. The U.S. cement industry, for example, was unable to meet demand in major markets. It was constricted by a frozen low-level price structure, faced expensive pollution control measures and watched heavy imports penetrating its markets from several European nations, Mexico and Canada.

Jan 1, 1973

By Eugene R. Rice

There are many methods for determining the meridian, but all of those in common use involve at least two separate observations, one for latitude and one for azimuth. Such observations made upon a south star at any hour are open to the objection of possible inaccuracy due to ignorance of the absolute refraction, and also to slow change in the altitude of the star when near the meridian. The method of observing a circum-polar star at elongation. besides requiring a separate observation for latitude, is open to the serious objection that clouds may obscure the star at the critical moment. Moreover, a tedious wait for the star to come to elongation is sometimes necessary. Many of us can recall 'long, cold, weary vigils, waiting for Polaris to reach elongation. For observing a circumpolar star at any hour, not only the latitude, but also the true time, must be known. This it is practically impossible to obtain, except in regions reached by the telegraph, and usually then one has to know the longitude also, in order to reduce " standard time" to " local time." The results obtained by this method, when the star is at culmination, are not very good, unless the true local time is absolutely known. The methods of obtaining the nleridian from the sun, by means of a solar attachment, or by direct observation, while good, are not absolute, by reason of refraction, change in declination of the sun, and small change in vertical angle, when the sun is near the meridian. For these two methods, latitude, time, and approximate longitude have to be known. In the method here described, only one observation is needed, and from it are computed azimuth, latitude, aud sidereal time. In other words, one call observe a circumpolar star—Polaris

Jan 1, 1911

By C. C. Harris Discussion by B. K. Loveday

B. K. Loveday (National Institute for Metallurgy, Johannesburg, Republic of South Africa) - The paper and subsequent technical note' describing a method of determining the parameters of the three-parameter size-distribution equation developed in the paper were read with much interest. This equation was also used at National Institute for Metallurgy (NIM) to describe size distributions in grinding tests, because it was necessary to have a single equation to describe the size distribution at any time during a test. A graphical method also was used to determine the three parameters, and the use of this method as an alternative to Professor Harris's latest method is discussed here. The three-parameter model can be expressed as follows: Eq. 1 can be rearranged and transformed to Yield a linear reiationship between Y and X (transformed) log

Jan 1, 1970

By J. R. Lucas, R. L. Frantz

Mine sealing programs for the alleviation of acid mine drainage were begun by the Federal Government in the '30's. As part of an acid mine research project to The Ohio State University, a field test was undertaken to determine the effectiveness of mine seals for reducing mine acid. Details of the tests made at the McDaniels mine show the feasibility of air-sealing and flooding an acid-producing drift coal mine. Work by the University continues. The Federal Government undertook in the early thirties an extensive mine sealing program for the alleviation of acid mine drainage. In the states of West Virginia, Ohio, and Pennsylvania many general summaries have been made on this program but no critical evaluation with supporting data has been found on the effectiveness of mine seals for reducing mine acid. Because of this it was decided to undertake a field testing program as part of an acid mine research project of the Engineering Experiment Station, The Ohio State University. The objective of this phase of the project was to develop and install a field research laboratory for acid mine drainage studies. Specifications for such a mine laboratory were developed and resulted from the following considerations: 1) Size and preservation—the test mine shou1d be of limited size to permit frequent and detailed examinations; it should be in a reasonably sound condition to permit safe entry. 2) Isolation—the mine should be physically separated from all other mines. 3) Openings—a minimum number would be desirable to reduce the sealing problem. 4) Structure—the mine especially near the openings should be structurally sound. 5) Acid production—the mine should be producing significant quantities of acid. After considerable searching, the McDaniels mine was selected in the Hocking coal field in Vinton County just above Lake Hope State Park in southeastern Ohio. The small drift mine in the middle Kittaning coal consisted of two small rooms with one mine opening about 6 ft above a seasonal stream bed. Before it was finally decided to seal the mine, a short study was made of the acid drainage over several months. Fig. 1 shows a plot of acidity (milligrams per liter), flow (gallons per minute), and acid production (pounds per day) vs time over the sampling period. Because the coal was overlain with a porous sandstone, the mine drainage was consistent the year around even though the mine was

Jan 1, 1961

By A. Raja, C. C. Harris

Apparatus for maintaining constant — but adjustable — pulp level and rate of froth removal are described. The results of preliminary experiments into the effect of scraping speed on the rate of solid and liquid recovery with a semi-batch system are presented. Glass spheres restricted to a narrow size range is the solid under investigation. Graphical methods for estimating the mass of recoverable material and the zero error are given. The semi-batch procedure1 is extensively used in laboratory flotation testing, though the method is subject to variability of moderate severity. Raffinot2 concluded from a statistical study of the difference between replicate tests, that the ptincipal source of errot was the test itself and not sampling or chemical analysis. These differences can be ascribed principally to changes in pulp volume and reagent concentration, and uncontrolled rate and depth of scraping. Semi-batch testing has been criticized1 on these grounds as a means of investigating flotation kinetics. This paper discusses and describes modifications to laboratory flotation equipment which reduce the number of manual operations and lead to improved control. Kinetic studies were the primary reason for developing the apparatus described. It should, however be a useful aid in normal flotation testing. Some preliminary results of experiments are presented.

Jan 1, 1967

By A. A. Toprac

The recurring problem of joint failures in ofjshore structures, coupled with the catastrophic collapse of many of these structures during Hurricane Hilda (1964), hay forced reconsideration of techniques presently used to design sfuctural joints. This paper presents results of studies conducted for this reconsiderat?on. Only right-angled T-joint,s and cross-joints where a brace was welded directly to the undisturbed surface of another tube (the chord) were considered. Tests were performed on seven T-joint and 12 oross-joint specimens of two types which were designed to give a broad but practicd range to the geometrical parameters believed to be of significance to the problem. These paramefers were expressed in dimensionless form. Each specimen of the T-joints was instrumented wirh both electrical resistance strain gauges and deflection dials. After the elastic tests were concluded, each specimen was loaded to failure by applying an axial tensile load to the brace. The cross-joints were tested to failure without measuring elastic strains. Theoretical solutions for the stresses in a cylindrical shell due to a distributed radial load over portions of its surface were numerically evaluated. The experimental results are compared with calculated values obtained using Bijlaard's and Dundrova's theoretical analyses. INTRODUCTION During the last IS years a large number of structures were built for the offshore exploration of oil both in the Gulf of Mexico and dong the Pacific Coast.' In all these offshore platforms, the tubular shape was extensively used since this shape provides outstanding strength in proportion to its weight, compared to other shapes, when all directions (x, y, z) are considered. Past use of tubes was hampered because of connection details. But with the advent of welding, it became no more difficult to connect tubular shapes than to connect rolled shapes. However, some problems have been encountered in actual construction in making welded joints that are adequate and yet economical. In trying to connect tubular members, designers have used a varied number of methods; consequently, some of the joints seem to be very expensive in detail while others appear weak and underdesigned. An inspection of offshore platforms owned by different companies indicates the use of a large number of joint arrangements and configurations. Such a variety of joint types in current service indicates the wide divergence of opinion that exists on how such joints should be designed, stiffened and strengthened. Fig. 1 shows the various types of connections that have been used in practice. This paper reviews the present state of art on tubular joints of the T and cross type, and presents results of experimental and analytical work being conducted at The U. of Texas and elsewhere. It is believed that such information will be of great help to designers for the formulation of proper design procedures for joints. CONNECTION PROBLEM Recently, cracks have been observed in several welded connections in offshore structures. Fortunately, until about 1 1/2 years ago, these failures have been localized and have not resulted in the collapse of structures or loss of life. For example, one platform installed in Louisiana during 1955 in about 60 ft of water had been subjected to four tropical hurricanes. This platform successfully withstood these forces and was later removed because operations at this location had been completed. Many joint failures were observed during the removal.

By Thomas C. Wilder

Jan 1, 1965

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Jan 1, 1938

By K. E. Merklin, F. D. DeVaney

Students of the modern blast furnace seem unanimously agreed that they are observing a major revolution in practice. Rather than changing construction and operation of the furnaces, most of the great advances now under way deal with the raw materials feed. Prepared burdens have gained increasing significance during recent years. Sizing, concentration, and agglomeration have all become bywords to greater production and reduced operating costs. The remarkable results with test furnaces in which self-fluxing sinter makes up part or all of the ore charge foretell even greater improvements. Other investigators have reported many of these advances, and it is enough to predict here that more and more operators will turn to the use of self-fluxing sinter. This change in the operator's requirements comes at a time when one major section of the iron ore regions, the Mesabi, is finding it difficult to maintain, let alone improve, the tonnage and grade of its shipping product. To meet the new demands with respect to quality and structure, the iron ore producers of this area turned first to screening, crushing, and concentrating intermediate ores. More recently, declining higher-grade reserves have led to multimillion-dollar investments in plants to treat the low-grade magnetic taconites.1,2 To yield a suitable concentrate, the Minnesota magnetic taconites must be ground to about 80 pct through 325 mesh, too fine to be charged directly to the blast furnace or to make acceptable feed to the sinter strand. The pelletizing process was developed to meet the structure requirements laid down by the blast furnace operators. Taconite producers are succeeding in their efforts just when the attention of the blast furnace man is being drawn to the great advantages of self-fluxing sinter.3 The taconite operators are ready with an alternative. Why not produce sclf-flus ing pellets? At the Hibbing laboratory of Pickands Mather & Co., where much of the early work was done that led to Erie Mining's 7.5-million ton taconite plant at Hoyt Lakes, Minn., preliminary investigations have been made. Present Taconite Operations: Details of this work will be clarified by a brief review of agglomeration practice in commercial taconite plants. After the taconite has been ground to about 80 pct through 325 mesh to liberate the magnetite grains, the ore is concentrated on magnetic separators, thickened, and filtered to about 10 pct moisture. This structure and moisture fit in closely with the conditions required to produce good balls. It has been found with taconite concentrates that at least 60 pct of the feed to the balling drum must be —325 mesh to obtain good ball compaction within reasonable time. The filter cake moisture usually permits a slight water addition at the balling drum, and further balling control is obtained by adding about 12 Ib of bentonite and 1 1/2 lb of soda ash per dry short ton of concentrate. These additives, and occasionally small quantities of fine coal, are thoroughly mixed with the filter cake ahead of balling. The swelling property of bentonite improves the green and dry strength of the balls so they can be handled without breakage until they are fired. Soda ash is added for pH control to insure maximum performance of the bentonite, and coal is added for more heat in the firing process when required. The balls, normally 3/8 to l-in. diam, are brought to a temperature of 2350" to 2500°F in the indurating furnace. Heat for this process comes from three sources: 1) fuel burned in the combustion chamber, 2) oxidation of the magnetite concentrates to hematite, and 3) coal added to the balls. Pellet strength is developed by grain growth and bridging and, if enough slag-forming constituents are present, by slag bonding. Conversion to hematite is usually close to 100 pct in the fired pellets. Batch Test Procedures: Initial studies of self-fluxing pellets were made by producing balls on a batch basis under carefully controlled laboratory conditions. The l-in. balls, uniform in size, were fired in an oxidizing atmosphere in a standard laboratory muffle furnace. The firing procedure consisted of

Jan 1, 1961

By E. C. Stephens

The eastern Washington— Idaho clay region stretches along the northeast margin of the Columbia basin for 150 mil es. The three better known and developed clay areas are Clayton, Wash., (2 miles north of Spokane); Mica, Wash., (10 miles southeast of Spokane); and Moscow-Deary-Bovill, Latah County, Idaho (about 80 to 90 miles southeast of Spokane) see Fig. 1. Clays from the eastern Washington— Idaho clay area have been mined for more than 50 years. At present Mica, Washington deposits are used by the Gladding—McBean & Co. to make a variety of bricks and ceramic products and Latah County, Idaho clays are used by the A. P. Green Fire Brick Co. to make refractories. The Anaconda Co. made an intensive investigation of the clay deposits in the northeastern Washington-!daho area in 1919 to determine the existence of a supply of raw materials from which alumina could be made. The greater part of the work, which included systematic drilling and shaft sinking, was concentrated at Mica, Wash. This was part of a research project carrted on by the Anaconda Metallurgical Research Dept. under the direction of Frederick Laist and F. Frick and it was terminated in 4920. V. D. Perry, Vice President and Chief Geologist for The Anaconda Co., in 1952 assigned the writer to make a preliminary study of clay and other potential sources of alumina ore in the Pacific Northwest with particular emphasis on those deposits which might be of future importance to The Anaconda Co9s. then new aluminurri plant at Columbia Falls, Mont.

Jan 1, 1961

By F. Haessner, M. Wilkens, U. Jakubowski

ThOUGH at present there is a wide range of possibilities for the quantitative determination of preferred orientations, pole figures of identical specimen material have not been determined by different methods as yet.''' In this paper a comparison of (Ill), (200), and (220) pole figures is presented which were obtained from a 95 pct cold-rolled high-purity cop- per sheet (99.9998 pct Cu), by three different methods. The three methods are: a) The combined X-ray reflection-transmission technique of plane samples by schulz3 and Decker, Asp, and Harker. 4 A Siemens texture goniometer was used. The experimental details are described elsewhere. 6 b) The X-ray reflection technique of spherical samples by Jetter and Boric.' A Siemens texture goniometer with some modifications was used. The samples were prepared by sticking 140 polished sheets together with an adhesive and machining a sphere (20 mm diam).* Additional

Jan 1, 1967

By L. F. Elkins

Water coming into wells with bottom water present in the Fosterton field, when their oil recovery was only 0.1 to 1.5 per cent of oil in place below the lowest perforation, confirms lack of shale barriers to vertical flow which also are not apparent in cores and electric logy. Low contrast of vertical and horizontal permeability, high mobility ratio betweerz oil and water zone and pos.rible rate effects due to gravity Combine to prevent easy analysis of water invasion pattern and efficiency by analogy or intuition. Theoretical analysis of performance including these factors using a new direct nurnerical .solution of potential distribution in a network led to unanticapted indications that water would under-run the entire oil reservoir with low volumetric coverage if supplied through natural influx or peripheral water injecfion below the oil-water contact. An unusual pattern of water injection is to he adopted in this recently unitized pool to provide more uniform water flooding in that two-thirds of the oil reservoir not underlain by bottom wafer. INTRODUCTION The Fosterton field, Southwestern Saskatchewan, Canada, was discovered in Jan., 1952. It produces at a depth of 3,100 ft from a pinch-out of the Roseray sand at the Lower Cretaceous-Jurassic unconformity. The field, covering 2,500 acres, contains 54 wells on 40-acre spacing. Development was essentially complete in June, 1954, but significant production did not start until May, 1955, when a pipeline outlet became available. Within one year rapid in- creases in gas-oil ratio and early encroachment of water created operating problems in the down-structure eastern half of the field and raised serious questions about reservoir performance and ultimate recovery. This paper describes the unusual behavior of water encroachment—on both well and reservoir bases—and the analyses made to interpret it. The field was unitized July 1, 1958, for water flooding. A somewhat unconventional

By F. J. Chernosky

Most previous studies of coal flotation utilized chemically pure reagents. Since such reagents are not available in quantity, a study of various wmmercially available reagents as frothers was undertaken. Flotation procedures similar to those used in a large number of commercial coal flotation plants were employed. The reagents used were compared on yield-selectivity-wst basis. The selectivity was found to be relatively constant with yields above 70% but the reagent cost varied greatly. The types of reagents available were compared. In the past, a number of papers have been written on the use of various reagents as coal flotation frothers. For the most part, these have been an attempt to correlate the intrinsic chemical and physical proper- ties of the reagents or reagent groups to the floata-bility of various fine coals. Because of the type or nature of evaluations made, chemically pure reagents were normally used. Generally, these reagents are unavailable in commercial quantities. Therefore, the results obtained with these reagents were usually limited in usefulness to the plant operator or metallurgist. This paper presents the results of a study in which commercially available forms of various reagents were used as flotation frothers. Flotation procedures which would conform in general to those employed in a large number of commercial coal flotation plants were utilized. The objective of the test was to compare these reagents on yield-selectivity-cost basis, that is, 1) the yields obtained, 2) the ash levels obtained and 3) the reagent cost relating to these results. REAGENTS The reagents employed have been grouped into the following chemical classes: 1) aliphatic alcohols, 2) terpines, 3) glycols (synthetic water-soluble

Jan 1, 1963

By C. S. Samis, D. P. Seraphim

In the presence of oxygen, galena is oxidized in an aqueous medium containing ammonium acetate in accordance with the following reaction: PbS + 1/2 0, + 2 NH~Ac -» PbAc, + So + 2 NH: + H2O. This reaction was studied in an autoclave under oxygen pressure by polarographic measurement of the concentration of lead ion in solution. Oxidation rate is parabolic. The reaction products are lead acetote and elemental sulfur, the latter forming a film on the galena crystal. Reaction kinetics appear to be determined by the diffusion of lead from the galena phase to the solution interface through the film of sulfur. RECENT applications of pressure leaching on a commercial scale have emphasized the metallurgical importance of the oxidation of sulfide minerals in aqueous media by oxygen under pressure. Research experience has shown that sulfates, thio-nates, and metal oxides are the products of humid oxidation of sulfide minerals in basic solutions. The metal oxides may be solubilized in the presence of a complexing ion.' Certain oxide minerals are also amenable to treatment by this type of oxidation.' Several kinetic studies have been made of reactions of this type. Stenhouse' found that pyrite (FeS?) oxidized in a sodium hydroxide solution to produce a soluble sulfate and an insoluble layer of iron oxide and that the kinetics of the reaction were controlled by oxygen diffusion through the oxide layer. Andersen' studied the oxidation of galena (PbS) in a sodium hydroxide solution under oxygen pressure. He found the lead and sulfur to be simultaneously oxidized to produce plum bite ions and sulfate ions, and that the reaction rate was proportional to the surface area of the galena. The kinetics appeared to be determined by the reaction of oxygen and water with the galena surface. In each of the above reactions the metal and sulfur components of the mineral were oxidized simultaneously and at equal rates. In the present study the alkaline medium has been replaced by an approximately neutral solution of ammonium acetate in which lead sulfate is soluble. Under the conditions no sulfate was produced and no sulfur could be detected in the solution. The metal component of the mineral was solubilized and the liberated sulfur remained as a film of elemental sulfur on the surface of the galena crystal. A kinetic study of this reaction was undertaken to establish the kinetic mechanism and to determine the rate controlling step. Specific reaction rates were determined by oxidizing crystals of galena of measured surface areas in an autoclave maintained at the desired temperature and oxygen pressure. The rate of reaction was followed by measuring the concentration of lead in the ammonium acetate solution with a cathode ray polarograph, employing stationary platinum electrodes incorporated in the autoclave. Experimental Materials and Equipment Crystals of galena obtained from Violamac Mines, Retallack, B. C., were selected for oxidation because

Jan 1, 1957

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,' 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-' e-:".'m'"'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.' 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' 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,' 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'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

By D. Geoffry Minnes

Nepheline syenite is a silica deficient crystalline rock consisting of albite and microcline feldspars and nepheline, together with varying but small amounts of mafic silicates and other accessory minerals. Nepheline-bearing rocks are widely distributed around the world but only in Canada, Norway, the Union of Soviet Socialist Republics, and the United States are deposits worked commercially. Because of its low melting point and fluxing ability, nepheline syenite was investigated in the early 1900s by many students of glass and ceramics. Although the nepheline syenite deposits in Methuen Township, Ont., Canada, were discovered as early as 1897 it wasn't until 1935 that the first mill was erected to produce nepheline syenite products. In Canada, nepheline syenite deposits are worked by Indusmin Ltd. and International Minerals and Chemical Corp. (Canada) Ltd. who have combined production capacity in excess of 1800 tpd. Between 1935 and 1972 seven million tons valued at $78 million were produced from the Methuen Township deposits. In Norway, the Norsk Nefelin Div. of Elkem Spigerverket has produced nepheline syenite from a deposit on Stjernoy Island in western Finnmark since early 1960. Between 1961 and 1972 the company produced 930,000 mt with an estimated value of $17 million. Nepheline syenite has been under investigation in the Union of Soviet Socialist Republics (USSR) since at least 1928. In 1951 the first commercial alumina works was brought on stream at Volkhov, near Leningrad, utilizing nepheline concentrates from the Kola peninsula as mill feed. Since then two others have been completed and more are planned. Large quantities of portland cement, sodium carbonate, and potassium carbonate are produced in conjunction with the alumina. In the United States, nepheline syenite has been produced for many years from deposits in central Arkansas by the Big Rock Stone and Materials Co. for construction aggregates and, since 1947, for roofing granules by the 3M Co. Chap. 16 on "Feldspar, Nepheline Syenite, and Aplite" in the 3rd ed. of Industrial Minerals and Rocks (Castle, and Gillson, 1960) and Nepheline Syenite Deposits of Southern Ontario (Hewitt, 1960) contain excellent accounts of earlier commercial development of nepheline syenite as a glass and ceramic material. Therefore this chapter deals mostly with the period since 1960 and with matters not previously reported in detail. An English monograph on Nepheline-Syenite and Phonolite (Allen et al., 1968) is a complete current survey of nepheline syenite which, with its very complete list of references. is an excellent source book. End Uses Nepheline syenite from the Canadian and Norwegian producers finds use primarily in the manufacture of glass and ceramics. One producer also makes several grades of nepheline syenite that are useful as extender pigments and fillers in paint, plastics, and rubber. In the Soviet Union nepheline is used in increasing quantities in the manufacture of alumina, alkali carbonates, and portland cement and to a lesser degree it is used in the manufacture of colored container glass.

Jan 1, 1975

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 M. Felsenthal

Engineers are frequently faced with the problem of having to predict oil recovery from a solution gas drive reservoir in the early life of a field. This is often the time when actual laboratory or field-derived gas-oil permeability (kg/k0) data are not yet available. Although excellent collections of k0/k0 data for various types of rocks may be found in the literature,1,2,3 a need exists for a more detailed correlation of k0/k0 data with core properties such as porosity, permeability, clay content or pore-size distribution. It is the purpose of this article to present this type of correlation for sandstone material. The correlation is based on laboratory tests performed on over 300 core samples from 19 reservoirs in the United States and Canada. EXPERIMENTAL Cores were analyzed by routine procedures, using samples of conventional size (7/8-in. diameter, 7/8-in long) cut parallel to the bedding planes. Air permeability was measured at 1.67 atm mean pressure in a Hassler-type apparatus. Porosity was determined with the aid of a Ruska bulk volume meter and a Boyle's Law rock volume meter, An evaporation method' was used to evaluate irreducible water saturations. Core samples were saturated with 25,000 ppm NaCl brine. The brine was reduced to the irreducible saturation, and the remainder of the pore space was filled with kerosene. This was followed by multiphase flow tests using the so-called "dispersed feed" technique.5 n this technique, gas and oil (kerosene and kerosene-saturated air) were dispersed with the aid of a porous Alun-durn feed head, the face of which contained a waffle-shaped system of Lucite-lined grooves. Oil entered the back side of the feed head and emerged at the raised areas of the front face. Gas was introduced directly into the system of grooves at the front face. The gas-oil mixture then entered the test core which was kept in capillary contact with the feed head. Permeabilities were determined from rate and pressure measurements and saturations from weights. All determinations were performed at equilibrium or steady-state conditions. Pore-size distributions were determined on selected samples by a mercury injection technique.6 GENERAL CORRELATIVE TRENDS When examining data from a given reservoir, it was noted that k0/k0 vs saturation curves became generally less steep as specific air permeability increased, a development that has a favorable effect on oil displacement efficiency by solution gas drive. This trend has also been reported by others in the literature.' An effect of porosity on k0/k0 data was also noted. This effect was not generally discernible in a study of relative permeability data for a given reservoir but became apparent when data for sandstone reservoirs of similar lithology but differing average porosity were compared. For instance, in a comparison of argillaceous and/or calcareous sandstones from 11 reservoirs ranging in average porosities from 14 to 28 per cent, a definite trend was noted, indicating that for a given permeability k0/k0 curves became less favorable (i.e., steeper) as porosity increased. A similar trend was observed for a group of comparatively clean sandstones from five reservoirs ranging in average porosities from 15 to 21 per cent. For a given permeability and porosity, comparatively clean sandstones gave more favorable k0/k0 curves than argillaceous and/or calcareous sandstone or chert reservoirs. The laboratory studies also showed that least favorable k0/k0 curves were exhibited by shaly sandstone, conglomerate, and sandstone containing carbon inclusions. Table 1 lists the various source reservoirs classified by lithology types. To facilitate a correlation of k0/k0 data with core characteristcis, it was found expedient to work with

By G. Thodos, D. E. Matschke

Cansiderable time and effort frequently are expended to establish, with a degree of confidence, the PVT behavior of pure substances. In particular, a great deal of experimental information contributed by a number of investigators is available in the literature. The data of each investigator, although significant in themselves, cannot be used with a high degree of confidence until they are compared with the continuum of information presented by others. Current interest in thermodynamic and transport properties, for not only the gaseous state but the con-densed state as well, requires that PVT infarmation be presented for both regions. The density dependence on temperature and pressure, when presented as a continuum, is of considerable value in itself, especially since the available equations of state fail to properly account for the PVT behavior in the condensed state. For this reason and to incorporate PVT data recently presented in the literature, this investigation was carried out. In their studies concerned with the thermodynamic properties of methane, Matthews and Hurd in 1946 utilized the data of Kvalnes and Gaddy and Olds, Reamer, Sage and Lacey to establish the PVT behavim of methane in the superheated region and the saturated liquid densities of Keyes, Taylor and Smithl in conjunction with the Clapeyron equation to develop the densities for the saturated envelope. Current activity sponsored by API Project No. 44 under the direction of F. D. Rossini has led to a tabular presentation of compressibility factors for gaseous methane in the superheated region.la These values were obtained by using smoothed residuals, developed from experimental data and the Ben edict-Webb-Rubin equation,' to establish internally consistent compressibility factors for the real gas. This approach offers probably the most precise presentation of PVT information for gaseous methane to date. The PVT behavior of methane also can be represented accurately by equations of state such as the Benedict-Webb-Rubin equation or the Martin-Hoa equation.' These equations, although valuable for analytically representing the PVT behavior, lack precision in the compressed-liquid region. The PVT data available in the literature for methane were utilized to obtain reduced densities that are presented in Figs. 1 and 2 as functions of reduced temperature with parameters of reduced pressure. The critical constants utilized for methane are those reported by Kobe and Lynn." These critical values, T, = 191.1°K, PC = 45.8 atm and p, = 0.162 gm/cc, produce a critical compressibility factor, z, = 0.289. The PVT information, as obtained from the literature, in many instances was not presented in an immediately

By K. E. Gray, M. S. Seth

In Part I of this work,1 equations of elasticity were formulated for transversely isotropic, axisymmetric, homogeneous, porous media exhibiting pore fluid pressure. Equations of elasticity and the thermal analogy method were used to determine transient horizontal, tangential, and vertical stresses and radial displacement in a semi-infinite cylindrical region when either a constant rate of pressure or a constant rate of flow is maintained at the wellbore. In this paper, the approach presented earlier is extended to finite reservoirs for the cases of (1) steady-state flow, (2) constant pressures at the well bore and outer boundary and (3) constant pressure at the wellbore and no flow at the outer boundary. Results of this work show that radial and tangential stress gradients are high near the wellbore but diminish rapidt; away from the well; the vertical stress gradient behaves in the same way but is less severe. Radial stresses are compressive or neutral, whereas tangential and vertical stresses may be tensile, neutral or com-pressive, depending upon the boundary conditions, the physical Properties of the system and the radial distance involved (vertical stresses are always compressive in an unbounded system1. For constant boundary pressures, both radial and tangential stresses increase with time whereas they both decrease for a closed outer boundary and constant pressure at the wellbore. The vertical stress decreases with time for both systems. For steady-state systems, radial displacement may be positive or negative, depending upon the dimensions of the system, the pressure differential and the porosity. Radial displacement may be positive or negative for a closed outer boundary but is positive for constant pressures at both boundaries. INTRODUCTION The importance, utility and complexity of a realistic appraisal of the stress state at and local to a wellbore were indicated in Part I. In this paper the analytical approach presented earlier is extended to finite, cylindrical reservoir geometry for the cases of (1) steady-state flow, (2) constant pressures at wellbore and outer boundary and (3) constant pressure at the wellbore and no flow at the outer boundary. Other than the outer boundary of the reservoir being finite, the physical system and assumptions pertinent thereto are the same as before. The reader may wish to review the mathematical development through Eq. 49 of Part I before proceeding here. SOLUTION FOR GENERAL BOUNDARY CONDITIONS THERMAL STRESSES AND DISPLACEMENTS Since normal stresses do not exist at the free boundaries of a system subjected to thermal stresses, the boundary conditions are

Jan 1, 1969