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By John R. Spencer

A capillary tube variable volume cell is described, which has operated satisfactorily over a range of 100°F and 3,500 psi to 550°F and 1,500 psi. The cell contents are entirely visible over the length of the capillary with the exception of a space at the top amounting to three per cent of the total volume. Observations on the critical behavior of simple systems have been greatly facilitated by the apparatus, it being possible to establish the critical conditions for a particular mixture in the course of a day's run. INTRODUCTION Many types of apparatus have been designed for obtaining data on the phase relationships of hydrocarbon systems. Such apparatus can in general be subdivided into two classifications; (l), indirect measurement of phase volume, and (2), direct visual observation of phase volume, each of which has outstanding advantages and disadvantages. Indirect measurement of phase volume requires the use of rather elaborate apparatus including internal probes in which are located the device for determining the locus of the interface between phases. Such equipment is by its very nature costly, and is complex from the standpoint of operating technique. Probing techniques can be used, however, over wide ranges of temperature and pressure with a high degree of reproducibility. Apparatus for visual observation of phase behavior obviously has the advantage of enabling the experimenter to see exactly what takes place, but because the material to be tested is contained in a cell constructed of both metal and glass, is limited severely as to the temperature range of operation. Furthermore. the maximum pressure usually is limited by the choice of material used for sealing the glass to the metal, and by the strength of the glass itself. In the interest of increased efficiency of observation, as much of the cell as possible should be visible to the eye. Glass capillary tubes have been used successfully but have always given difficulty at the metal-to-glass seal. An apparatus has been devised to overcome the problems of sealing and resistance to temperature effects that have heretofore been the limiting factor with glass apparatus in the observation of phase volumes at elevated temperature and pressure. APPARATUS The objective which dictated the general arrangement of the apparatus (Figs. 1 and 2) was simplicity of operation. The air bath, A, was constructed of an iron framework to which was attached approximately one inch of glass wool bats which were covered on the outside with "Masonite." A roughly octagonal center piece was installed to provide forced circulation of the air by the fan, B, past the heaters, D, cell, F, and thermoregulator, C, respectively. The entire top of the box is removable to facilitate charging of the cell and to permit easy maintenance. Two windows are provided before and behind the cell to allow the operator to observe the contents against the background fluorescent light, E. The heaters,

Jan 1, 1951

By Fortunato Pereira Gamba

The Department of Narino (formerly included in the Department of Cauca) is a narrow band about 170 km. (100 miles) wide in the southern part of the Republic of Colombia, near the boundary of Ecuador, as showu in the sketch-map, Fig. 1. Its capital is Pasto, a small city of 25,000 inhabitants; the pri~icipal towns are T?querres, Cumbal, Ypiales, Barbacoas, and Tumaco. The port on the Pacific ocean is Tumaco, and traffic in the interior is carried partly on the Patia river (steam navigation to the fluvial port of Barbacoas), and afterwards overland over poor roads by human bearers or on mule-back.

Jan 1, 1913

By M. S. Tsai, Y. D. Chuang, H. M. Wu

To contact the commercial OPAP-kerosene solution with CH3OH – H20 solution, we used the appropriate concentration of DOPAP / MOPAP solvent. By using this treated OPAP solvent, uranium can be recovered from wet-process phosphoric acid. Electric DC power is supplied on the dual side of the ion-exchange membrane of a specially designed box-type mixer settler. U(VI) is reduced to U(IV) in the cathode and U(IV) is oxidized to U(VI) in the anode. Uranium is extracted in the cathode by treating it with OPAP solvent. Next the uranium is stripped from the loaded OPAP solvent by concentrated phosphoric acid in the anode. After 300 hours of continuous operation total recovery of uranium is as much as 95%.

Jan 1, 1984

By Eric Jette

IN thermodynamic studies of gas mixtures and liquid solutions, the respective problems have been greatly simplified by the use of two general limiting laws; Dalton's law of partial pressures and Raoult's law. It is generally recognized that these two laws have a common physical and chemical basis which may be stated as follows: The law may be expected to be strictly valid only for systems in which the different molecular species are so nearly the same in their physical and chemical properties that a molecule is unable to recognize whether its neighbor is one of its own kind or not. Positive and negative deviations from both laws are frequently encountered. The occurrence of negative deviations in both gases and liquids is ascribed to attractive forces which, in the more extreme cases, may be so large in magnitude and so highly specific in character as to lead to the formation of definite chemical compounds. Positive deviations in gases develop only at higher pressures where the intermolecular distances are so decreased that factors such as molecular size and shape, which ultimately become concerned with the repulsive forces, come into play. In liquid mixtures, positive deviations are generally considered as due to differences in the symmetrical (nonpolar) fields of force which surround the various molecular species and which are supposed to give rise to a tendency for each species to associate with its own kind and thus to "squeeze out" the other variety. Fundamentally this also involves the existence of repulsive forces between unlike molecules. If the fields of force are unsymmetrical (polar) a tendency towards compound formation results. Stated in more exact terms, strict adherence to the law means that the "activity" (or any adequate measure of this quantity) of a component in a mixture is a linear function of the molecular (or atomic)

Jan 1, 1934

By S. Zador, C. B. Alcock, K. Sudo

Measurements have been made of the standard free enevgies of formation of the sulfates of cobalt, Cupric copper, nickel, and ferric iron in the temperature range of 750° to 950°C. Dynamic gas-solid techniques have been employed in which oxide-sulfate and basic sulfate mixtures were placed in a stream of gas of controlled SO3 potentials. Thermal analysis and thermogvavimetry were used as detection methods, and it was found THE formation of sulfates during the roasting of sulfide ores is now considered to arise in many cases from the interaction of sulfur trioxide in the gas and the metal oxide which is formed on the sulfide as a first step.' As a preliminary to the investigation of the kinetics of sulfate formation during roasting, measurements have been made of equilibria from which the free energies of formation of cobalt, copper, nickel, and iron sulfates can be that the range of temperatures which could be investigated and the choice of method was largely controlled by the kinetics of these gas-solid reactions. The results are compared with previous results obtained from static measurements with which they agree quite well, and calculations have been made employing themal data to interrelate the present results with those for other sulfates. calculated. The method used has been to expose the solid sulfate (or basic sulfate) to a controlled flowing gas mixture of SO,, 02, and SOs and to observe the temperature of decomposition. The onset of decomposition was detected by thermal analysis or thermogravimetry. EXPERIMENTAL METHODS The thermal-analysis method was similar to that employed by Dewing and Richardson.' The sulfate was dehydrated at 250°C in air, and placed in a small alumina crucible which was held by a quartz ring in the hot zone of a horizontal furnace. The reaction tube of this furnace was made of mullite.

Jan 1, 1965

By R. N. Kust, J. C. Agarwal, H. E. Barner, N. Beecher, D. S. Davies

Kennecott Copper Corp. has developed a new hydro-metallurgical process for extracting nickel, copper, cobalt and molybdenum from manganese nodules. This process (KCC Cuprion Process) utilizes a reduction leach operating at atmospheric pressure in the temperature range of 45 OC to 50°C and has been successfully demonstrated in a continuous pilot plant processing 350 kg/d of nodule ore. The chemistry, basic flowsheet and operating characteristics are presented and discussed.

Jan 1, 1980

By K. F. Unrug

Eastern coalfields have been extensively strip mined. In the past, contour mining left vast areas of post-mining highwalls and benches. Thin seams, which cannot be feasibly mined with conventional methods, quite often contain substantial reserves of high quality coal. Unconventional secondary recovery methods may permit economical production of that coal, increased use of reserves, and provide resources for restoration of orphaned land. Technical and rock mechanics implications of secondary mining methods are discussed to determine their limitations and the objectives of required research.

Jan 1, 1986

By Thomas N. Williamson, Victor Zeni

A 6-ft diam core drilling machine has successfully completed seven mine shafts in Virginia and West Virginia to depths as great as 465 ft. There is no practical depth limitation to this new system-a potential method in formations not easily penetrated with other large-scale drilling programs-and higher penetration rates and larger diameters are possible in some formations already being drilled successfully by other methods. The core barrel on the machine is fitted with rolling cutters such as those used on oil field rotary bits, so that less torque is required than with other large- scale drilling systems. The core is made with a wider kerf than is achieved with other coring methods, providing more working room for core drilling.

Jan 4, 1957

By E. T. Peters, L. E. Tanner

In the course of a study concerned with the rnechanical behavior of the intermetallic compound CO3V, both structural observations and anomalous electrical-resistivity behavior indicated the presence of a new high-temperature phase in an alloy with the stoichiometric composition, Co-22.4 wt pet V. The evidence, which is given below, suggests that the new phase is situated between the low-temperature ordered hexagonal phase, k,1, 2and the high-temperature disordered fee solid solution, a,3 within a small range of temperature in the vicinity of 1070°C. Structural studies included X-ray diffraction analysis* and electron-transmission microscopy examination* of stoichiometric composition speci- mens homogenized for 1 hr at 1200oC and either air-cooled or water-quenched. The air-cooled specimens yielded X-ray diffraction evidence of the k phase, while electron microscopy revealed a microstructure of both heavily and moderately faulted regions as shown in Fig. 1. The high density of stacking faults (or fine twins) in region A is reminiscent of hexagonal cobalt following its allotropic transformation.4 Selected-area diffraction from this region revealed distinct superlattice reflections of the ordered hexagonal phase, as well as continuous rel-streaks which were normal to the fault planes in the micrograph. The latter is indicative of extremely small spacings between the faults.' Regions such as ß were found to be only partially transformed to the k phase. Attempts to study the antiphase domain structure by either bright- or dark-field techniques were unsuccessful in these initial studies. This was due to the low intensity of the superlattice reflections arising from the closeness of the cobalt and vanadium scattering factors. Quenching Co3V from above Tc appears to suppress the formation of the k phase. Both X-ray and electron-diffraction results indicated that the disordered phase, a, was partially ordered during severe cooling and that the structure of the ordered phase was of the L12 (Cu3Au) type,6 designated here as a'. As in the case of the hexagonal phase, examination of the domain structure was unsuccessful; however, significant information concerning the morphology of this condition was revealed by the appearance of dislocation arrays. In particular, it

Jan 1, 1965

By Ian M. Thomson, Robert W. Greene

Last August, American Commercial Barge Line Co. (ACBL) began moving coal from mines on the old Camp Breckinridge property in Western Kentucky to TVA's new 2600 MW steam plant at Cumberland City, Tenn. By April of 1973, this movement will reach a level of 7 million tpy. TVA bought the coal rights to this property from the General Services Administration in 1965 for approximately $7 million and is now in possession of reserves containing about 120 million tons of recoverable No. 9 coal, and about the same recoverable amount of No. 11 coal. TVA then contracted through competitive bidding with Peabody Coal Co. to mine the No. 9 seam through two slope shafts. The mines are about 300-ft deep and are separated by the one major fault on this property. The mine portals are approximately 3 ½ mi apart, with the northern portal being over nine miles distant from the Ohio River.

Jan 1, 1971

By M. R. Hoover, J. H. Kim, S. J. Kloda, R. E. Carmola

Feed preparation circuits, which involve such unit processes as size reduction, classification, and beneficiation are inherently a capital and operating cost intensive part of synthetic fuels plants. These circuits, as encountered in similar minerals industry operations, have until now been designed more or less by individual experience and preference mainly because of the large number of variables involved. As a first step towards a computer-aided design tool, a flowsheet simulator has been developed based on an executive program which can connect and drive modular subroutines according to the proposed circuit. The most efficient and appropriate mathematical models were selected as modular sub- routines among available sources such as SPOC, ASPEN, and DOE. Advantages and limitations of this kind of approach are discussed from the system architecture and methodology transfer standpoints with special emphasis on synfuels circuits.

Jan 1, 1983

By L. W. Saperstein, J. C. Mills, L. B. Phelps

Selective placement of toxic mine spoil has been advocated as a means of reducing environ¬mental pollution at the source. However, methods of burial to control environmental damage are not well understood. Using the finite element method, this paper investigates the burial of toxic material within low permeability packages below the water table. The effects of differing package and spoil permeabilities, anisotropy, and infiltration are modeled to provide information about their effect on the flow system. Projections can then be made that will assist in the design of the toxic spoil package to limit the amount of ground water flowing through them.

Jan 1, 1986

By C. R. Pelley

This paper describes the analytical characteristics of Western subbituminous coal and the manner in which these characteristics apply to their use in a utility-sized steam generator. It compares these characteristics with those of typical Midwestern coal and Eastern bituminous coal. The paper also reviews in detail the design considerations that must receive attention when various blends of these three coals, or any combinations thereof, are planned to be used. This research paper describes variations in analytical and utilization characteristics when coals from different origins are blended in order to achieve a predetermined sulfur content for the purpose of predicting sulfur oxides emissions as they affect environmental regulations and the resulting alterations in utilization characteristics such blending would cause, and how such blends of coal would affect a utility-sized steam generator.

Jan 1, 1979

By Y. P. Chugh, R. F. Roethe

Surface coal mining productivity in the US and Illinois has declined since 1969. The US Department of Energy conducted an analysis in 1980 of the causes of declining productivity in different states. This paper presents a detailed analysis of changes in overall productivity and productivity in different functions, such as overburden preparation and stripping, reclamation, and coal handling, from 1970 to 1982. Statisical analysis techniques, including multiple regression were used in the study.

Jan 1, 1985

By Joseph Jensen, J. B. Stevens

The history of the normal oil field is supposed to show an oil graph starting high in flush production, descending more or less steeply into the curve of settled production and dropping gradually to the vanishing point of economical operation. Together with this, somewhere in the early history of the field, there appears from a vanishing point a graph showing the production of water. During the period of settled production this graph rises higher and, toward the close, unless extensive work is done in the line of correction, rises far above the oil graph to the point at which the cost of operation terminates profitable pumping. Fields that start out with a high relative content of water are generally very short-lived. Fields that never develop a water problem are exceedingly rare. The McKittrick oil field, Kern County, California, with 840 acres of proved ground, 300 wells and a present recovery per acre of 94,598 bbl. from 1898 to Aug. 1, 1930, presents a study which is an apparent reversal of the outlined normal history. Though the history of the field now covers over 30 years of operation, it is still too early and the conditions too unique to project the graph of production to completion. The present conditions and directions of change are most interesting, in that the curve of oil production is remarkably flat and the curve of water invasion, after reaching an appalling height, has shown a definite reversal and a continued decline for 10 years. Early drilling in the McKittrick field was in or prior to 1898. Development continued steadily to 1918 when the present limitations of the field were determined. Shut-offs, according to accepted practice of the time, were made by driving the shoe into a shale stratum or into a tamped-in bridge of sand, rosin and clay. Records of early days speak of three waters: (1) surface water which was fresh; (2) an intermediate sulfur water, encountered below the top oil or tar sand; (3) bottom salt water. In different portions of the field any one of these waters let into a well by faulty completion might require immediate correction to obtain satisfactory production. In many wells,

Jan 1, 1931

THE first award of the James Douglas gold medal for achievement in non-ferrous metallurgy was made to Frederick Laist, of the Anaconda Copper Mining Co., and the presentation ceremony was a feature of the annual banquet of the Institute at the Waldorf, on Feb. 21. Frederick Laist was born in Cincinnati, Ohio, Oct. 30, 1878. In his early youth his parents moved to California where, in 1901, Mr. Laist graduated from the University of California, in the course of chemical en-gineering. For one year after graduation he was an in-structor in chemistry at the University of Utah. Fol-lowing this he was employed as a chemist in the lab-oratory of the Washoe Reduction Works of the Anaconda Copper Mining Co., where in successive stages he has occupied the position of chief chemist, blast-furnace superintend-ent, assistant superintend-ent of the entire plant, superintendent, and finally manager of the Anaconda company's reduction plants in Montana, which position he now holds. Mr. Laist, in his labora-tory work, manifested great interest in the hydrometal-lurgy of copper and zinc. As chief chemist at Anaconda, he brought the laboratory to a high degree of efficiency.

Jan 3, 1923

By W. M. Dressel, A. Visnapuu

The Bureau of Mines, U.S. Department of the Interior, has upgraded high-iron domestic chromite concentrate to high-chromium concentrate by a laboratory carbonyl process. The chromite concentrate product has a chromium-to-iron ratio in excess of 3:l compared with the starting concentrate ratio of 1.6:1. The high-iron chromite was first reduced to convert the iron oxides to the metal, and then treated with carbon monoxide at elevated pressures and low temperatures to convert the metallic iron fraction to iron pentacarbonyl. Carbonylation was accelerated by the addition of hydrogen sulfide in small quantities. A constant flow of carbon monoxide swept the iron pentacarbonyl formed in the reactor out through a pressure-reducing valve. The mixture of carbon monoxide and iron pentacarbonyl at atmospheric pressure was then passed through a heated section to decompose the iron pentacarbonyl to carbon monoxide and iron, whereupon the latter plated out on the heated surface. Carbon monoxide pressure, temperature, and promoter trends for enhanced carbonylation are presented.

Jan 1, 1984

By Owen Rice

CHANGES in coke hardness affect the working of the blast furnace, for soft coke is an obstacle to proper furnace operation. Soft coke is due to a low hydrogen-oxygen ratio in the coal charged; increasing this ratio increases the hardness of the coke. The best means of determining the hardness of coke is the combined tumbler and ball-mill. Soft coke is a great hindrance to proper blast-furnace operation and changes in coke hardness affect the working of the furnace. The best method of determining the hardness of coke is by using a combination tumbler-ball-mill. Soft coke is due to a low hydrogen-oxygen ratio in the coal charged. An increase of this ratio improves the hardness of the resulting coke. WHAT IS GOOD COKE? It is not always appreciated that the correct answer may be such a reliable forecast to the physical condition of the blast furnace, and incidentally its entire operation, that among the ordinary variations in other raw materials and also in operating conditions, it assumes a position of primary significance. Inasmuch as coke forms two-thirds of the total bulk of material charged, this assertion will not seem exaggerated, and in the subsequent discussion its applicability will be presented. Coke is the ideal blast-furnace fuel because it is strong and hard enough to resist the crushing and grinding effects of the furnace burden, and its porosity allows the ready passage of gas upward through the charge, and rapid combustion before the tuyeres. Coke deprived of its strength and with a cell structure physically frail and chemically susceptible to solution by carbon dioxide, has its chief asset eliminated. When the melting zones are approached the fluid cinder trickling toward the hearth will envelope the small pieces of coke and form a sticky mass that will retard the free passage of gas. Blast pressure will then rise, driving

Jan 1, 1921

By W. A. Walker, G. W. Ostroot

An increase in the number of deep wells being drilled where extreme bottom-hole temperatures are encountered, and the anticipated drilling of wells where temperatures in the range of 500°F or higher may occur, has brought about a comprehensive investigation of cementing materials and of the techniques involved in their proper usage at these elevated temperatures. Included are developments in cements, retarders, weighting materials and other cement additives which make it possible to formulate a variety of compositions to help resolve the cementing problems of these extreme well conditions. The problems associated with the selection and testing of cements are discussed, and a resume of field results is included. Previous studies on strength retrogression indicate that caution should be exercised in the selection of a cementing composition for use in high-temperature wells. It now appears that, by the addition of silica flour as a stabilizing additive to certain cements, compositions covering a wide range of slurry densities can be designed to meet extreme well conditions without strength retrogression. Improvements in cement retarders make it possible to produce a four-hour thickening time at static temperatures up to 500°F. This temperature is considerably higher than conditions presently being encountered in drilling and completion work. Inert weighting materials, used to produce 20-lb/gal or heavier cement slurries, are reviewed. INTRODUCTION As the search for oil continues, the number of wells being drilled to depths of 10,000 ft or below has continued to increase over the past decade. During 1959, there were 50,893 wells drilled in the United States for a total of 209 million ft of hole. Of this total, approximately 4.45 per cent were drilled below 10,000 ft and 0.30 per cent below 15,000 ft, with a record depth of 25,340 ft recorded (Table 1). With the drilling of this record-shattering hole comes the question, "How deep can wells be drilled?".' Limitations with respect to equipment (surface and subsurface), cementing materials and techniques would cause some concern; however, a panel of experts have agreed that the U. S. oil industry has the equipment and know-how to drill a 50,000-ft hole. The greatest deterrent would be the 700°F temperature they would anticipate encountering at this depth. Although the number of wells drilled under what is generally considered hot-hole conditions (230°F and higher) has been relatively high, each well often presents distinctly individual problems and requires separate consideration and selection of special materials, techniques and equipment. At the present time there are over 30 additives and special cements available for use in "tailoring" a cementing composition for a specific well. It is not uncommon to use three or four different additives with the basic cement to produce the desired slurry characteristics. A generally accepted procedure is to make laboratory tests on selected cementing compositions prior to pumping them into wells deeper than 12,000 ft, or where static temperatures are in the range of 260°F or higher. In some instances, it is recommended that laboratory tests be made where less severe well conditions are encountered. Prior to selecting a cementing composition for a particular well, key personnel representing the operator, drilling contractor and service company should meet to determine that each individual is acquainted with every detail which might influence cementing results and to discuss the execution of the job. For cementing hot-holes, a number of factors must be evaluated before proceeding with the operation. Consideration must be given to the following. 1. Thickening time—The slurry must remain fluid for a sufficient length of time to allow displacement down the casing and up the annular space in a primary cementing job or, in squeeze-cementing, adequate thickening time for both the build-up of a satisfactory squeeze pressure and the reversing out of excess cement. The thickening time of standard retarded cements will often be too short under extreme temperature conditions, thus involving special formulations and requiring laboratory tests to determine the proper amount of additional retarder to obtain the desired pumpability.

Jan 1, 1951