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By M. A. Elliott

The technology of gasifying coal to produce synthesis and pipeline gas has advanced significantly in the Past 20 to 30 years. This period has seen the extensive use of oxygen in coal gasification, the development of suspension gasification processes and fluidized-bed gasifiers, the operation of various gasification processes at elevated pressures, and operation of gasifiers under slagging conditions. These developments are discussed, and their application to commercial and pilot plant gasifiers is reviewed. Typical processes for synthesis gas production are described, and operating results are compared. Pipeline or high-Btu gas may be produced from coal either by catalytic conversion of synthesis gas to methane, or by the direct reaction of coal with hydrogen (hydrogasification) to produce a methane-rich gas. Neither of these methods has been applied commercially, but developments pertaining to each of them are reviewed, and general processing schemes are discussed. The use of coal as a raw material for manufacturing gas has a long and distinguished history. In fact, the gas industry began in the early 1800's when William Murdock demonstrated that it was feasible to produce and distribute gas made by retorting coal. Coal was used exclusively for gas manufacture until the middle of the 19th centruy, when Lowe invented the carbureted water gas process. In that process, coke was one of the raw materials used, so coal was still an important factor in gas manufacture. However the availability and relatively low cost of natural gas in the United States, and its widespread distribution by long-distance pipelines in recent years, has virtually eliminated the use of coal as a raw material for gas manufacture in this country. It should not be inferred from the foregoing that the technology of coal gasification has remained static in the United States and abroad. In fact, in the past two decades many new concepts have been developed in both the science and the technology of gasification. This progress has been a result of the considerable expansion in research on the fundamental chemistry and physics of gasification reactions, and in development work on gasification processes. This expansion in effort stems in part from increased interest in the use of gas as a raw material for the synthesis of chemicals and liquid fuels, and in part from the need to develop methods for gasifying coal and other solid fossil fuels to ensure a long-range supply of energy in the form of gaseous fuel. In these uses of gas, synthesis gas, a mixture of hydrogen and carbon monoxide in various proportions, is the starting material. It may be converted catalytically to gaseous and liquid hydrocarbons and other chemicals, or to hydrogen for use in hydrogenation or reduction reactions. Since coal is our most abundant fossil fuel, it is inevitable that one day it will regain its prominence as a raw material for gas manufacture. It is of interest, therefore, to consider the present status of gasification technology, directing attention particularly to advances made in recent years. Inasmuch as many comprehensive treatises l-3 and review4-7 of gasification technology are available, no attempt will be made in the present review to cover all processes in detail. Instead, the discussion will be concerned chiefly with typical processes embodying the advances that are most likely to be generally applied. ADVANCES IN GASIFICATION TECHNOLOGY For purposes of this discussion the starting point will be the conventional processes that were used for many years for the complete gasification of coal. These were: 1) carbonization in coke ovens followed by gasification of coke with air and steam in cyclic water-gas generators, and 2) fixed-bed air-blown producers. Both of these methods have obvious deficiencies when we consider that the ideal complete gasification process would be a single-stage, continuous

Jan 1, 1961

By D. W. Smith, Robert F. Mehl

It has been shown by numerous studies that the orientations of new metal crystals are determined by the orientations of the crystals in the original matrix, whether these new crystals are formed by recrystalliza-tion, by precipitation from solid solutions, or by transitions in the solid state. The orientations of crystals formed by recrystallization of cold-worked metals that bear preferred orientations are occasionally simply related to the initial preferred orientation; often, however, the relationship is not simple, but complicated and obscure in origin.1 The orientations of crystals formed by precipitation from solid solutions have been shown by many studies in this and other countries to be determined by the orientation of the crystals of the solid solution stable at the higher temperatures, though here again complicated cases have been found and no general theory is available.2 Related to this latter class are the relationships found in crystals formed by suppressed transforma-

Jan 1, 1935

By D. W. Smith, Robert F. Mehl

It has been shown by numerous studies that the orientations of new metal crystals are determined by the orientations of the crystals in the original matrix, whether these new crystals are formed by recrystalliza-tion, by precipitation from solid solutions, or by transitions in the solid state. The orientations of crystals formed by recrystallization of cold-worked metals that bear preferred orientations are occasionally simply related to the initial preferred orientation; often, however, the relationship is not simple, but complicated and obscure in origin.1 The orientations of crystals formed by precipitation from solid solutions have been shown by many studies in this and other countries to be determined by the orientation of the crystals of the solid solution stable at the higher temperatures, though here again complicated cases have been found and no general theory is available.2 Related to this latter class are the relationships found in crystals formed by suppressed transforma-

Jan 1, 1935

By J. L. Gillson

Joseph H. Birman (Chairman, Dept. of Geolcgy, Occidental College, Los Angeles, Calif.) Many thanks to J. L. Gillson for so comprehensive a survey of the titanium sand deposits of the world. Over the past two years, the writer studied rather carefully some of the Cretaceous ilmenite deposits in New Mexico and Colorado, including the Sanostee deposit shown in Gillson' s map, Fig. 6. The deposits were geologically mapped and sampled, surveyed by magnetometer, and the Sanostee deposit was drilled. Moat of the genetic interpretations made by Gillson concerning the recent sedimentary ilmenites can be clearly read in the Cre-taceous deposits in New Mexico. The deposits are in marine regressive members of the Mesaverde group. The deposits trend within a few degrees of N 55° W and persistence of this trend through both distance and time (the deposits are in different members of the Mesaverde group) implies that the deposits are offshore bar accumulations. Heavy mineral content ranges from about 10 pct to more than 50 pet. Thicknesses are from 4 ft to as much as 20 ft, widths range from 150 to 600 ft, and lengths range from a few thousand feet to a few miles. All are locally or completely overlain by carbonaceous shale and thin coal. The deposits are strongly altered, and from X-ray diffraction the principal titanium alteration product appears to be anatase. Drilling of the Sanostee deposit shows that the alteration is not related to the present erosion surface but took place at the site of deposition and before burial by the overlying sediments. Iron oxide derived from the alteration cements the grains and is the chief coloring agent in the immediately overlying shales. In the Sanostee deposit, there is virtually no feldspar, the gangue mineral being almost exclusively quartz. Sorting is excellent, but the quartz grains are subangular to angular. Petrographic examination reveals that the angularity is not due to overgrowths. Therefore, short distance transport is implied. The mineralogical composition suggests a low relief granitic terrane as the source area. Feldspar may have been decomposed by weathering at the source, but an alternative preferred by the writer is that each of the deposits represents a long-term concentration site (for example a large sand bar) which was continually being deprived of light minerals by wave action and selective transport. Feldspar may have been mechanically reduced in size more quickly than the quartz, and thus its rate of removal may have exceeded that of quartz. Concentration of heavy minerals would thus occur until the marine regression removed the zone of maximum wave energy from the site. Chemical alteration would then become the most important process until burial by encroaching swamp deposits.

Jan 1, 1961

By R. D. Pehlke, J. V. Gluck

AS a portion of a general study of liquid-metal thermodynamics, high-temperature galvanic cells were used to study the effect of added dilute solutes on the activity of zinc in dilute solution with molten bismuth in the range 450° to 650°C. 1,2 The cells were of the type The experimental procedures have been described previously.1 In the course of studies conducted in the bismuth-rich corner of the systems Bi-Zn-Au and Bi-Zn-Cu, marked discontinuities were observed in the electromotive force-temperature relations for a number of the experimental compositions. Above the discontinuity temperatures, the relations, which were linear, exhibited slopes similar to the binary alloy of the same mole fraction zinc, as shown in Figs. I and 2. Below the discontinuity temperatures, the slopes were markedly different, but the relations remained linear. In general, as the amount of the third eletnent was increased, the slope of the lower portion of the relations tended to become less positive. The slopes of electromotive force-temperature relations reflect the entropy of mixing of zinc and, therefore, the occurrence of a discontinuity marks the transition between two different equilibrium situations involving the solution of zinc. A number of other investigators3-5 have used such observations to determine liquidus boundaries in binary alloys. Since the upper portions of the ternary electromotive force-temperature relations of this study had the same slopes as the binary alloys, the discontinuities are interpreted as marking the transition between the single-phase liquid region and the underlying two- and three-phase regions. Reference to the Zn-Bi equilibrium diagram6 confirms that the binary alloys were single-phase liquids at the experimental temperatures. Fig. I shows the electromotive force-temperature relations for the alloys containing Bi-Zn-Au and Fig. 2 shows similar relations for the Bi-Zn-Cu alloys. In the lower portion of each figure, the temperature of the discontinuity is plotted vs the mole fraction of the added solute at the various levels of zinc concentra- tion. Cross-plots from these curves at constant temperature permitted the construction of the partial liquidus surface isotherms shown in Figs. 3 and 4.

Jan 1, 1967

By C. E. Melbye

A serious problem confronted the city of Gunnison early in 1958 in that, for a few months during each spring runoff, the water supply derived from the Gunnison River became polluted to an unsafe point. The city management had the choice of building a new filter plant to replace the old unworkable one or drilling wells to develop a ground water supply. The cost of a new filter plant was estimated at $180,000 compared to $50,000 for 6 wells, pumps, and additional water lines, hence their decision to attempt the development of sufficient ground water. Six wells at 300 gpm per well were estimated as necessary to handle the peak usage of 1800 gpm, compared to only 600 gpm winter usage. Although the water table is only about 7 feet below the surface, existing private wells drilled at random locations were producing much less than 300 gpm. The problem was to find sufficient quantities from about 6 wells. Since the presence of an ancient bedrock channel was suspected, which would be expected to localize greater quantities of water, the city of Gunnison authorized a resistivity survey to investigate bedrock topography below unconsolidated gravels. Survey results were highly satisfactory and led to the preparation of a fairly detailed bedrock contour map, Fig. 1. This map was used in selection of all well sites. The city of Gunnison is situated in a flat, broad, Quaternary gravel-filled valley (terrain dips south at 20 feet per mile) at the junction of the Gunnison River and Tomichi Creek. The valley, about 2-4 miles wide, is bordered by hills of Tertiary volcanics to the northwest, Cretaceous and Jurassic sediments to the north and northeast, and pre-Cambrian granite and gneiss to the south. One previous deep test well at the west end of the city hit pre-Cambrian granite at 496 feet, which, allowing for 40 feet of surface gravels, makes the older sedimentary section 456 feet thick. This section is probably all Jurassic Morrison formation, consisting of the Saltwash sandstone overlain by the much thicker section of Brushy Basin shales and mudstones. According to the driller's logs, each well was bottomed in what is believed to be Brushy Basin shale. FIELD PROCEDURE A standard Gish-Rooney type of resistivity apparatus was employed, which used 45-volt dry batteries as a direct-current power source. Applied voltages could be selected from 45 volts to a 270-volt maximum. Copper-coated steel stakes were employed as current electrodes and porous porcelain pots as potential electrodes to avoid possible polarization effects with direct current. The expanding Wenner electrode configuration was utilized for this investigation and measurements were made at 20 40, 60, 80, and 100-foot spacings,

Jan 1, 1961

By M. N. Shetty

LARGE copper whiskers (-100 p) of 11111 orientation were tested in a floor-model Instron testing machine, at liquid nitrogen temperature. (Testing methods will appear elsewhere.) Whiskers deformed by twinning after some initial deformation. A load-elongation curve at the onset of twinning is reproduced in Fig. 1. Twinning was confirmed by taking a back-reflection Laue picture, using a slit colli-mator, which showed distinct splitting of reflections. The tensile stress reached just before twinning is about 1.4 x 107 g per sq cm (-7.0 x106 g per sq cm—resolved shear stress) which drops to 1.2 x107 g per sq cm (-6 x 106 g per sq cm—resolved). This twinning stress is about five to ten times larger than the value for bulk single crystals of copper deformed at 77°K (-106 g per sq cm—resolved). Twinning models based on Cottrell-Bilby's pole mechanism are discussed in detail by Venables.' In the present work a mechanism based on the idea of failure of a Lomer-Cottrell barrier by recombination will be proposed. An L-C barrier may fail either by recombination or by dissociation.3 Fig. 2 provides the necessary information. It shows that the stress necessary to break such a barrier is about 1.8 x 107 g per sq cm by recombination and 4 x 107 g per sq cm by dissociation at 77°K. The twinning stress reached by whiskers is comparable to the stress level required for failure of an L-C barrier by recombination. (Stroh himself points out that his calculations should not be taken too literally.) We consider a segment of the L-C dislocation which has recombined (AB in Fig. 3) over a length to form the total dislocation which then glides in the

Jan 1, 1965

By J. C. Bokros, A. S. Schwartz

The irradiation-induced densification of pyrolytic carbon has been shown to take place by a simple first-order rate process. The values of the densification constant, kd, for isotropic carbons are 1.0 x 10-22, 1.4 X 10-22 and 2.8 X 10-22 (nut)-1 at irradiation temperatures of 520o, 670°, and 1000oC, respectively. The apparent activation energy obtained from the temperature dependence of kd for isotropic carbons is about 0.2 ev. Estimates of the maximum stresses that develop in isotropic carbons owing to shrinkage onto an unyielding support show that stresses in excess of 15,000 psi may be avoided during irradiatian at 600" and 1000°C if the initial coating density is kept above 1.5 and 1.9 g per cu cw, respectively. If a carbon coating on an unyielding support is not completely isotropic, stresses may continue to build up at high neutron exposures after densification is complete because of continued anisotropic distortion. Stresses in excess of 15,000 psi from this source may be avoided during irradiation at 1000°C if' the Bacon anisotropy factor is kept below 1.3. A variety of applications of carbon and graphite in nuclear technology has stimulated numerous studies of the effect of neutron irradiation on these materials One of the most interesting problems associated with the use of carbons and graphites in the high fast neutron fluxes of nuclear reactors arises as a consequence of the neutron-induced dimensional changes that occur during irradiation. Energetic neutrons displace car- bon atoms from their lattice positions; and, depending on the temperature, the interstitials and vacancies produced migrate to form clusters, recombine, or are annihilated at dislocations or crystallite boundaries. The competition of various sinks for the point defects results in structure-sensitive bulk-dimensional changes that vary with temperature in a complicated way. This paper deals with the neutron-induced dimensional changes in turbostratic carbons that are being used as coatings on nuclear fuel particles. Details of the structure of these carbons and the variations of their structure with deposition conditions have been reported.'-3 It has been shown in previous work that the neutron-

Jan 1, 1968

By W. L. Connell, O&apos

The properties of some heavy liquids which can be used in sink-float separations are discussed with major emphasis being given to the halogenated hydrocarbons. Data are presented on density, viscosity, thermal characteristics and the effects of moisture and temperature on the corrosiveness of the liquids towards various materials of construction. The toxicity of these materials, the hazards involved in handling them, and the procedures for handling them safely are also discussed. True liquids have certain advantages over colloidal suspensions for sink-float separation of minerals which makes their use especially advantageous when close separations, fine particle sizes or water-soluble minerals are to be treated. For best separating results, the medium should have an easily controlled, uniform, stable density. Here, true liquids have the advantages of allowing closer control of density and of not requiring agitation to maintain a uniform den- sity in the equipment. Low viscosities are desired in a separating liquid so that rapid separations of fine material can be made. Many liquids have lower viscosities than the colloidal suspensions at operating gravities of 1.4 to 5.0. For economic reasons and to prevent contamination of the product, the separating medium must be easily and completely removed from the ore. Normally, true liquids must be more completely removed than the cheaper suspensions and thus cause more problems in this area. The fact that the medium should not react with the minerals, air, water or the common materials of construction limits the choice of liquids which can be used, but many are available which are sufficiently stable. A more serious objection to the use of true liquids is that many of them present a toxic hazard to operating personnel and users of the product. Most true liquids are toxic to some extent, but modem knowledge of toxicity allows us to recognize the hazards inherent in handling them and enables us to design around them. Three types of true liquids are available for this use: 1) Halogenated hydrocarbons cover the gravity range from 1.2 to 3.3. They are generally more volatile and less viscous than the other liquids.

Jan 1, 1963

By B. H. Caudle, L. G. Loncarie

Pilot flooding is one method of evaluating a proposed secondary recovery project. However, the amount and rate of oil recovery from an unconfined pilot area is not usually the same as from an equal area in a large-scale flood. This is true because fluids are free to move across the boundary of a pilot area. The result is that some of the oil produced in a pilot flood may come from outside the designated area and some of the displaced oil may leave the pilot area completely. This paper presents the results of fluid-flow model studies on a five-spot pilot flood. Mobility ratios between 0.1 and to have been studied. The effects of changing the ratio of injection to withdrawal rates are shown. INTRODUCTION A small-scale field test, or pilot flood, is an accepted method for evaluating the applicability of a secondary recovery operation and the economic potential of that operation for a reservoir. The pilot flood is carried on in the same manner, with the same injected materials and at the same pressures as would be used were the secondary recovery program to be expanded to a larger area of the field or to the entire field. If the reservoir fluid and reservoir rock properties are the same in the pilot area as in the rest of the reservoir, the production, injection and other pertinent data associated with the pilot test will represent and measure what should be expected from a full-scale development of this secondary recovery program. There is one major exception which, unfortunately, has been overlooked by many and which has been awaiting quantitative definition. This is the sweep-out pattern the reservoir engineer must use in interpreting the pilot flood and in extrapolating it to the full-scale development. The sweep-out area in a pilot flood is not contained within the five-spot pattern. Further, there is oil flow into and/or out of the five-spot during a pilot test. Thus, production data from pilots must be interpreted with this different flow system and sweep pattern in mind. We have studied the sweep-out pattern that will exist for some conditions of operation of pilot flooding a single five-spot (four injection wells and one producer). In our study, reported here, we have assumed that the reservoir is relatively homogeneous and of uniform thickness in the pilot area. The results of this study en-able the engineer to predict the recovery, injection requirements and project life for a full-scale operation from the pilot flooding data. The effects of various injection to withdrawal-rate ratios and mobility ratios in a relatively gas-free (10 per cent pore volume or less) system are shown. Experimental Method The technique used in this study was the same as that for the X-ray shadowgraph studies of sweep-out pattern efficiencies.' The model of the pilot and surrounding area was made from a uniform packing of round-grain sand consolidated with an epoxy resin. Fig. 1 shows the relation between the model and the pilot area. Only one-eighth of the pilot area had to be represented in the model because we assumed equal injec-

By Lawrence S. Darken

STAFF: Editor, Gerhord Derge Cornegie Institute of Technology Schenley Pork Pittsburgh 13, Pa. Editorial Assistant, M. A. Redmerski Production Editor, Otto T. Johnson THE METALLURGICAL SOCIETY: J. S. Smart, Jr., President; C. C. Long, Past-President; K. L. Fetters, Vice President; T. D. Jones, Treasurer; R. W. Shearman, Secretary. PUBLICATIONS COMMITTEE OF THE METALLURGICAL SOCIETY: C. L. McCabe, Chairman; H. L. Bishop, K. L. Fetters, J. J. Harwood, W. A. Krivsky, F. C. Longenberg, R. E. Lund, W. 0. Philbrook, L. L. Seigle, R. L. Smith, and F. L. Vogal. Review and selection of manuscripts is under the supervision of the following Publications Committees: Extractive Metallurgy Division: C. L. McCabe, Chairman; R. E. Lund, Vice-chairman; D. H. Baker, Jr., W. A. Krivsky, R. A. Lewis, Paul Qusneau, A. S. Russell, R, E. Shinkoskey, W. W. Stephens, and M. E. Wadsworth. Institute of Metals Division: L. L.Seigle, Chair-man, P. A. Back, J. J. Backer, l.l. Bessen, J. 0. Betterton, Jr., J. 8. Clark, R. S. Davis, A. E. Dwight, R. W. Fountain, R. B. Gordon, C. D. Graham, Jr., R. W. Guard, J. C. Gurland, E. L. Harmon, J. J. Hager, A. A. Hendrickson, M. Harmon, J. N. Hobstatter, H. H. Johnson, Jr., H. 5. Kolish, R. R. Nash, T. N. Rhodin, R. H. Richman, W. Rostokar, P. G. Shawmon, C. W. Spencer, L. Slifkin, J. K. Stanley, C. D. Starr, R. Steinitz, and H. C. Stumpf. Iron and Steel Division: H. L. Bishop, Chairman; 2. E. Boni, F. C. Langenberg, J. B. Wagstaff, and T. V. Wainwright. Published bimonthly by the American Institute of Mining, Metallurgical, and Petroleum Engineers, Inc., 29 West 39th Street, New York 18, N. Y. Telephone: PEnnsylvania 6-9220. Subscription PetroleumEngineers,$30 per year for non-AIME members in United States and North, South, and Central America; 332, foreign; $5 for AlME members. Single copies, $4.00, single copies foreign, $5.00. The AlME is not responsible for any statement mode or opinion expressed in its publications . . . Copyright 1%1 by the American Institute of Mining, Metallurgical, and Petroleum Engineers, Inc. . . . Registered cable address; AIME New York ..Indexed in Engineering Index, Industrial Arts Index, and Chemical Abstracts.. .Second class postage paid at New York, N. Y., and Ann Arbor, Mich. Volume 221, Number 4.

Jan 1, 1962

By William B. Hughes

The rubber-sleeve core barrel was developed to improve core recovery from unconsolidated sands, where it is most difficult to obtain cores with conventional barrels. The use of a rubber-sleeve core retainer, together with other departures from clsual design, has required a considerable amount of testing to prove its op-erability. Tests run in shallow experimental holes and in drilling wells in the U. S. and Vemzuela have, to a large extent, proved the operation of the barrel. Internal mechanism troubles, such as sandbinding of the sleeve, have been largely overcome. Cores have been recovered from completely unconsolidated sands where conventional coring has almost been abandoned because of poor recovery. In addition to retaining the core until brought to the surface, the barrel gives a "packaged-ar-cut" core, which is coilverzient for handling and transportatiorz. In the initial work, drag blade cutters, roller cutters, and tungsten carbide insert cutters were usrd for cutting unconsolidated sands. Further bit head development is presently being conducted using diamond heads in unconsolidated sands where shaler, hard sands, and limestones are encountered in adjacent formations. Thir work should render the barrel capable of cratting and recovering most types of formations, possibly including broken and frac- tured fornlations. This development is being carried on in cooperation with a diamond bit manufacturer. INTRODUCTIO N For many years the oil industry has needed greater recovery of cores from unconsolidated formations. Conventional equipment has been used to core unconsolidated sands with little success. Specifically, a core barrel was needed which would recover unconsolidated sands in a condition that would give useful reservoir information. DEVELOPMENT OF 'THE RUBBER-SLEEVE CORE BARREL Basic Requirements of Unconsolidated Sand Corino The basic need was defined as a core barrel that would obtain a continuous unconsolidated core with sand grains in place as deposited in the formation. A preliminary survey of coring equipment and search of the literature pointed out the weaknesses of conventional core barrels. Laboratory tests using unconsolidated sand in a metal tube simulated actual sand movement into the core barrel during conventional coring. In conventional barrels the core sometimes crumbles and bridges, or fails under compressive column action, becomes oversize, and wedges against the walls of the inner barrel. The core barrel requirements established by the surveys and preliminary tests are as follows. 1. The core should be held to- gether as it is cut so it cannot crumble and bridge against the walls of the coring tool, care being taken not to permit damage from fluid circulation. 2. The core should be continuously supported as it is cut so it will not have to support itself in compression. 3. The core should be packaged in the barrel to retain an undisturbed condition during the trip out of the well. The packaging should be such that the core can be removed from the barrel and shipped to the core analysis laboratory without physical disturbance or alteration of fluid content by exposure to the atmosphere. Operation of the Rubber-Sleeve Core Barrel The rubber-sleeve core barrel (Fig. 1) meets the basic requirements for the recovery of unconsolidated sands.

By H. T. Kennedy, J. E. Little

An empirical equation for the prediction of the viscosity of several pure paraffin hydrocarbons and nitrogen is presented. It involves temperature, pressure and six constants of the material, and it applies reliably to both liquids and gases. The equation is similar in form to van der Waal's equation of state. For the paraffin hydrocarbons methane through r-hexane and nitrogen, an average absolute deviation of 1.9 percent was obtained on 1,006 data points described in the literature by 14 authors. When this equation is extended to complex, liquid hydrocarbon mixtures, a correlation was obtained with an average absolute deviation of 9.9 percent. INTRODUCTION Equations describing the flow of gas and liquid through porous media contain the viscosity coefficient of the fluid. If other pertinent variables remain constant, the volume rate of flow is inversely proportional to this coefficient. In dealing with condensate fluids and volatile oils, however, the compositional effects resulting from changing pressure materially affect the viscosity. The effect of compositional changes also may be significant in certain secondary recovery or pressure maintenance processes, notably miscible displacement or gas injection. Early attempts to describe the performance of reservoirs utilized a volumetric material balance method wherein gas and liquid in the reservoir were identified as produced gas and liquid at the surface. This method of analysis proved adequate for reservoirs at moderate temperature and pressure that contained gas with moderately low amounts of condensable materials. The volumetric material balance procedures for "black oil" reservoirs leave much to be desired when applied to condensate and volatile oil reservoirs because phase behavior and compositional changes are relatively more important in these cases. The alternative is a compositional material balance, which in turn, requires a correlation of properties of the reservoir fluid with composition. This paper supplies this correlation in regard to viscosity, for reservoir crude oils. REVIEW OF LITERATURE The literature contains many empirical equations describing the effects of composition, temperature and pressure on the viscosities of pure liquids and binary liquid mixtures. However, the applicability of a majority of these equations is limited to very low pressures and to a small number of systems. Most of them, when applied to complex hydrocarbon systems, are of little value. The lack of utility of the majority of equations results from the fact that they were developed to show the separate effect of temperature, pressure or composition on viscosity, but not to predict the viscosity as a function of all three variables. And with the few exceptions noted below, they were developed to apply to much simpler systems than hydrocarbon mixtures. Eakin1 developed an equation for the viscosity of pure light hydrocarbons applicable in the gas, liquid and dense fluid regions, and in its most general form is written as µ - µo =A(ebP - e-cpk) The pure component viscosity at atmospheric pressure and temperature T, µo, was calculated using the Sutherland equation: µo = BT3/2/T + S The constants in Eakin's equation permitted the term e-CPk to become quite small at high densities (above 0.215 gm/cc), and the general equation would simplify to

Jan 1, 1969

By W. R. Hibbard

Evidence is presented which confirms previous findings that models of solution strengthening depending solely on lattice parameter changes are incomplete. Direct evidence for the Suzuki interaction of chemical effects was obtained from alloys with constant lattice parameter, for which solution strengthening was nearly independent of temperature from 300° to 20°K. SOLUTION hardening principles have been reviewed recently by Parker and Hazlett.' In addition, the interactions of dislocations and solute atoms were reviewed by Cottrell.' It is not proposed to review this information again here, but to refer only to those details which are pertinent to the developments which have occurred since these papers were published. Literature Survey To set the stage, it has been known for some time that solid solutions are stronger than the pure parent metals, and that the strength increases with increasing amounts of alloying element. One of the most extensive earlier investigations was that of Lacy and Gensamer,3 who reported that the solid solution strengthening of iron is a power function of the composition, that the relative strengthening is a function of the solubility limit, and that the rate of strain hardening is a function of the amount of solution hardening. Thus, the slope of the plastic portion of the stress-strain curve increases with increasing yield strength. An approach to the development of principles resulted from work by Gulyeav,4 who reported that the strengthening effect of solid solution alloys is periodic in character when plotted as a function of the atomic number of the solute. A more quantitative approach was to relate the amount of solution hardening to the lattice parameter of a solid solution. This was done quite early by Norbury,5 and later by Brick, Martin, and Angier,6 Frye and Hume-Rothery,7 and French and Hibbard. This relationship is only approximate in character. The next development was to relate the amount of solution hardening to lattice stress, as proposed by Frye and co-workers.9 They calculated what they called ionic overlap from the lattice parameter changes represented as a change in volume, using Bridgman's hydrostatic compression equation. The resulting correlation was somewhat improved as compared to the simple correlation with lattice parameter. The next step was carried out by Dorn, Pietrow-sky, and Tietz,10 who suggested an effect of valence differences in addition to the effect of lattice parameter. Their proposed parameter shows flow stress as a single valued function of the concentration and a relationship involving these two atomic variables. In addition, they contributed new data on the temperature dependence of solution hardening which indicated that it was a strong function of temperature for aluminum alloys. Allen, Schofield, and Tate11 carried the valency effect even further by reporting data indicating that with a given solvent element the stress-strain curve is a function of electron density, entirely neglecting the size factor, which varied by a factor of two. This evidence led to a quantum mechanical calculation by Cottrell, Hunter, and Nabarro,12 based on the formation of a dipole around an edge disloca-

Jan 1, 1959

By W. A. Burns

Vertical flow is an important mechanism in many petroleum reservoirs. Yet no adequate method has heretofore been proposed for determining the in-situ vertical permeability in a reasonable length of time. Core measurements of vertical permeability do not necessarily represent effective in-situ values. Cores may be representative of only localized pockets of high or low permeability, and total reliance on cores might cause one to overlook the presence of vertical fractures altogether. Conventional single-well tests, interference tests, and pulse tests commonly are used to determine horizontal transmissibility, khh/u, but generally are not designed to measure vertical trans-missibility or other groups containing vertical permeability, ku. A new well test described here provides a measure of in-situ vertical permeability as well as the previously measurable horizontal permeability. This "vertical test" determines the vertical diffusivity, kv/gcu, and horizontal transmissibility, khd1/u (where dl is the length of injection or production perforations). The test is basically a short-term interference or pulse test normally lasting less than a day. Conventional down-hole equipment is used between two isolated sets of perforations in the same well, as shown in Fig. 1. A "layer-cake" description of a reservoir can be obtained by running two or more vertical tests in the same well, each over different vertical intervals. Each test can be analyzed for the effective vertical and horizontal properties of the interval tested. In addition, a vertical well test can determine the effective- ness of a shale barrier or tight zone by testing across it. Field use to date of vertical testing has confirmed its utility in reservoir description. Mathematical Basis Interpretation of vertical tests for ku and kh is based on comparison of measured pressure response with computer-generated response. Pressure behavior during a vertical test in a homogeneous, anisotropic, infinite-acting reservoir (infinite in radial extent and bounded in both directions vertically) is given by the diffusion equation for slightly compressible fluids with negligible gravity effects.l A schematic diagram of the problem is presented in Fig. 2, and an analytic solution, based on the image

Jan 1, 1970

By K. J. Gill, P. Chiotti

Thermal, metallographic, and vapor pressure data were obtained to establish the phase diagram for the thorium-zinc system. Four compounds corresponding to the stoichiometric formulas Th2Zn, ThZn2, ThZn4, and Th2Zn17 were observed. The melting points of these compounds under constrained vapor conditions were found to be 1055°, 1105°, 1095°, and 1015°C respectively. Four eutectics exist in this system with the following eutectic temperatures and thorium contents in wt pct: 1040°C, 89 Th; 945°C, 79 Th; 1045°C, 55 Th; and 995°C, 35 Th. The standard free energy, enthalpy, and entropy of formation for the compounds were determined from zinc vapor pressure data. ALTHOUGH the thorium-zinc system has been of technical importance in the commercial production of thorium and more recently of interest to some proposed pyrometallurgical separations processes for reactor fuels or blanket materials no detailed investigation of this system has been made in the past. Some previous work has been reviewed by Hanssen.1 The existence of four compounds, Th2Zn17, ThZn4, ThZn2, and Th2Zn has been established and their crystal structures have been studied by X-ray diffraction techniques.2-4 Smirnov et al.,5 determined the solubility of thorium in zinc and investigated the two-phase region between Th2Zn17 and zinc. They calculated some of the thermodynamic properties for these alloys from emf measurements on the cells Th/ThCl4(fused)/Cl2, C and Th2Zn17(s)+ Zn (l)/ThCl4(fused)/Cl2, C. The possibility of reaction between the anode materials and fused thorium tetrachloride to produce a lower valent thorium salt would have to be resolved in order to evaluate the results obtained. The purpose of the present investigation is to establish the phase diagram for the thorium-zinc system and to determine the standard free energy, enthalpy, and entropy of formation for the compounds formed. MATERIALS AND EXPERIMENTAL PROCEDURES The metals employed in the preparation of alloys were Bunker Hill slab zinc, 99.99 pct pure and Ames Lalboratory thorium. The major impurities in the thorium in parts per million were oxygen—1250, carbon—350, iron—100, nitrogen-75, and silicon—70. The metals in the form of several small massive pieces, total weight about 30 g, were cleaned with acid, washed with water and acetone, and dried just prior to their use for alloy preparation. Tantalum containers were found to be suitable for all the alloys studied and were used throughout this investigation. The metals were sealed inside of small 1-in.-diam tantalum crucibles by welding on preformed tantalum covers. A small thermocouple well made from 1/8-in.-diam tantalum tubing was welded in the bottom of each crucible. These crucibles were enclosed in

Jan 1, 1962

By R. L. Caldwell, E. E. Glenn, L. J. Norton, A. J. D. Straus, S. V. Holcomb, J. Zemanek

A new and unique logging tool, called the Borehole Televiewer (BHTV), has been developed to inspect boreholes and to evaluate formations. Even though geologists and engineers have had only about 3 years' experience with the BHTV, the thinking of many of them has been radically influenced by the fascinating and revealing "log-picture" recorded with the tool. The BHTV fills a need for a logging tool that can produce a direct and descriptive record of the physical properties of the borehole environment. Although primarily developed to evaluate fractured reservoirs, the BHTV has been used successfully to solve a variety of problems related to formation evaluation and borehole inspection. Geologists and petroleum engineers have been confounded for many years by the problems of locating and evaluating fractures. Interpretation of the usual resistivity, acoustic or radioactivity logs, as well as the analysis of cores, for evaluation of fractured reservoirs is extremely difficult and often not definitive. This is understandable since analysis of cores from fractured formations has reported variously: (a) low porosity, (b) no effective permeability, (c) lack of any matrix oil saturation and (d) oil stains on fracture planes as the only indications of potential production.14 In recent years acoustic amplitude logs have been introduced and used with varying degrees of success to locate fractures.8'9'11"13 Conventional amplitude logs at best give only qualitative answers where quantitative ones are desired. The logs reveal nothing of the orientation of the fractures. In addition to these logs, various types of cameras, television, and rubber impression packers have been used for borehole inspection. (See Appendix.) The BHTV logging tool supplies both the quantitative and the orientation answers about fractures. The borehole can be filled with any homogeneous, gas-free liquid such as fresh water, saturated brine, crude oil or drilling muds. This tool takes an "acoustic picture" of the borehole wall. The resulting log is a representation of the borehole wall as if it were split vertically and laid flat. The log is oriented with respect to magnetic north. Any physical changes in the borehole wall are seen as changes in picture intensity. In this way, fractures, deformation or pits are reflected on the log. Tool Description The fundamental parts of the BHTV are shown in Fig. 1. A piezoelectric transducer probes the borehole wall with bursts of acoustic energy. A flux-gate magnetometer senses the earth's magnetic field and provides the means for determining the orientation of the log. A motor rotates the transducer and mag-

Jan 1, 1970

By W. C. Peters, M. W. Pullen, C. A. Bays

During the past three and a half years considerable improvement in the techniques of solution extraction of salt has been made by the use of wells which are cross-connected by hydraulic fracture at the base of the salt. Fracture is initiated by the application of hydraulic pressure. Underreaming and perforating techniques are used to control initiation. The fracture is then extended by continuous pumping until a pressure communication is obtained. Pressure communication is followed by washing-through to obtain a low-pressure connection. Well construction using non-shrinking cements that will bond with the salt and with associated strata is essential to the process. The connecting procedure described permits solution to attack the salt deposit from its base upward, thereby permitting greater recovery, fewer well repairs, better saturation of brine, and overall economy of development and operation. The fracture method of cross-connection requires special pumping of the fluid and is limited by present experience to initial well spacings up to about 1200 feet. The method has been used in bedded salts and is applicable for wells in salt domes. Since spring of 1956, new developnents in salt extraction wells have followed procedures substantially different from those in prior use. Although multiple well systems, connected either by the natural consequence of the solution process or by undercutting under protective pads, have been used previously, the past three and a half years have brought about new designs and new operation procedures based on cross-connection of the wells using hydraulic fracture. To date these techniques have been applied largely in the bedded salt deposits of Michigan, Ontario, Ohio, West Virginia, and New York. To the writers' knowledge they have not been used in salt dome wells. The methods have not yet been in use for a sufficient period to permit any statistical comparison with the older methods. It is evident from experience to date that the methods result in higher recoveries, lower capital and operating costs, better saturation of produced brine, reduced well maintenance and repair, and in considerably fewer production units to insure

Jan 1, 1961

The income of the Institute is derived mainly from dues, advertising in 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, 1939

By C. G. Dunn, P. K. Koh

The primary recrystallization textures of 11 single crystals cold rolled 70 pct were determined. The effect of crystal orientation on recrystallization behavior was investigated also and found to be large. An exception was found to the relationship that strong components of the recrystolliza-tion texture are rotated from the cold rolled texture by 30° about <110> axes, but generally this relationship was found to hold quite well. Evidence supporting oriented nucleotion was found and discussed in terms of probable active slip systems and <110> edge dislocations. THE present paper is one of a series&apos;.&apos; on recrys-tallization phenomena in cold rolled 31/4 Si-Fe single crystals and is mainly concerned with the textures produced on recrystallizing from stable end orientations. Data for the cold rolled textures of the crystals used have been reported by Koh and Dunn." Their results showed that the sharpness of the cold rolled textures varied throughout the range of stable end orientations and that the tendency to re-crystallize was related to the sharpness of the cold rolled texture, wherein the rate of recrystallization increased and the size of recrystallization grains decreased with decreasing sharpness of the cold rolled texture. In the project under consideration the cold rolled crystals involved a range of initial orientations that, together with those studied earlier,&apos; provide information on several points. The first point is whether the recrystallization texture from a (111) [112] cold rolled texture, a stable end orientation that can be approached from different directions, correlates in any way with the initial orientation before cold rolling, or whether the recrystallization texture is entirely determined by the observable features of the cold rolled texture. The second point involves a preliminary study to see if the main components of the recrystallization textures correlate with the most probable active slip systems. The third point is to determine what effect departure from slip on one slip system has on the tendency to recrystallize. Experimental Procedure Nine specimens from a previous investigation and two additional ones from thicker stock (lot D) but of similar composition to the others were used in the present work. The latter two crystals, like the nine, were cold rolled to a reduction in thickness of 70 pct and the amount of widening was determined. Depending on their primary recrystallization behavior, the cold rolled crystals were given short or long anneals at temperatures of 980°C or higher. Table I summarizes the data on initial orientations, the textures obtained by cold rolling, and the anneals given to provide samples for the present work. Fine grained specimens were thinned to 0.002 in. thickness and placed in an integrating specimen holder. Chart recordings using a transmission X-ray method and MoKa radiation were obtained for diffraction from (110) planes. This method,&apos;,3 which gives data for all of the pole figure except a central region of 30" radius, proved sufficient to give generally five, and sometimes six, of the six possible pole concentration areas of any one component of the texture. These data, therefore, were generally adequate for a positive identification of each component present. The first texture obtained for specimen B-2 was poorly defined because of too coarse a grain structure and therefore too few crystals in each component for satisfactory X-ray reflections. The same

Jan 1, 1957