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Duval Corporation, the copper -producing subsidiary of Pennzoil United, Incorporated, operates two plants south of Tucson, Arizona: Esperanza and Sierrita. The newest, the Sierrita mine and mill, came into full production in 1971 at a rate of 72,000 tpd (now 87,000 tpd) which at that time made it the largest designed copper plant in the world. In 1968, the largest milling units then available were selected; these included fourteen 16$ ft by 19 ft long ball mills (5 m by 5. 9 m), each equipped with a 3,000 hp motor. The primary crushing plant contains two 60 in. by 89 in. Allis- Chalmers gyratories; each is constructed for two-side dumping by 120- and 150-ton trucks. Access to the maintenance areas to service the drive motors, eccentrics, apron feeders, and speedup conveyor is through hatches between the crushers. This area also contains a good- sized elevator and a stairway. The rather shallow dump pocket, the 300 -ton crushed ore pocket, and the overall design make for a fine, compact arrangement for two 60 in. crushers installed in a total height of 89 ft (27. 13 m) from dump level to top-of-concrete at the lowest level beneath the collecting or speedup belt. This efficient layout is reflected in the short changeout time for mantle and concaves (8 and 30 hours respectively) and the low crushing cost of $0.0416 per ton (first half of 1975). The crushers are installed on 64 ft (19.5 m) centers (Bougainville and Palabora, both with 54 in. crushers, are 55 and 43 ft or 16.76 and 13. 1 m respectively). The switchgear room is located between the truck dumping positions on one side of the installation and the hydroset units on the other side, with dust collecting equipment mounted over the latter. Protection of these units from rocks falling from the trucks is provided by concrete walls. Truck dumping is controlled from a central 25 ft high (7.6 m) control room, which permits fine observation of operations. Removal of oversize boulders from the dump pockets is done with a hydraulic grapple or a rock hook or sling attached to the auxiliary crane hook. Spare mantle stands and a maintenance room with a zinc melting furnace are located at one end of the surface facilities. The maintenance room is equipped with an access door for the crane, which is equipped with 80- and 20-ton hoists. The two 84 in. (2. 135 m) apron feeders receiving the 6 in. (152 mm) crushed rock discharge onto a 72 in. (1. 83 m) collecting and wear belt operated at a speed compatible with the 60 in. (1.524 m) takeaway belt running at a speed of 630 fpm (192 mpm). This belt feeds a 54 in.

Jan 1, 1978

By Arthur C. Simmons

Production of oil within the state of Pennsylvania in 1940 was slightly more than the 1939 total, and this increase was due entirely to the new flush Music Mountain field south and west of the main Bradford pool. The influence and magnitude of Music Mountain production will be separately described, inasmuch as it is an important producing unit within the state. Production Bradford Field The production listed herein for Bradford field includes only the part of the field that is within the state of Pennsylvania. Approximately 4000 bbl. per day, or 10 per cent of the total Production of Bradford field comes from Cattaraugus County, New York, and should properly be attributed to production obtained within the New York state area, although locally and economically the Bradford field, situated both in New York State and Pennsylvania, is included as a single statistical unit. The 1940 average production in the Bradford field was 34,831 bbl. per day, as compared with a daily average in 1939 of 35,340 bbl., or a decrease from 1939 of 509 bbl. per day. The decrease in production from the Pennsylvania portion of the Bradford field would have been more pronounced if a portion of the crude from the Music Mountain field were not included with the statistics for Bradford field. The decline can be attributed largely to the fact that more properties of lower average recovery were being drilled in 1939 and 1940 than in previous years, and apparently a subnormal amount of drilling occurred in 1938 and 1939, when about 2100 wells were drilled each year. The full effect of the 1940 drilling is not felt immediately and undoubtedly will affect the producing period of 1941. It appears probable that the water-flood area in the Bradford field has reached a definite peak unless some unusual economic condition should cause abnormal prices and an excessive rate of development such as occurred in 1936 and 1937. Virtually all of the production in the Bradford field was obtained by water-flooding methods, as natural or stripper wells are uneconomical and air and gas repressuring have not proved so efficient as water-flooding as a secondary recovery method. Central and Southern Pennsylvania Central and southern Pennsylvania produced a total of 4,604,763 bbl. of oil during the calendar year of 1940; that is, an increase over the 1939 total of 166,728 bbl. The daily average production was 12,581 bbl., or an increase over 1939 of 422 bbl. per day. Table I includes the total oil production for the state of Pennsylvania for the years 1937 to 1940, inclusive, and the daily average for each of these years. It is impractical to make a complete subdivision by districts, consequently the only segregation is the production from the Bradford field (within the state of Penn-

Jan 1, 1941

By C. E. Siebenthal

produce attractive and consequently more salable products. It would seem, however, that if solder and babbitt were cast in closed molds, just as good practical results would be obtained by the user, without his being able to give preference to solders of unnecessarily higher grade on account of their appearance. It would be hopeless for any one. manufacturer of solder to undertake a change of this kind, but if all manufacturers of solder agreed upon it, they would be able, in my opinion, to get the users of solder to take, and to approve by their practical tests, metals containing less tin than they have been accustomed to. The same is true with regard to babbitt metals. An illustration of how, in the use of an alloy, appearance sometimes is deceptive, is to be found in the case of what may be called intermediate grades of babbitt. I am thoroughly convinced that high-tin or high-lead babbitts are better than those containing both lead and tin with relatively high percentages of each. A high-tin babbitt should not contain more than about 10 per cent. of lead, and a high-lead babbitt should not contain more than 10 per cent. of tin, unless the percentage of antimony can be correspondingly increased. The intermediate babbitts, such as those that contain from 30 to 70 per cent. of lead or tin, may give nice appearing castings that flow easily, but they have not the serviceability of the high-lead or high-tin babbitts. Their hardness diminishes very rapidly as the temperature rises, and they have a relatively low softening point due to the eutectic components present. The Cadmium Supply of the united States* C. E. Siebenthal, † Washington., D. C.—From being one of the most maligned of metals—a veritable bugaboo—cadmium has almost overnight become respectable, though its slender claim to respectability rests almost wholly on the possibility of its substitution for tin. Preliminary to any campaign for such substitution, particularly for enforced substitution, the possible supply of cadmium should be determined as closely as possible; for that reason the statistical inquiry of which this paper embodies the results was undertaken. Production Cadmium is marketed in two forms, as metallic cadmium, in sticks or bars, and as cadmium sulfide, the pigment. The metal has found its greatest field of use in this country as a component of an easily fusible alloy that is used in automatic fire extinguishers. The sulfide is used to some extent in paints but chiefly to give color and luster to glass and porcelain. The metal was first made in this country by the Grasselli Chemical

Jan 1, 1919

All the TECHNICAL PUBLICATIONS and CONTRIBUTIONS published in 1939 are available at Institute headquarters, unless otherwise noted. They are also on file in many public, university and technical libraries and, when so indicated in the list, may be found in the TRANSACTIONS. TECHNICAL PUBLICATIONS in Classes A-Metal Mining, B-Milling and Concen-tration, H-Industrial Minerals, and ;I-Mining Geology are distributed in MINING TECHNOLOGY, which is issued every other month. Technical Publications in Classes C-Iron. and Steel Division, D-Nonferrous Metallurgy and E-Institute of Metals Division are distributed in METALS TECHNOLOGY, which is issued twice quarterly. TECHNICAL PUBLICATIONS in Class G-Petroleum Division are distributed in PETRO-LEUM TECHNOLOGY, which is issued quarterly. TECHNICAL PUBLICATIONS in Classes F-Coal Division, J-Mineral Industry Education Division, K-Mining Administra-tion, and L-Geophysical Methods of Exploration are issued as separate pamphlets. An Institute member is entitled to one copy of any TECHNICAL PUBLICATION or CON-TRIBUTION. Copies of TECHNICAL PUBLICATIONS listed have been mailed to members of the Institute according to their registration by classes. CONTRIBUTIONS and Other TECHNICAL PUBLICATIONS will be sent upon request. A member relay purchase an additional copy of a TECHNICAL PUBLICATION Or a CONTRIBUTION at One cent a page; minimum charge, 25¢. Nonmembers may purchase any CONTRIBUTION or a TECHNICAL PUBLICATION Of the F, J, K, or L classes at the same rate, but the nonmember price per copy for METALS TECHNOLOGY, MINING TECHNOLOGY or PETROLEUM TECHNOLOGY is $1. TECHNICAL PUBLICATIONS (separate pamphlet form), $2 per annum; Canadian and foreign postage 50 cents extra. METALS TECHNOLOGY, $7 per annum; Canadian and foreign postage 50 cents extra (Iron and Steel Division and Institute of Metals Division ferrous and nonferrous papers). MINING TECHNOLOGY, $6 per annum; Canadian and foreign postage 50 cents extra (metal mining, milling and concentration, Industrial Minerals Division, and mining geology papers). PETROLEUM TECHNOLOGY, $4 per annum; Canadian and foreign postage 50 cents extra. Bound volumes have been mailed to members that have requested them, and MINING AND METALLURGY is mailed each month. A member is entitled to one volume a year on his membership and lie may purchase for $2.50 one copy of a volume not already received; additional copies of 'the same volume, $5. Nonmembers may pur-chase the volumes listed, at $5 each, plus 60 cents for Canadian or foreign postage. Extra single copies of MINING AND METALLURGY, 25¢ current issue, back numbers 500 each to members; to nonmembers 50¢ current issue and $1 each, back issues. Subscription price to nonmembers and to members for extra copies, $3 per annum plus $1 for Canadian or foreign postage.

Jan 1, 1939

By A. Kenneth Schellinger, O. Cutler Shepard

Overgrinding, Or the breaking of ore particles into sizes smaller than required for liberation, is a first-magnitude problem in grinding for concentration processes. The conventional ball mill-classifier circuit used in commercial grinding produces mineral particles that are all ground to pass an upper size limit, while the proportion of very fine sizes, or slimes, is uncon rolled. Calculations based on measurements made in commercial plants which were grinding ore for flotation concentration indicate that about go pct of the energy used in grinding is consumed in useless overgrinding.1 In addition to accounting for the consumption of a large amount of energy, over-grinding is detrimental to the flotation process. Overground slime coats larger partitles and inhibits selective action by the flotation reagents on particles which by themselves could be separated very well. A further difficulty is that extremely finely ground minerals do not respond satisfactorily to flotation-collecting reagents, and both selection and recovery decrease markedly with particles finer than 5 to 10 microns.2 conventional classifier-ball mill circuits inherently tend to overgrind the valuable minerals more than the gangue minerals because most valuable minerals are of higher density and are softer and more friable than the gangue minerals. The rem- edy to this situation would seem to be a separating mechanism which would separate free valuable mineral particles regardless of size and density considerations and a mechanism which would operate in the grinding mill so that valuable mineral grains would be removed from the grinding machine as soon as they are freed. A consideration of these ideas led the authors to the conception of a simultaneous grinding and flotation mechanism. So far as the authors are aware, such a machine has never been tried, even on a laboratory scale. Development oF Apparatus and Experimental Method Apparatus development went through several stages before a really workable machine was devised. Work was started with a large cast-iron mortar 7½ in. in diameter and 8 in- deep. A cast-iron disk Was mounted on the end of a vertical shaft SO that it fitted loosely into the bottom of the mortar. On top of the disk four radial cleats ¼ in. high were bolted to agitate the ball charge as the disk, or impeller, rotated. The vertical shaft was driven at 100 rpm by a mechanism improvised from an old coffee-mill type of grinder. A hole was drilled into the bottom of the mortar through which compressed air was introduced for frothing. In operation, more charges of Ore which had been crushed to pass an 8-mesh screen were placed in the bowl along with water and suitable reagents. The impeller was then started and the compressed air turned On so that the ore was ground while being exposed to air bubbles. Mineralized froth was

Jan 1, 1949

By H. J. Modi, P. L. De Bruyn

IN recent years interest has been aroused in flotation rate studies both from a technical and a more practical aspect. With increasing fineness of grind becoming a necessity in treatment of low grade ores, difference:; in flotation rates of various size ranges will assume importance in the evaluation of overall recovery results. Theoretical analysis of flotation kinetics was initiated by Schuhmann,' who sought to define flotation rate of a given mineral and specified size range in terms of certain physical variables of the flotation system. Using as a basis for his analysis the bubble-particle encounter hypothesis previously advanced by Gaudin,' Schuhmann writes for the rate of flotation (R,.) of particles of average size x, Rx = PcPa(x) V F. [1] In this relation Pc and Pa represent, respectively, the probability of collision between particle and gas bubble in a given time interval and the probability of adhesion of particle to the bubble after collision. Rigorously speaking, the term PC does not have the significance of a probability factor, since it depends on the time interval and therefore can be numerically greater than unity. The term c(x) expresses the concentration of particles of an average size x in the flotation cell in weight per unit volume of pulp, and V denotes the total volume of pulp in the cell. The product, P,c(x)V, defines the frequency of particle-bubble collisl.on, and when it is multiplied by P,, the number of collisions per unit time resulting in successful adherence is obtained. The factor, F, measures the froth stability and is introduced because after fruitful bubble-particle contact some particles may still riot reach the froth launder. Coalescence of bubbles in the froth column or too short a bubble life could account for this effect. Schuhmann also introduced the concept of "specific flotation rate" (Q) to allow for the relative abundance of different mineral species in the flotation pulp. The specific flotation rate, having the dimension of reciprocal time, is defined as Eq. 2: Qx =Rx/c(x)v [2] and it also follows from Eq. 1 that Qx = PcPaF. [31 The theoretical aspects of flotation kinetics were also considered by Sutherland,3 who tried to improve Eq. 1 by expressing the probability factors in terms of such physical variables as particle radius (x), bubble radius (X), velocity of bubble relative to particle (v), the number of bubbles per unit volume of pulp (N) and the induction period (A) necessary for air-mineral adhesion. According to Sutherland's treatment, the rate equation, Eq. 1, transforms to R, = [3pX x v N] [sech2 (3 v ?/4 X) ] ?c(x) V [4] where the first term in brackets on the right-hand

Jan 1, 1957

By D. B. Carson, D. L. Katz

Natural gases under pressure form crystalline hydrates with water. Experimental data are reported on four-phase equilibrium for the methane-propane-water, methanc-pentane-water, and methane-hexane-water systems. Temperatures and pressures for equilibrium between gas, water-rich liquid, hydrocarbon-rich liquid, and hydrate were measured, as well as the percentages of methane and propane in the hydrate. The data indicate that natural gas hydrate behaves as a solid solution and that pentanes and heavier hydrocarbons do not enter into the solid phase. Vapor-solid equilibrium constants are presented that permit the approximation of the conditions for hydrate formation, from the composition of a gas. Introduction Natural gas hydrates have been the object of considerable research in recent years, because of the trouble they have caused in the natural-gas and natural-gasoline industries. Natural gas hydrates are white crystalline compounds of water and gas, which, under pressure, exist at temperatures considerably above the freezing point of water. Because of the relatively high temperatures at which the hydrates exist, they become a nuisance in high-pressure gas operations where water is present, since their formation causes partial or complete plugging of valves and pipes. From a practical standpoint, the trouble incident to hydrate formation has been solved by dehydration of the gas before it enters the plant or pipe line, or by other remedial measures. Extensive work on gas hydrates in the latter part of the nineteenth century, by Villardl and others, gave data on methane hydrate and on ethane hydrate. Schroeder summarized these theoretical studies2 Hammerschmidt3 introduced the information on gas hydrates to the gas industry and Dcaton and Frost4-6 gathered a considerable number of data on the behavior of natural gas hydrates. Recent papers7,8 have extended both the data and the theory of these hydrates. At present, data are available on tem-peraturcs and pressures of hydrate forma. tion for pure methane, ethane, propane, n-butane, methane-ethane mixtures, meth-ane-propane mixtures, methane-butane mixtures, and some Is natural gases, all- in the Presence of excess water. However, up to the Present time no method has been available for predicting the temperature at given pressures or the pressure at given at at which natural gases will form hydrates if hydrates with water. 'This Paper Presents data on the methane-propane-water, methane-pentane-water and methane-hex-""e water systems in four phases, one of which is the hydrate. he application of the phase rule to the methane-~ro~ane-water data Proves that hydrates behave as solid solutions. The data of this paper and those in the literature were used to develop vapor-solid. equilibrium constants,8 which permit prediction of conditions of hydrate formation from the analysis of a natural gas.

Jan 1, 1942

The great Bingham Canyon mine and mill complex of Magna, Arthur, and Bonneville had their beginning in a 300 ton per day operation which was commenced by Daniel C. Jackling and his associates in 1904 as the Utah Copper Company. This small plant was quickly expanded to 500 tons per day and eventually Kennecott, the Utah Copper successor, was processing about 45,000 tons per day of ore in each of its mills, Magna and Arthur. Finally, in 1966, the Bonneville crushing and grinding plant was added to produce a slurry of ground ore for flotation concentration at the expanded Magna and Arthur mills. Bonneville is one of the few railroad dump primary gyratory crushing plants constructed in recent years; another which is described in this Monograph is Cuajone in Peru, started in 1976. Two others are the Climax Henderson unit and the Phelps Dodge Tyrone crusher, which has been fed by trucks since it commenced operation. The Bonneville, Henderson, and Cuajone crushers are all located considerable distances from their mines, hence the use of rail haulage. Shovels in the Bingham pit are 8 to 15 yd capacity; and ore is sent to the Bonneville crusher in 100 ton rail cars, where they are dumped, two at a time, by a hydraulically driven rotary dumper. Ahead of the 54 in. by 74 in. Allis-Chalmers gyratory are two grizzlies, each 27 ft 9 in. (8.46 m) long with bar spacings of 4 ½ in. (114 mm) at the feed end and 6 in. (152 mm) at the discharge end. Grizzlies are sloped at 38. Oversize rocks are re- moved from the crusher pocket by an overhead crane, and the crusher produces a nominal 6 in. (152 mm) product. Rail cars are dumped in the direction away from the crusher, and water sprays at the dumper level and in the rock boxes are used for dust suppression. There are two 72 in. by 19 ft (1.83 m by 5. 8 m) apron feeders under the 500 st cr'ushed ore pocket and two more under the grizzly undersize pocket. Feeder speeds are variable up to 72 fpm. Grizzly undersize is dropped to the feeder pocket by three shelves forming a rock ladder attached to the pocket walls. Each pair of apron feeders, one for crushed ore and one for grizzly undersize, discharge to a 72 in. (1. 83 m) picking belt for tramp removal; this belt feeds one of two 54 in. (1.37 m) feeder conveyors which in turn discharge to a 60 in. (1. 52 m) takeaway belt operating at 175-300 fpm (53.3 - 97.4 mpm). Both picking belts are equipped with metal detectors and tramp iron magnets, and a separate 30 in. (760 mm) conveyor is used to remove tramp material.

Jan 1, 1978

By Lester C. Uren

Tars paper reviews the industrial trends and changes in educational concepts that have led to the development of the modern petroleum engineering curriculum. A trend toward emphasis on engineering fundamentals is noted. While most universities are committed to the traditional four-year engineering program, it is agreed that more than four years is necessary for academic preparation of the petroleum engineer in all phases of his profession. The author proposes a coordinated program of undergraduate and graduate training that will permit of adherence to the general pattern of the present four-year engineering course, with provision for extension of the program into specialized graduate courses of professional character. In the latter, emphasis may vary with the interests and objectives of the individual student. A specific undergraduate curriculum is proposed in which upward of 80 per cent of the available time is devoted to engineering fundamentals. A broad survey of the professional field is afforded in courses grouped in the third and fourth undergraduate years, but detailed treatment of the professional aspects of petroleum engineering is reserved for the graduate program. INTRODUCTION Of necessity, engineering curricula must ever be changing to reflect the new techniques, the changing concepts that are presented as the engineering industries develop and unfold. Particularly is this true of the younger engineering curricula representing comparatively new and rapidly changing industries such as the petroleum industry. Institutions that planned their petroleum engineering curricula a decade or two ago now find that the petroleum industry has become vastly more technical in its requirements. En¬tirely new methods and techniques have come into vogue and must be given place in the curriculum, and some of these are of a character that demands changing emphasis in the fundamental preparatory subjects. College and university faculties cannot complacently assume that curricula in this field that were considered appropriate 10 or 20 years ago still reflect the needs of the industry that they are designed to serve. If they do, their graduates will be poorly equipped to meet the requirements imposed upon them by a rapidly changing industry. Perhaps it is not too much to expect academic authorities to anticipate the trends of industry and equip their graduates with what they will need to attain leadership 10 or 20 years after graduation. Whether or not this desirable objective is possible, there is no excuse for allowing curricula to fall behind the current needs of industry. DURATION OF CURRICULUM The majority of our engineering schools and colleges still adhere to the four-year curricula and there appears to be a definite sentiment among many engineers engaged in industry that work should be so planned that the engineering student may secure the essential academic preparation for his profession in a terminal four-year program. Yet, in recent years, it has become increasingly apparent that four years of

Jan 1, 1941

By Horace W. Hindry

This paper presents the ingredients composing a type of oil-base mud that has been successfully used in drilling oil horizons in California, the effect of ingredient concentrations on physical properties, methods of handling at the well and possible advantages of a waterless drilling fluid with excellent plastering properties. INTRODUCTION AN oil-base mud is a rotary drilling fluid in which oil has been substituted for water as the principal liquid ingredient. In recent years such a mud has been developed and used successfully for drilling the oil horizons of wells in various California fields. There are several types of oil-base mud, but only the type that is currently used to any appreciable extent will be considered at this time. The oil-base drilling-mud compositions used by Shell Oil Company, Incorporated have been covered by several patent applications on which patents are expected to issue at an early date. The purpose of this paper is to present data on the fundamental design of the mud; the ingredients used and their specifications; the effect of ingredient concentration on physical properties; the selection of the proper mud; the facilities needed for handling the mud; and a general discussion [oil] drilling with oil-base mud. In view of the early stage of development of oil-base mud, the great number of variables, and the almost unlimited possible combinations of these variables, which in turn require extensive laboratory study, there are certain irregularities and omissions in the data presented here. However, it is believed that sufficient data are at hand to permit a fairly complete analysis of the characteristics of oil-base muds. In view of the excellent plastering properties of oil-base mud when properly proportioned, its use should: (I) minimize the possibility of impairing the natural flow potentialities of the producing horizon such as that resulting from infiltration of water from water-base muds; (2) permit smaller clearances for setting liners, since the mud sheath has no appreciable thickness; (3) eliminate the possibility of clogging the perforations of the liner with thick mud sheath; (4) facilitate the removal of the mud sheath from the walls of the hole, for its mud sheath has no appreciable strength; (5) assist in drilling through formations, such as "heaving shale," where water wetting appears to be a source of difficulty. (6) permit cores to be obtained without contamination from drilling water. FUNDAMENTAL DESIGN OF AN OIL-BASE MUD In the design of any rotary drilling mud it is necessary to select materials that will fulfill the following requirements: (I) act as the liquid medium and regulate the viscosity; (2) impart initial and final plastering properties; (3) give gel strength and structure in order to prevent settling; (4) serve as a weighting material. The

Jan 1, 1941

By Don B. Carson, Donald L. Katz

NATURAL gases under pressure form crystal-line hydrates with water. Experimental data are reported on four-phase equilibrium for the methane-propane-water, methane-pentane-water, and methane-hexane-water systems. Temperatures and pressures for equilibrium between gas, water-rich liquid, hydrocarbonrich liquid, and hydrate were measured, as well as the percentages of methane and propane in the hydrate. The data indicate that natural gas hydrate behaves as a solid solution and that pentanes and heavier hydrocarbons do not enter into the solid phase. Vapor-solid equilibrium constants are presented that permit the approximation of the conditions for hydrate formation, from the composition of a gas. INTRODUCTION Natural gas hydrates have been the object of considerable research in recent years, because of the trouble they have caused in the natural-gas and natural gasoline industries. Natural gas hydrates are white crystalline compounds of water and gas, which, under pressure, exist at temperatures considerably above the freezing point of water. Because of the relatively high temperatures at which the hydrates exist, they become a nuisance in high-pressure gas operations where water is present, since their formation causes partial or complete plugging of valves and pipes. From a practical standpoint, the trouble incident to hydrate formation has been solved by dehydration of the gas before it enters the plant or pipe line, or by other remedial measures. Extensive work on gas hydrates in the latter part of the nineteenth century, by Villard1 and others, gave data on methane hydrate and on ethane hydrate. Schroeder summarized these theoretical studies.2 Hammerschmidt3 introduced the information on gas hydrates to the gas industry and Deaton and Frost4-6 gathered a considerable number of data on the behavior of natural gas hydrates. Recent papers7,8 have extended both the data and the theory of these hydrates. At present, data are available on temperatures and pressures of hydrate formation for pure methane, ethane, propane, n-butane, methane-ethane mixtures, methane-propane mixtures, methane-butane mixtures, and some 15 natural gases, all in the presence of excess water. However, up to the present time no method has been available for predicting the temperature at given pressures or the pressure at given temperatures at which natural gases will form hydrates if saturated with water. This paper pre¬sents data on the methane-propane-water, methane-pentane-water and methane-hexane water systems in four phases, one of which is the hydrate. The application of the phase rule to the methane-propane-water data proves that hydrates behave as solid solutions. The data of this paper and those in the literature were used to develop vapor-solid equilibrium constants,8 which permit prediction of conditions of hydrate formation from the analysis of a natural gas.

Jan 1, 1941

By H. W. Page

Petroleum requirements since V-J day have been appreciably higher than predicted. Foreign operations now exceed maximum wartime levels by about 14 per cent. Domestic operations since V-J day have averaged 92 Per cent of the wartime peak. In spite of maximum foreign refinery runs, large exports of all products, except residual fuel oil, are necessary to meet foreign demand. During the next few years it is expected that foreign operations will continue at capacity, including new installations, but that, because of increases in foreign demand, exports will continue at about their present level. Domestic operations will increase during this period and crude production probably will exceed maximum efficient rates. Even after 10 years some exports probably will be required, but eventually these will be supplanted by increased output of foreign refineries, except for small tributary exports. The increase in domestic requirements will exceed the decline in exports. Unless findings of crude oil exceed present expectations, the increasing demand will be met by increased imports and synthetic methods-—such as the Hydrocarbon Synthesis Process for conversion of natural gas and coal to gasoline and distillates. Catalytic cracking installations will increase as crude availability decreases. This will help to meet the increasing demand for gasoline but will intensify the domestic shortage of residual fuel oil. Eventually larger imports will be required to satisfy the demand for this product. Introduction Under the pressure of the wartime period, there was time only occasionaly to look ahead in anticipation of what the postwar era held for the petroleum industry. Perhaps the general expectation was that a rather pronounced decline in the level of industry petroleum operations would take place shortly after the end of the war, with the impact felt mainly on the economy of the United States- It is of interest now, nine months after V-J day, to take inventory of the near-term situation and see what significant forces are at work. With this as a starting point, it should be possible to engage in something more satisfactory than pure speculation concerning trends in the immediate future and 10 to 20 years ahead. Present and Near-term Situation During the nine-month period following V-J day, foreign crude oil production and rebery operations have actually increased the These activities were at maximum capacity on V-J day but the continuation of drilling programs, the completion of new and rehabilitated refineries and of transportation facilities during the Past nine months have increased the foreign capacity. This added capacity has been fully utilized. Foreign crude oil production in May 1946 is about 14 per cent higher than during July 1945 and refining operations some 12 per cent higher' During the same period there has been a falling off in similar activities within the

Jan 1, 1947

By G. L. Hassler, E. Bruner

An apparatus and method is described whereby the relation between saturation and capillary pressure under decreasing saturation can be quickly determined for small core samples. The initially saturated core is cen-trifuged at increasing rates and the average saturation is measured at each rate with the aid of a stroboscope device. A theory and calculation procedure is given whereby the accelerations and saturation values can be converted into a true curve of capillary pressure versus saturation. The present work differs from previously described use of the centrifuge to obtain capillary-pressure curves of core samples3 in that the core is centrifuged alone, so that the whole range of saturations required by the properties of the sample and the radially varying centrifugal force occurs within the sample. The calculation procedure nevertheless secures correct results from simply obtained values of the average saturation. The apparatus described was developed in connection with studies of capillary pressure and wetting of oil-field rocks, and the paper provides the apparatus background for a previous publication' dealing more fully with the uses and implications of the data in petroleum engineering. The method is applicable, however, to general combinations of immiscible fluids and porous or comminuted solids, and may be useful in other fields. Introduction The importance of capillary phenomena in determining the behavior of liquids in porous media has long been recognized. The concept of capillary Pressure was early formulated, and in recent Years discussions of the application of the laws of capillarity to oil field problems have appeared.l-3 One reason why progress in the application of capillary phenomena to the solution of problems of reservoir mechanics has not been more rapid has been the lack of a, satisfactory technique for measuring the capillary pressures in reservoir rocks. It is the principal purpose of this paper to describe a method by which the relation between capillary pressure and saturation can be determined for small consolidated core samples which have been extracted and resaturated, Capillary Diaphragm Perhaps the most direct way to measure the capillary pressure in a rock is to make piezometric contact with the wetting liquid through a diaphragm of porous material with high displacement pressure saturated with the liquid in question.3-6 The liquid in the diaphragm assumes the pressure of the liquid in the core, which can then be measured with a manometer, while the atmospheric air is prevented by capillarity from entering the diaphragm and affecting the pressure measurements as long as the displacement pressure of the diaphragm is not exceeded. With an apparatus of the type illustrated schematically in Fig. I, the relation between capillary pressure and saturation can be measured for a small core sample by starting with the core saturated 100 per cent, applyillg successively greater suctions

Jan 1, 1945

By Nathaniel Arbiter, Arthur F. Taggart

The fact that the floatability of minerals with fatty-acid collectors changes as the pH of a pulp varies was utilized in the early days of flotation, when sulphuric acid was used with oleic acid to float sphalerite and galena. from gangues which themselves float with fatty acids in alkaline pulps. Gaudin1 showed that this difference in floatability is a regular function of the extent of the change in pH. The present paper offers an explanation of the phenomenon, and on the basis thereof sets up recommendations for control of soap-flotation operations. Experimental Parallelism between floatability of a mineral in a given environment and its contact angle in that environment is so well established,2 and the contact angle is so readily and rapidly measurable, that contact angles have been used throughout the experimental work to indicate relative floatability. Experiments comprised contact-angle measurements on a number of representative minerals and metals, and a variety of subsidiary tests designed to check and to amplify the contact-angle indications. Contact-angle measurements were made by the method described in detail by del Giudice.3 Sequence of procedure for determination of the points of Fig. I was: I. Polish specimen. Most specimens yielded zero contact angle after polishing; a few showed a slight "cling." Cling is characteristic of specimens that pit on polishing; it is due to a residue of organic contamination, originally on the particle surface, which persists in the pits. The cling did not change total contact angle after conditioning, and is not, therefore, additive in the upper part of the curves of Fig. I. It may have broadened the bases of the curves for the affected minerals slightly. 2. The specimen was next conditioned in soap solution for 5 minutes. 3. The conditioned particle was transferred, under conditions that precluded surface drying, to an aqueous solution of the pH desired and contact angle determined. 4. The particle was thereupon transferred, again without surface drying, to water. The confirmatory tests will be described at the places pertinent in the argument. Discussion of Results Gaudin and Vincent4 have shown that contact angles with heptoic acid as a collector decrease for a given specimen when the concentration of collector present falls below a certain value. A similar reduction in angle occurs with collector-conditioned particles that are visibly slime-coated, and varies roughly with the extent of coating. Since in the last case the reduction in angle is certainly due to reduction in the proportion of total conditioned mineral surface presented to the bubble, the authors believe that the same condition prevails in the first case cited, and that similar reduction in angle and floatability will occur whenever starvation quantities of collector are present, whether by design or by reason of excessive consumption.

Jan 1, 1943

By H. H. Reamer, B. H. Sage

Attempts have been made to predict the volumetric and phase behavior of naturally occurring hydrocarbon mix-turesl-6 but these methods have not been extended to the higher pressures and tem-peratures that are currently encountered in some producing formations. Furthermore, the methods of prediction at present avail-able have not been tested in a sufficient number of cases to ensure their applica-bility to all naturally occurring hydrocar-bon mixtures, even at the lower pressures and temperatures. For these reasons the behavior of a number of hydrocarbon mix-tures from a field in which the subsurface pressures are above 4500 lb. per sq. in.t and the temperatures are in the neighbor-hood of 250°F. was investigated. Method The objective of this program was to determine the volumetric behavior of ma-terial as it existed in the reservoir as a function of pressure, temperature and com-position. Strictly speaking, this cannot be accomplished in any simple fashion. How- ever, the variations in composition that are encountered within a producing reservoir may be approximated roughly by means of mixtures made up of two arbitrarily chosen constituents. Experience indicates that the liquid and gas phases from a high-pressure gas trap afford a simple source of material for this purpose. Throughout this discus-sion the samples of the gas phase and liquid phase from the production trap will be called the "trap-gas sample" and the "trap-liquid sample," respectively. The volumetric behavior of both of the trap samples was determined throughout the temperature interval between 100" and 250°F. at pressures up to 5000 lb. per sq. in. In addition, the behavior of eight different mixtures containing varying proportions of the two trap samples was studied throughout the same temperature and pressure intervals. The experimental results yielded information concerning the specific volume of the material as a function of pressure, temperature and the relative quantity of the trap samples. The relative amount of each of the paraffin hydrocarbons of lower molecular weight than n-hexane was determined for each of the trap samples. In addition, the specific weight, viscosity and average molecular weight of the hexanes-and-heavier fraction of the trap-liquid sample were determined as well as similar information for each of five fractions separated from this material by distillation. From these data the weight fractions of each of the components from methane through pentane were determined for the trap samples and eight systematically chosen mixtures. Materials The gas and liquid samples were obtained from the production trap of a well in the Rio Bravo field in California during the fall of 1939. Information concerning the condi- 70

Jan 1, 1941

By Shiou-Chuan Sun

There are several postulations for the mechanism of slime-coating. Incel proposed the electrostatic hypothesis, del Giudice2 suggested the chemical theory; Bankoff3 reported that slime-coating is inhibited whenever the surfaces of the slime particles are ionized sufficiently for Brownian movement to occur, and is facilitated when they are not. These postulations were examined by experiments involving the Burton tube, the cataphoretic cell, and slime-coating. The techniques involved will be described elsewhere in this paper. The electrostatic hypothesis, supported by migration experiments in a Burton tube, was abandoned by del Giudice.2 Experiments of mineral migration in a Burton tube. after the idea of Ince with modification, indicated that this apparatus was inefficient for accurate observation. A cataphoretic cell was constructed. The experimental data, as shown in this paper, enable the correlation and advancing of this hypothesis. Del Giudice's chemical hypothesis considered that slime particles are attached to the galena surfaces by a cement formed as the result of a metathetical reaction between the sulphide and the slime particles. Applying this hypothesis, the calcite slime particles were cemented to the galena surface by the formation of a cementing lead carbonate. In a similar way, lead silicate was considered as the cement of quartz slime coating on galena. Experiments verifying this hypothesis were carried out according to the following procedure: Fresh mineral particles selected from the central part of the broken lumps and examined first under a microscope for ascertaining a clean surface were placed in a small beaker (1.5-in. dia. by 2.5 in. deep) half filled with one kind of slime pulp. The dilution of all slime pulp was 4:I and the particle size of slime was minus 400-mesh. After agitation for 5 min. the specimen was removed by a sharp-end tong and washed gently three times in three separate distilled water baths. It was dried before a small electrical fan and examined immediately under a microscope. A photograph was made of the observation. With reference to the published solubilities,' several of these experiments, which contradict the chemical hypothesis, are listed as following: I. The coating of fluorite slime on the galena surface was light but the coating of galena slime on the fluorite surface was heavy. In a similar way, the coating of quartz slime on the galena was fairly light, but the coating of galena slime on the quartz particle was heavy. According to the chemical hypothesis, using the same constituents and regardless of which is the slime, the density of the coating should be expected to be the same. This, however, as shown above, is not true. Moreover, fluorite (CaF2), having a solubility of 16 mg.4a per liter of water, should not be

Jan 1, 1943

By H. W. Graham

AS these annual occasions in honor of Henry Marion Howe continue through the years: there is progressively less likelihood that the lecturer will have had personal knowledge of Dr. Howe. The present speaker is one of those who unfortunately had no opportunity to come under the inspiring presence of this great metallurgist. A review of Howe's work shows it to cover a comprehensive range of interests and to evidence an impressive richness of detail. Not only was Howe at home in the laboratory, but he was familiar with the processes of iron and steel making and had a real understanding of them. His writings include much that is descriptive of processes with a wealth of material that is becoming of increasing historical value. He recorded his studies of the theoretical aspects of processes and published at least two process classifications, one in 1890 that was lengthy and somewhat theoretical, and a second in 1906 that was more of a practical listing. Wide as Howe's field of interest was, it is significant of the circumstances of his time that he gave- little consideration to raw materials or to their effect on iron and steel making processes. In 1933, Waterhouse, Howe lecturer for that year, presented a descriptive summary of the major steel making processes, and in 1946 Joseph discussed the blast furnace process. Otherwise Howe lectures have not dealt with processes as major subjects. In today's lecture, with no effort to describe the mechanical arrangements of iron and steel making facilities, it is proposed to examine the essential technological elements of the processes, to explore the inter-relation of these elements, and particularly to seek recognition and understanding of those factors which determine why certain processes are or are not used. The discussion of this lecture will deal with the major well-known large tonnage processes, with only such attention to processes of minor tonnage and special character as may be warranted for explanation by contrast. Subject to the errors of generalization and the shortcomings of condensation involved in presentation limited to a single hour, it is proposed to examine broadly but intensively those operations which convert raw materials into steel. It is an innovation for a Howe lecturer to discuss the raw materials of the iron and steel industry, but the changing circumstances of passing years intensify the influence of raw materials on processes and require the metallurgist to be alert for the process adjustments that may become advisable or mandatory. For a half century the metallurgical processing of iron and steel has followed a surprisingly straight path, but this does not necessarily mean that there are no curves in the road ahead. Ages ago primitive man came to know iron in its metallic form, not only by the

Jan 1, 1948

By E. T. Turkdogan, P. Grieveson

It is shown experimentally that, by making use of the coupled S-O reaction in ionic melts, it is possible to transfer slclJur or oxygen from a lozv to a high chemical potential through an ionic nzenzbrane. This uphill transfer of sulfur is accompanied by a counter downhill transfer of oxygen and vice versa. The Materials balance shows that the amoulits of sul -fur and oxygen lost or gained by one system are the same as those gained or lost by the other systenz — the two systejns being separated by an iofzic membmne. The systems used in these experi?nents were solid Mn-MnS-Mno and liquid Fe-S-0. Sufficient results were obtained Lo study the kinetics of the transfer and the indications are that the counter diffusion of sulfide and oxide iojzs in the membrane is the rate controlling process. WHEN an ionic oxide-melt reacts with an atmosphere containing sulfur and oxygen-bear ing gases the following reaction occurs: 1/2 S2 (gas) +O2- (melt) = S2- (melt) + 1/2 0, (gas) [1] Under the restrictions that i) electric conductance in the melt is purely ionic and ii) each constituent element in the melt does not change valence, the solution of an atom of sulfur in the melt will result in the evolution of an atom of oxygen, so that the electric neutrality is maintained. For a given temperature and melt composition, the equilibrium concentration of sulfur in the melt is determined by the ratio, po2 /ps2 , in the gas phase and not by the individual partial pressures of oxygen and sulfur. This has been demonstrated by a number of investigators, for example by Richardson and withers', Fincham and Richardson,la by St Pierre and Chipman,' and by Turkdogan and Darken.3 In his Howe Memorial Lecture for 1961, Darken discussed the possibility of uphill pumping of sulfur through an ionic membrane at the expense of oxygen. TO test the validity of this concept associated with coupled reactions, experiments were carried out in the following manner. A presintered mixture of Mn-MnS-MnO and prefused mixture of Fe-S-0, contained in platinum and iridium crucibles, respectively, and separated by a thin layer of soda-glass (to act as an ionic membrane), were placed side by side in an evacuated silica capsule and sealed. This was then kept at 1400°K for a required time to allow Reaction [11 to occur via the ionic membrane. When partial equilibrium is reached, the ratios Po2 /pS2, for systems on either side of the membrane, are equal and the flux of sulfur and oxygen through the membrane becomes zero, although the individual partial pressures po2 andp,, in these two systems may differ considerably.

Jan 1, 1962

By Shiou-Chuan Sun

There are several postulations for the mechanism of slime-coating. Incel proposed the electrostatic hypothesis, del Giudice2 suggested the chemical theory; Bankoff3 reported that slime-coating is inhibited whenever the surfaces of the slime particles are ionized sufficiently for Brownian movement to occur, and is facilitated when they are not. These postulations were examined by experiments involving the Burton tube, the cataphoretic cell, and slime-coating. The techniques involved will be described elsewhere in this paper. The electrostatic hypothesis, supported by migration experiments in a Burton tube, was abandoned by del Giudice.2 Experiments of mineral migration in a Burton tube. after the idea of Ince with modification, indicated that this apparatus was inefficient for accurate observation. A cataphoretic cell was constructed. The experimental data, as shown in this paper, enable the correlation and advancing of this hypothesis. Del Giudice's chemical hypothesis considered that slime particles are attached to the galena surfaces by a cement formed as the result of a metathetical reaction between the sulphide and the slime particles. Applying this hypothesis, the calcite slime particles were cemented to the galena surface by the formation of a cementing lead carbonate. In a similar way, lead silicate was considered as the cement of quartz slime coating on galena. Experiments verifying this hypothesis were carried out according to the following procedure: Fresh mineral particles selected from the central part of the broken lumps and examined first under a microscope for ascertaining a clean surface were placed in a small beaker (1.5-in. dia. by 2.5 in. deep) half filled with one kind of slime pulp. The dilution of all slime pulp was 4:I and the particle size of slime was minus 400-mesh. After agitation for 5 min. the specimen was removed by a sharp-end tong and washed gently three times in three separate distilled water baths. It was dried before a small electrical fan and examined immediately under a microscope. A photograph was made of the observation. With reference to the published solubilities,' several of these experiments, which contradict the chemical hypothesis, are listed as following: I. The coating of fluorite slime on the galena surface was light but the coating of galena slime on the fluorite surface was heavy. In a similar way, the coating of quartz slime on the galena was fairly light, but the coating of galena slime on the quartz particle was heavy. According to the chemical hypothesis, using the same constituents and regardless of which is the slime, the density of the coating should be expected to be the same. This, however, as shown above, is not true. Moreover, fluorite (CaF2), having a solubility of 16 mg.4a per liter of water, should not be

Jan 1, 1943

By H. H. Reamer, B. H. Sage

Attempts have been made to predict the volumetric and phase behavior of naturally occurring hydrocarbon mix-turesl-6 but these methods have not been extended to the higher pressures and tem-peratures that are currently encountered in some producing formations. Furthermore, the methods of prediction at present avail-able have not been tested in a sufficient number of cases to ensure their applica-bility to all naturally occurring hydrocar-bon mixtures, even at the lower pressures and temperatures. For these reasons the behavior of a number of hydrocarbon mix-tures from a field in which the subsurface pressures are above 4500 lb. per sq. in.t and the temperatures are in the neighbor-hood of 250°F. was investigated. Method The objective of this program was to determine the volumetric behavior of ma-terial as it existed in the reservoir as a function of pressure, temperature and com-position. Strictly speaking, this cannot be accomplished in any simple fashion. How- ever, the variations in composition that are encountered within a producing reservoir may be approximated roughly by means of mixtures made up of two arbitrarily chosen constituents. Experience indicates that the liquid and gas phases from a high-pressure gas trap afford a simple source of material for this purpose. Throughout this discus-sion the samples of the gas phase and liquid phase from the production trap will be called the "trap-gas sample" and the "trap-liquid sample," respectively. The volumetric behavior of both of the trap samples was determined throughout the temperature interval between 100" and 250°F. at pressures up to 5000 lb. per sq. in. In addition, the behavior of eight different mixtures containing varying proportions of the two trap samples was studied throughout the same temperature and pressure intervals. The experimental results yielded information concerning the specific volume of the material as a function of pressure, temperature and the relative quantity of the trap samples. The relative amount of each of the paraffin hydrocarbons of lower molecular weight than n-hexane was determined for each of the trap samples. In addition, the specific weight, viscosity and average molecular weight of the hexanes-and-heavier fraction of the trap-liquid sample were determined as well as similar information for each of five fractions separated from this material by distillation. From these data the weight fractions of each of the components from methane through pentane were determined for the trap samples and eight systematically chosen mixtures. Materials The gas and liquid samples were obtained from the production trap of a well in the Rio Bravo field in California during the fall of 1939. Information concerning the condi- 70

Jan 1, 1941