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In 1962, minerals beneficiation showed definite signs of coming out of the doldrums into which it has drifted after the uranium boom. Demand by steelmakers for high-grade iron pellets has created the need for concentrating plants to upgrade specular hematite by spiral concentration or flotation and magnetites by magnetic means and flotation. According to a paper given at the AMC annual meeting by C. S. Arms of Pickands Mather, "the shipment of pellets, started in the mid-1950's, has increased to 17.6 million tons in 1961 from North American operations. Many plants already underway will raise this production to about 42 million tons by 1965. This will be a very sizeable percentage of the total iron ore production contemplated by that date." Iron ore concentration methods are gradually raising the assay of pellets into the 65 to 69% Fe range and lowering silica to the 4 to 7% range. Quebec Cartier's Lac Jeannine concentrator went into operation in late 1961 and all grinding units were running by 1962. The Iron Ore Co. of Canada's new Carol Lake plant was started in mid-1962.

Jan 2, 1963

By Sumner M. Anderson

Any discussion of outside support to Latin American mineral industries must concede at once the pre-eminent role of U. S. industry and business. American capital has developed the great copper resources of Chile and Peru, the lead-zinc of Peru and Mexico, the bauxite of Surinam and Jamaica, the petroleum and iron ore of Venezuela. American consumers have provided the market for their products. U. S. companies operating south of the border have trained Latin American geologists, engineers, chemists, and skilled labor—including metal, mineral, and fuel technicians—to new and greater competence. The industrial demands of World War II drastically altered world economics and concepts of U. S. foreign mineral requirements. In this country discovery of vital mineral resources fell far behind the alarming depletion rates, and there was new appreciation of the actual and potential importance of the world's less extensively explored areas. During the war and afterward, the task of supplying the nation's mineral requirements became greater than private industry could carry alone, and the Government assumed a position of continuing support. In Latin America, as elsewhere, this support applies in three categories: banking, procurement, and technical assistance. The first two are now generally accepted as necessary Government functions; the third has often been misunderstood and misinterpreted, although it has given rise to legitimate controversy. There have been major accomplishments in all three categories, as well as some errors of judgment. Since the beginning of World War 11, U. S. Government financing, procurement, and technical assistance have been applied on a large scale to a wide range of commodities and services throughout the free world. The present discussion—under the separate headings mentioned—will concern only the support related to a single industrial group in a single geographic area. During the War Federal banking was conducted on an emergency scale by temporary agencies created to meet the abnormal circumstances. Unfortunately, there are no readily available data on these activities that would permit evaluating loans and credits extended for mineral projects in Latin America. The only agency operating in this field since World War II is the Export-Import Bank, under its own authority and to some extent from credits authorized by the Office of Defense Mobilization. The Bank can offer more capital—on more favorable terms—than is available from most Latin American banks, and its staff of engineers evidently can appraise loan applications more favorably than commercial banks in this country are willing to do. The risks seem to be justified, as defaults have been well under 1 pct of total loans. From V-J day 1945 to the end of 1957, mineral loans to Latin America have been authorized for projects totaling $541.63 million in eight countries. In order of magnitude of credits, they have been made to Brazil, Peru, Chile, Mexico, Argentina, Venezuela, Guatemala, and Bolivia. In order of magnitude by industries. they are for development and expansion of steel mills, copper, manganese, nitrate plants, iron ore, zinc plants, sulfur plants, cement plants, tungsten, coal, and lead. Loan Distribution: By far the largest loans have been $307.9 million for iron and steel projects in Brazil, Chile, Mexico, Argentina, and Peru: $100.4 for developing the great low-grade copper deposits of southern Peru; and $55.3 million for developing manganese deposits in the Territory of Amapa, Brazil. Others range from $20.8 million for a zinc smelter in central Peru to $19 thousand for iron-mine trucking equipment in Chile. It has been noted that 59 pct of the loans have been to foreign companies, 14 pct to companies of mixed foreign and American capital, and 27 pct to American mining companies. About 40 pct of the total authorizations has been disbursed so far. In addition to these amounts, the Strategic Materials Division of the Economic Cooperation Admin-

Jan 1, 1959

By F. Petkovich, M. P. Sudbury

Development of a new method of treating flotation concentrates for the preparation of feed suitable for direct charging to blast furnaces or converters is described. The method takes advantage of the fact that pyrrhotite contained in the concentrates can be made to undergo exothermic reactions which, under properly controlled conditions, result information of oxidation products that serve to cement the concentrate particles together. Thus green concentrates either in the form of pellets or briquettes containing 5 to 8 pct moisture not only were hardened, but also completely dried autogenously by continuous countercu,vrent shaft treatment with air. The process was developed through pilot plant operations ranging from 35 1b per hr to 2.5 tph, culminating in products evaluation tests on a railway-car scale. Falconbridge Nickel Mines Ltd., Falconbridge, Ont., have practised sintering, on a travelling grate machine, for many years to prepare a pyr-rhotite-bearing Cu-Ni sulfide flotation concentrate for blast furnace smelting. In recent years the development of new mines, and the construction of concentration plants some 40 miles from the smelter has increased the quantity of concentrate shipped, and encouraged the search for a method of producing dry, hard pellets or briquettes suitable for direct charging to a blast furnace or converter, and capable of withstanding considerable handling. The cementing properties of pyrrhotite oxidation products were discovered during a search for a suitable agglomeration method for sulfide concentrates, and were exploited in a process subsequently developed for autogenously drying and hardening pellets and briquettes of pyrrhotite-bearing Cu-Ni sulfide flotation concentrate. EARLY TEST WORK The production of hard, dry pellets of concentrate filter cake was attempted in the drying plant of one of the new concentrators. While soft pellets were produced containing 5 pct moisture, attempts at further drying resulted in disintegration of the pellets and intolerable dusting. The plant therefore was controlled to produce a concentrate containing about 6 pct moisture. The partially dried concentrate, which was shipped to Falconbridge for sintering, tended to heat spontaneously in transit. An at- tempt to briquette the moist concentrate at Falconbridge, in a plant incorporating a muller, a 20-in. roll briquetting press, and a steam-heated travelling grate oven, was more successful, although the equipment corroded rapidly due to the acid nature of the concentrate after spontaneous heating had occurred. LABORATORY STUDIES OF SPONTANEOUS HEATING OF CONCENTRATE The spontaneous heating of partially dried concentrate was studied in the laboratory. Moist concen-

Jan 1, 1961

By Robert Bakish, William D. Robertson

AFTER more than fifty years of investigation and continuing failure in service, a satisfactory mechanism to explain stress corrosion cracking in homogeneous alloys is still lacking. The relative chemical activity of grain boundaries and adjacent grains, inferred from the boundary structure, has been used to explain intergranular cracking in a brass.' This concept is probably correct as a general hypothesis, but it requires much more extensive development in order to explain satisfactorily the observed phenomena. For example, the specific function of the solute in an alloy must be considered, because intergranular failure does not occur in pure metals,' which are structurally similar to homogeneous alloys. Also, in this connection, an inter crystalline fracture path in binary copper alloys can be changed to a transcrystalline path by relatively small ternary additions.' The fracture path in ß brass is predominantly transcrystalline,' in contrast with an inter crystalline path in a brass. Whether the two different fracture paths are the result of a difference in composition, crystal structure, or the state of long range order is unknown and cannot be determined with ß brass, because only the ordered state can be obtained at room temperature. The study of chemical activity at structural sites in the Cu-Zn system is restricted by the formation of opaque films in an ammonia environment in which stress corrosion cracking is generally observed. Furthermore, both components of the alloy are chemically active and the interpretation of observations is therefore relatively complicated. The Cu-Au system is a better choice for the purpose of studying structural factors. In particular, CuAu is very susceptible to cracking in ferric chloride and opaque films are not formed in this solution; it may be obtained in different states of long and short range order; and, finally, only copper is oxidized in dilute ferric chloride, which considerably simplifies the chemical problem. To provide information necessary for a more general explanation of stress corrosion cracking in homogeneous solid solutions, the following structural factors have been investigated in a Cu-Au alloy having a composition corresponding to Cu,Au: 1) the effect of long and short range order; 2) the structural sites from which copper is removed from the annealed and cold worked polycrystalline alloy; and 3) the effect of annealing time and temperature on structural reactions in the cold worked alloy. Experimental Procedure A Cu-Au alloy of nominal Cu3Au composition was cast from cathode copper and high purity gold and fabricated into sheet and wire. Chemical analysis for copper and gold indicated 48.92 wt pct Cu and 51.01 pct Au. Quantitative spectrographic analysis indicated 0.01 pct Ag, 0.002 pct Pd, 0.001 pct Pb, and 0.002 pct Fe, with traces of magnesium, silicon, and zinc. Presumably most of the remaining 0.055 pct corresponds to the limits of analytical precision. Heat treatments of wire and sheet were conducted in argon or vacuum. Wire specimens, 0.064 in. diam, were heated for 1 hr at 850 °C to establish a definite

Jan 1, 1957

By W. A. Tiller, J. D. Harrison

HOT pressing of powder particles has gained importance recently, since it affords a method in which high densities are rapidly attained. In a recent study on hot pressing of alumina powders, Mangsen, Lam-bertson, and Best1 have shown within the limits of their experiment, the validity the rate equation for densification in hot pressing, originally proposed by Murray, Livey, and Williams.2 i.e., where D = fraction of theoretical density, t = time, P = pressure and 77 is the viscosity, all in appropriate units. This equation was derived from earlier work of Shuttleworth and Mackenzie3 which is based on the closing of spherical pores under the action of surface tension. The integrated form of this equation yields a straight-line relation between log (1 - D) and t. Such conditions were found by Felten4 to be true only after extended periods of pressing. In an endeavor to quantitatively evaluate the exactitude of this equation in the initial sintering stage, i.e., prior to sealing of the pores, spherical anti-

Jan 1, 1962

By AIME AIME

The XCVIIth meeting of the Institute for the reading and discussion of papers will be held at Spokane, Wash., beginning Monday, Sept. 27, 1909, as already announced in Special Circulars of May 8 and Aug. 14, 1909, and in the Bulletins for June, July, and August. The meeting will be preceded by a tour through Yellow stone Park and visits to Butte and Anaconda, and will be followed by visits to the Coeur d'Alene district, to the Alaska-Yukon-Pacific Exposition at Seattle, to the mining- and smelting-plants near Salt Lake, and to the iron- and lead- and zinc-plants at Pueblo. The special train for the party' will leave Chicago, September 16, and return about October 12. Details of the itinerary are given later in this announcement. The Secretary of the Spokane Local Committee is Lyndon K. Armstrong, 615 Hyde Block, Spokane, Wash., to whom should be addressed all inquiries concerning local matters. The control of the papers and proceedings will remain in charge of the Institute office, as usual. It is greatly to be desired, both in behalf of the Institute and in recognition of the many courtesies to be extended on the trip, that the excursion party be made larger. Exceptional facilities to visit the many mines and smelters have been freely provided; and members are requested to make all reasonable effort to attend the meeting at Spokane and participate in the excursions. For those who cannot join in the entire trip, it may be possible to provide special Pullman accommodations after leaving Yellowstone Park. In order to make the necessary arrangement, however, the names of members and guests contemplating this partial trip should be sent at once to Theodore Dwight, 29 West 39th Street, New York City. The general cost of the trip per member will be $300, which includes transportation, berth, and meals for the entire trip from

Sep 1, 1909

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 Jack L. Taylor

As expected from similar crystal structures and favorable atomic size factors, titanium, vanadium, and molybdenum are completely soluble in one another above the transformation temperature of titanium. The fl phase parameters of the continuous solid solution are shown graphically. Limiting compositions for retained fl phase have been determined. VANADIUM and molybdenum both have body-centered-cubic structures at all temperatures and, from the atomic diameter comparison factor, 3.9 pct, would be expected to form a complete series of solid solutions. The existence of complete solubility has been confirmed by work' at the Jet Propulsion Laboratory. Furthermore, vanadium and molybdenum have favorable atomic size factors to form complete binary solid solutions with the B phase, high temperature form of titanium, which also has body-centered-cubic structure. Pietro-kowsky and Duwez' and Hansen et al." have established the existence of the complete series of solutions in these binary systems. It would be logical, therefore, to expect that p-titanium, vanadium, and molybdenum would be completely soluble in one

Jan 1, 1957

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 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 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 Henry Rawdon

THE following note describing the behavior of copper under rather unusual conditions is offered here for its suggestiveness rather than as a complete study of the question. The examinations described were made because of a request for information concerning the embrittlement of copper when heated in a molten salt bath (sodium chloride) for the purpose of cleaning it, as well as for softening it. It is well known that metals may be rendered very brittle by electrolytic action, in aqueous solutions, in all probability by the action of nascent hydrogen, and it was suspected that perhaps the embrittlement of the copper by means of the molten salt was produced in a somewhat similar manner. It was found that the copper was in contact with iron (or steel) while immersed in the molten salt, through the occasional use of an iron stirring rod, iron forceps for handling the pieces, and an iron pot for containing the fused salt. In the electrochemical potential series iron and copper stand some distance apart, copper being electronegative to the iron. Assuming that the two metals bear a similar relation to each other, when immersed in a bath of molten salt, as they do in an aqueous solution, they would be expected to form a galvanic couple, the copper being the cathode. By this means the copper might be embrittled, as often happens in aqueous solutions, by the action of the liberated hydrogen. In this case, however, the embrittlement must be attributed to some other agent than hydrogen. To demonstrate how copper may be embrittled under these conditions, two small rods, one of copper and the other of mild steel, approximately 3/8 in. (9.5 mm.) in diameter, were immersed in a bath of sodium chloride that had been heated somewhat above its fusion point (melting point of sodium chloride is 819° C.) and an electromotive force of approximately 6 volts from a storage battery was impressed upon the system. The copper was made the cathode and the action was continued for

Jan 2, 1920

By Joseph Daniels

IN connection with a study of the feasibility of establishing a blast-furnace industry in the Puget Sound region of Washington, possible sources of ore supplies along the Pacific rim were investigated. Many of the South American countries are known to contain important resources of iron, particularly Brazil and Chile. This latter country, because of its position on the west coast and the easy accessibility of its de- posits, appeared to be a logical place to consider as a potential supply for the Pacific Northwest. Accordingly, a brief field study was made of the deposits in September, 1924. Attention was confined to a limited number of properties on the west coast in the provinces of Antofagasta, Atacama, and Coquimbo. Passing consideration was given to the question of coal resources, and a short visit was made to a blast-funace plant at Corral in southern Chile which had been operated for a limited period as a producer of pig iron. In the following paper, a brief outline is given of the general observations made and of the salient facts rioted in the time available for the general study.

Jan 1, 1926

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 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 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 J. C. Martin

Equations for three-phase, three-dimensional, compressible flow (including capillarity) are reduced to two-dimensional relations by a partial integration. This reduction allows three-dimensional flow problems to be treated with mathematics for only two spatial dimensions. The results can be used to formulate flow equations for two-dimensional reservoir simulators in which the effects of capillarity and fluid segregation in the third dimension are represented. Such reservoir simulators would retain many of the aduantages of two-dimensional simulators while simulating three-dimensional effects. The principal restriction of the method is that the thickness of the reservoir should be small, compared to the distance across the reservoir. INTRODUCTION In recent years, computers have been used to calculate the performances of many reservoirs. Most of the detailed calculations, however, are based on finite difference solutions of the flow equations, and present day computers are seldom able to handle a sufficient number of cells to produce entirely satisfactory solutions, even for reservoirs represented by two-dimensional arrays of cells. The situation becomes much worse when one wishes to approximate the reservoir by a three-dimensional array. A great saving in computation or a more detailed solution can be obtained for many reservoirs by using the partial integration of the equations of flow presented in this paper. The integration reduces the three-dimensional equations to two-dimensional relations; and, for studies of two-dimensional flows in vertical cross-sections, the equations are reduced to one-dimensional relations. Most reservoir performance calculations currently are based on one- or two-dimensional flow re1ations.l-3 In some cases flow in the third dimension is approximated by assuming a particular type of vertical saturation distribution, such as gravity segregation.l.2. The relations developed in this paper approach those for segregated flow as the capillary pressures approach zero, and they approach those for uniformly distributed saturations as the capillary pressures are increased. For this analysis, the ratio of the reservoir's thickness to the maximum distance across it must be small. The capillary pressures between the oil and water should also be small compared to the maximum pressure difference in the reservoir. This requirement is met by most reservoirs. It is assumed that the capillary-pressure curves are well defined, whether or not hysteresis effects are included. Also, the reservoir must have sufficient vertical permeability to allow the fluids to segregate. The results presented here provide a firm theoretical foundation to Coats' et aL5 assumption of vertical equilibrium and extend the relations to three-phase flow. Coats' assumption of vertical equilibrium, which he verified by calculations and experiment, is developed here mathematically from basic flow equations. DISCUSSION SATURATION AND PRESSURE DISTRIBUTIONS Appendix A presents a mathematical analysis of fluid flow in reservoirs where the ratio of thickness to maximum distance across the reservoir is small. The results indicate: (1) that the fluids along any line perpendicular to such a reservoir's upper surface are in static capillary equilibrium (vertical equilibrium); (2) that, to a first approximation, the fluid pressures and properties are functions of only areal position in the reservoir and time; and (3) that hydrostatic pressure gradients exist along any line perpendicular to the reservoir's upper surface. The results might be expected after studying several physical considerations. First, no flow is allowed normal to the upper and lower reservoir boundaries, which are relatively close together.

Jan 1, 1969

By Edward W. Parker

(Toronto Meeting, July, 1907.) NOTE.-The material from which this paper has been prepared was collected for the U. S. Geological Survey Bulletin, Contributions to Economic Geology, 1906, and appears also, though in somewhat more extended form without illustrations, in that publication. ALTHOUGH the briquetting of coals and lignites has been carried on for many years in Europe, and has reached a particularly high state of development in France, Belgium, and Germany, it has made comparatively little progress in the United States. The causes for the backwardness of the United States in this regard are several, and first among them has been the abundant supply of cheap raw fuel with which the manufactured article has to compete. With our millions of acres of coal-productive territory, from which the product can in most cases be cheaply extracted, it has appeared in many districts more economical to waste the slack or culm, which con¬stitutes a considerable percentage -of the product, than to attempt to save it at the additional expense required for briquetting. It is for this reason that the view in all sections of the anthracite-region of Pennsylvania is marred by the unsightly culm-banks which encumber the ground, and that in some of the bituminous-districts one sees huge piles of unmarketable- slack allowed to burn up in order to get rid of them. When the coal is of a coking quality, or when the slack can be used for steaming-purposes, these losses are not sustained, but many thousands of tons of what might be converted into usable fuel have been wasted every year simply because of the increased expense involved in its preparation.

Sep 1, 1907

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.