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By Joseph Pogue

IT is well known that one of the cornerstones of economic theory is the so-called law of supply and demand, which, really, is a group of economic laws, one of which may be succinctly stated A rise in price tends, sooner or later, to increase supply. It is the fear that, in the case of petroleum, a limited' natural resource, a point will soon be reached when supply will not respond adequately to price advances, which in recent years has prompted a movement for oil conservation. This movement has lately taken concrete shape in the appointment of 'a Federal Oil Conservation Board by the President. An important aspect of the law of supply and demand is that the supply of any commodity, is not an entity per se, but is a factor of price. Supply, without the specification of, price, has no exact meaning; and, in practice supply cannot be divorced from considerations of price. Mathematically, supply may be expressed by the formula SP, which means that supply varies with price, just as the value of 10 raised to the x power varies with x. In its technical usage, supply is the, quantity of a commodity that is bought currently on the market at a given price. In the case of a natural resource, however, this quantity will eventually depend not alone on price but on the physical volume of the reserve that exists and that, in consequence, can respond to the stimulus of price. If this reserve is fixed in size, we must sooner or later reach a point where supply can no longer respond to price in the usual degree and a permanent shortage will develop which no advance in price can correct, except in so far as higher prices may curtail demand or improve the efficiency of utilization. This statement brings us to the examination of amore fundamental aspect of the law of supply and demand as applied to natural resources; namely, that natural-resource reserves are not fixed in size: just as the current supply of a natural-resource commodity is a function of price, so its reserve is likewise a resultant of price. Natural-resource reserves; therefore, have no exact meaning without the specification of price, and in practice their measurement. cannot be divorced from considerations of

Jan 3, 1925

By Frank R. Milliken

This paper is a running commentary on metallurgical problems and developments, stressing ilmenite flotation, since the start of operations five years ago, at the mill of National Lead Company, Titanium Division, MacIntyre Development, Tahawus, New York. In early 1941, when world conditions threatened to cut off the supply of ilmenite (obtained largely from India) to this country, the National Lead Company started to develop and bring into production their MacIntyre Development. This operation supplied the bulk of the ilmenite used during the war period for the manufacture of the much needed titanium pigments. MacIntyre Development is at Tahawus, New York, on the headwaters of the Hud- son River in the center of the scenic Adirondack Mountains. A general description of the operation was given in the Adirondack Issue of Mining and Metallurgy for November 1943. Operating tonnages and production have increased since 1943, however. Nearly 10,000 tons of.ore and waste is broken and loaded daily in the open-pit mine. About half of this tonnage is ore, from which is produced nearly 800 tons of ilmenite concentrate and 1600 tons of magnetite concentrate daily. Ore—types From an ore-dressing standpoint, there are five rather distinct ore types and two waste-rock types in the mine. The ore types are shown in Table I. The anorthosite waste is a coarse-grained white rock, largely labradorite feldspar. The gabbro waste is generally finer grained, and contains, in addition to feldspar, 35 to 75 pct iron silicates such as hornblende, in garnet and biotite. A minor mineral mineralogically, but important metallurgically, is apatite. A few calcite

Jan 1, 1949

By A. L. Field, P. H. Royster

Bureau of Mines Technical Paper 189 consists of a record of the scientific data obtained in the iron blast-furnace slag investigation which is reported in Technical Paper 187, "Slag Viscosity Tables for Blastfurnace Work." It includes a description of the method of preparing the synthetic melts, construction of an improved electric furnace, and refinements in laboratory methods of measurement. Only the general features of the work and the conclusions drawn from the experimental data can be given attention here. Silicates in the Liquid State In the manufacture of refractories, Portland cement, glass, and porcelain, and in pyrometallurgical operations, importance attaches to the behavior of-silicate compounds at temperatures beyond the range of common experience. This field of research has not been investigated as carefully as its scientific and industrial importance would seem to warrant. Probably the most important of the unsolved problems in the chernistry of silicates is the question of their stability in the liquid state. That little progress toward the solution of this problem has been made is not strange if there be borne in mind the difficulties attending experiments made at temperatures at which silicates become fluid, and the comparatively short time since it became possible to measure these temperatures. On the other 'hand, considerable progress has been made in the study of the compounds in the solid state because of the directness and simplicity of methods of optical examination. Important advances have been made by the Geophysical Laboratory at Washington in recent years. An extended study has been made there of saturated solutions representing a considerable number of binary and ternary systems of the more common refractory oxides. The methods

Jan 1, 1918

By C. A. Mitke

In the Southwest, mcchanical ventilation of metal mines has been receiving consideration for many years. The United Verde Copper Co., in Jerome, has used large mine fans for ventilation and fire-fighting purposes for at lcast 15 years, while the Copper Qucen Branch of the Phelps Dodge Corpn. commenced installing mechanical ventilation in its various divisions 10 years ago.' Since then, with few exceptions, every large mine in this part of the country has installed and put in operation a mechanical ventilating system. The properties of some of these companies consist of from two to six divisions, or separate mines, each of which requires an independent ventilating system. In other words, thirteen copper mining companies, with an aggregate tonnage, when operating at capacity, of approximately 50,000 tons a day, have installed mechanical ventilating systems in their mines. All these mines are within a radius of approximately 200 miles, which constitutes the largest copper-producing area in the world. The capacities of mechanical ventilating installations in these mines range from 100,000 to 300,000 cu. ft. of air per minute, depending on the size of the mine, character of the workings, tonnage produced, etc. The latter varies from 300 to 20,000 tons per day. The mines include both high- and low-grade deposits, the greatest depth of the former, at present, being approximately 2500 ft.; and of the latter, 1200 ft. The volumes of air at present being coursed through the mines are from 60,000 up to 225,000 cu. ft. of air per minute,which, in their relation to the undcrground working force, range from 200 to 800 cu. ft. of air per man, per minute. While not to be taken as criteria, these figures are indicative of the character of the ventilation furnished.

Jan 1, 1923

By C. A. Mitke

In the Southwest, mcchanical ventilation of metal mines has been receiving consideration for many years. The United Verde Copper Co., in Jerome, has used large mine fans for ventilation and fire-fighting purposes for at lcast 15 years, while the Copper Qucen Branch of the Phelps Dodge Corpn. commenced installing mechanical ventilation in its various divisions 10 years ago.' Since then, with few exceptions, every large mine in this part of the country has installed and put in operation a mechanical ventilating system. The properties of some of these companies consist of from two to six divisions, or separate mines, each of which requires an independent ventilating system. In other words, thirteen copper mining companies, with an aggregate tonnage, when operating at capacity, of approximately 50,000 tons a day, have installed mechanical ventilating systems in their mines. All these mines are within a radius of approximately 200 miles, which constitutes the largest copper-producing area in the world. The capacities of mechanical ventilating installations in these mines range from 100,000 to 300,000 cu. ft. of air per minute, depending on the size of the mine, character of the workings, tonnage produced, etc. The latter varies from 300 to 20,000 tons per day. The mines include both high- and low-grade deposits, the greatest depth of the former, at present, being approximately 2500 ft.; and of the latter, 1200 ft. The volumes of air at present being coursed through the mines are from 60,000 up to 225,000 cu. ft. of air per minute,which, in their relation to the undcrground working force, range from 200 to 800 cu. ft. of air per man, per minute. While not to be taken as criteria, these figures are indicative of the character of the ventilation furnished.

Jan 1, 1923

By F. P. Dewey

The first systematic attempt of the National Museum to gather material representing the economic geology and metallurgy of the country was made in connection with the Centennial Exhibition. The department may be considered as having originated then, althongh it was not formally inaugurated until December, 1882. Previous to the Centennial, all the illustrations of economic geology had been included in the mineral collection, and the illustrations of metallurgy were so very few that they had also been included with the minerals. When the museum began its collections for the Centennial, the subject of the mineral resources of tile United States was placed in the hands of Professor Wm. P. Blake, who was eminently fitted to undertake the work by his experience at various international exhibitions and his extensive acquaintance with the mining industry of the country. Professor Blake prepared a broad and exhaustive plan for this purpose, and the very large collection shown at Philadelphia was well calculated to set forth the vast mineral wealth of the country. The history of the department proper may conveniently be divided into three periods : first, the formative period, during which the Centennial material was mainly administered upon, ending Jnly 1, 1884, with the beginning of the preparation for the New Orleans Exposition; second, the New Orleans Exposition period, from July 1, 1884, to June 30, 1887, during which the collections for the New Orleans Exposition were made, exhibited at New Orleans, returned to Washington, and installed permanently in the museum; third, the southwest-court period, from July 1, 1887, to October 1, 1889, during which the collections were arranged in the southwest court of the museum.

Jan 1, 1891

By William Sharp

DISCOVERY of new ore in the Eureka district, Nevada, as a result of bold and persistent exploration based on a geologic interpretation of structure has recently aroused wide comment in mining circles. It may therefore be of interest to the profession to have a summary of the historical background and an account of the recent program of development. The mines of Eureka, discovered in the late 1860's, were the first important silverlead mines in the United States. They have a production record of more than fifty-one million dollars.1 After the ore bodies were apparently bottomed in the 1880's, repeated attempts to find new ore were unsuccessful until 1940, when a diamond-drill hole cut a 40-ft width of sulphide ore 1409 ft below the 841-ft level of the Locan shaft. The next hole cut 30 ft, of ore and three additional holes drilled in 1943 and 1944 showed the ore body to be continuous, Shaft sinking to reach and open up the ore body has been in progress since 1945. GEOLOGY Stratigraphy The ore in the Eureka district occurs in a series of Cambrian sediments which is exposed through a thickness of over 6000 ft. The stratigraphic column is as follows:2 [THICKNESS, FI ORDOVICIAN Pogonip limestone (upper part). Thin bedded limestone with some chert. UPPER CAMBRIAN: Pogonip limestone (lower part). Thin-bedded limestone (with shaly limestone and chert).... 425+ Dunderberg shale. Shale (clay and calcareous shale) and thin bedded limestone340+ Hamburg dolomite. Dolomite and limestonegoo+ MIDDLE CAMBRIAN: Secret Canyon shale. Shale and thin-bedded limestone1,035 Geddes limestone. Carbonaceous, flaggy limestone with some shale partings 335 MIDDLE (?) AND LOWER CAMBRIAN: Eldorado dolomite. Dolomite and limestone2,000 LOWER CAMBRIAN: Prospect Mountain quartzite. Quartzite with occasional inter calated conglomerate and shale 1,660+ The Prospect Mountain quartzite has been subdivided into two formations: Upper part, Pioche shale. Shale, quartzite with some intercalated limestone (Lower Cambrian fossils)-200 ft. Lower part, Prospect Mountain quart zite proper-I,460+ft. Total thickness6,695+] Much the most productive of these formations has been the Eldorado dolomite, which yielded more than $42,000,000 at Ruby Hill and an additional amount

Jan 1, 1947

Jan 1, 1905

By M. A. Steinberg, J. Wulff, R. Kamm

In a previous paper1 from this laboratory, the development of a lead grid method for exploring the distribution of strain and density within metal powder compacts was described. In that work thin lead foil with rectangular holes cut at regular intervals was inserted with the powder fill, the arrangement pressed and then radiographed to permit measurement of the deformation of the lead grid. Densities at each grid element obtained in this manner were plotted as a function of the die dimensions. From such plots it was found that the densest part of a compact pressed from one side (the top) is at the top outer region and the least dense at the bottom outer region of the specimen. The axial density maximum occurs more often nearer the bottom than at the top. As a result of such exploratory measurements, it appeared reasonable to conclude that variations in density could be attributed in the main to die wall friction. Thus compacts of large diameter appeared relatively uniform in density except where the die fill had been uneven. Finally it was found that lubrication of the finely finished die cavity contributed more to magnitude and uniformity of density within the compact than interparticle lubrication. Since publication of the above results, it was found that circular-hole grids could be more accurately made and, when deformed within the powder, more readily measured and analyzed. Much of the former work was repeated and new results which include the effect of lubrication, compact height, pressure, speed of pressing and vacuum pressing are reported in the present paper. Circular-hole Grids and Analyses OF Radiographs Commercial lead sheet 0.008 in. in thickness was used in all the work reported. The 0.0938-in. diam holes were punched in the sheet on 1/8-in. centers to an accuracy of 0.001 in. The finished grid used contained eight or more holes in a row and from I to 24 rows. The lead sheet was clamped between two pairs of brass strips bolted to a small milling machine table which was itself bolted to a bench in correct position near a vise which held the punch. Travel of the lead grid in two dimensions was controlled by two steel lead screws calibrated in 0.001-in. divisions. A stripper plate was used on the punch to avoid distortion of the lead foil. A high carbon-high chromium (chrocar) one-piece steel die was used throughout the work. The die cavity was 1.125 in. in diam and the clearance between plungers and die wall was 0.001 in. The die was also used for pressing from both ends with two long plungers. Finally, lapping of die and plungers gave a surface whose rms value On an Abbot profilometer was 5 micro-in. The die walls and plungers were, except where otherwise noted, lubricated with a stearic acid suspension in benzene. This was put on in multiple layers and allowed to dry before filling the die.

Jan 1, 1949

By J. Lohrenz, C. R. Clark, B. G. Bray

Procedures to calculate the viscosities of in situ reservoir gases and liquids from their composition have been developed and evaluated. Given a composition expressed in methane through heptanes-plus, hydrogen sulfide, nitrogen and carbon dioxide together with the molecular weight and specific gravity of the heptanes-plus fraction, the procedures are capable of calculating the viscosity of the gas or liquid at the desired temperature and pressure. The procedure for reservoir liquids was developed using the residual viscosity concept and the theory of corresponding states, and was evaluated by comparing experimental and calculated results for 260 different reservoir oils ranging from black to highly volatile. The average absolute deviation was 16 per cent. This is the first known procedure for calculating the viscosity of reservoir liquids from their compositions as normally available, i.e., including the heptanes-plus fraction. The procedure for reservoir gases uses a sequence of previously published correlations. Evaluation of the procedure was accomplished by comparison of 300 calculated and experimental viscosities for high-pressure gar mixtures in the literature. The average absolute deviation was 4 per cent. The calculations are useful for (I) determining viscosities in compositional material balance computations and (2) predicting the viscosity decrease which occurs when gases, LPG, or carbon dioxide dissolve in reservoir oils. INTRODUCTION Methods to predict viscosities of reservoir fluids from the normally available field-measured variables have been presented. Beal,1 Standing,2 and Chew and Connally3 orrelated oil viscosities with temperature, pressure, oil gravity and gas-oil ratio. Carr, Kobayashi, and Burrows4 and Katz et al.5 have presented correlations for reservoir gas viscosities as a function of temperature, pressure and gas gravity. Lie all intensive physical properties, viscosity is completely described by the following function: Eq. 1 simply states that viscosity is a function of pressure, temperature and composition. These previous correlations1- hay be viewed as modifications of Eq. 1, wherein one assumes more simple functions may be used. The assumptions are practical, because the composition is frequently not known. Further, the assumptions are sufficiently valid so that these correlations are frequently used for reservoir engineering computations. In compositional material balance"' computations, the compositions of the reservoir gases and oils are known. The calculation of the viscosities of these fluids using this composition information is required for a true and complete compositional material balance. For reservoir gases, Carr, Kobayashi and Burrows4 have presented a suitable compositional correlation. For reservoir oils, no correlation is available, and data from reservoir fluid analyses have been used7-9 for compositional material balance calculations.* From a theoretical point of view, this is entirely invalid. The reservoir fluid analysis, whether flash, differential, or other process, does not duplicate the compositions which occur during the actual reservoir depletion process, therefore the viscosities measured during reservoir fluid analysis are not those which occur in the reservoir. From a practical point of view, the "error" of using viscosities from reservoir fluid analysis is of varying and unknown significance. One can say qualitatively that the error is greatest where compositional effects are greatest, i.e., for volatile oil and gas condensate reservoirs and pressure maintenance operations. The first requirement to obtain a quantitative estimate of the significance of the error is to develop a reliable compositional correlation for the viscmities of reservoir oils. No such correlation has been available. Consistent with this requirement, the objective of this study was to develop a procedure to predict the viscosity of reservoir fluids from their compositions. Normally, the compositions of reservoir fluids are available expressed as mole fractions of hydrogen sulfide, nitrogen, carbon dioxide and the hydrocarbons methane through the heptane-plus fraction, with the average molecular weight and specific gravity of the latter. The final correlation was to use the composition in this form. While the more challenging objective of the study was the development of a correlation for the viscosities of reservoir oils, the viscosities of reservoir gases were also studied. The end result of the study was a procedure to calculate the viscosities of reservoir gases and liquids suitable

Jan 1, 1965

Jan 1, 1892

By Robert Glass Cleland

THE DEATH of William E. Dodge occurred at a time when, all unwittingly, the company in which he had so long been the dominant factor was about to break with its old practices, its old traditions, its old interests, and transfer its major activities three fourths of the way across the continent and engage in an enterprise that differed almost as much from the original Phelps Dodge undertakings as the rough, arid mountains of the new region differed from the green hills and valleys of New England. To understand the effect of this transformation upon the fortunes of Phelps Dodge, one must change the setting of the present narrative from the familiar locale of the Atlantic seaboard to the land of "distance, silence, and solitude," that men called Arizona. In 1880 that Territory was one of the last frontiers of the Old West. To the Spaniards it had been a land of mystery and fable, the limit of the King's settlements, the far edge of the rim of Christendom. Through it Coronado; in a vain effort to find the fabulous Cities of Cibola, had led "the most brilliant company ever assembled in the Indies to go in search of new lands." Below its southern border, Father Kino, the "steel-thewed" Jesuit described by his

Jan 1, 1952

By E. A. Nesbitt

A new permanent-magnet material has been developed with unusual mechanical as well as magnetic properties. Specimens that have been cast or subjected to a small amount of hot reduction by rolling or swaging may be machined, punched, tapped or drilled. The composition range of the alloys is 30 to 52 per cent iron, 36 to 62 per cent cobalt and 4 to 16 per cent vanadium. After being either quenched, annealed or given the usual cold finishing passes and then heated for 2 hr. at 600°C., such materials have a magnetic energy product of 1.0 X 106 gauss-oersteds. This product is equivalent to that of the well-known Honda steel (36 per cent Co, 4W, 2 Cr, 0.8 C. 0.3 Mn, balance Fe). Material handled in the manner just described does not depend on cold-working for its magnetic properties, and is known as Vicalloy I. The preferred composition for Vicalloy I is 38.5 per cent iron, 52 per cent cobalt and 9.5 per cent vanadium. When the alloys are first hot-worked, then considerably reduced in area by cold-swaging, drawing or groove rolling and then heat-treated, the magnetic energy product measured in the direction of previous extension is increased to 2.0 to 3.5 X 106 gauss-oersteds. These higher values have been obtained only after cold reductions in area of 75 to 95 per cent. Material handled in this manner is known as Vicalloy II and the preferred composi-

Jan 1, 1947

By E. A. Nesbitt

A new permanent-magnet material has been developed with unusual mechanical as well as magnetic properties. Specimens that have been cast or subjected to a small amount of hot reduction by rolling or swaging may be machined, punched, tapped or drilled. The composition range of the alloys is 30 to 52 per cent iron, 36 to 62 per cent cobalt and 4 to 16 per cent vanadium. After being either quenched, annealed or given the usual cold finishing passes and then heated for 2 hr. at 600°C., such materials have a magnetic energy product of 1.0 X 106 gauss-oersteds. This product is equivalent to that of the well-known Honda steel (36 per cent Co, 4W, 2 Cr, 0.8 C. 0.3 Mn, balance Fe). Material handled in the manner just described does not depend on cold-working for its magnetic properties, and is known as Vicalloy I. The preferred composition for Vicalloy I is 38.5 per cent iron, 52 per cent cobalt and 9.5 per cent vanadium. When the alloys are first hot-worked, then considerably reduced in area by cold-swaging, drawing or groove rolling and then heat-treated, the magnetic energy product measured in the direction of previous extension is increased to 2.0 to 3.5 X 106 gauss-oersteds. These higher values have been obtained only after cold reductions in area of 75 to 95 per cent. Material handled in this manner is known as Vicalloy II and the preferred composi-

Jan 1, 1947

By W. B. Agocs

IN August 1954 a low altitude test geophysical survey was made in the Green Pond area of Morris County, New Jersey, with a Gulf Research and Development Co. Model II total magnetic field variation magnetometer mounted in a Sikorsky S-55 helicopter. The test was made in this area to compare the results of a high precision, very low altitude magnetometer survey with an existing ground magnetic survey in this area having known magnetite concentrations, so that the method could be used in areas of difficult access for the detailing of airborne magnetometer anomalies of interest in place of ground surveys. The load capacity of the Sikorsky S-55 permitted installation of a recording scintillation counter so that a radioactivity survey would be made simultaneously with the magnetometer survey. The area surveyed is located at approximately 41°00'N and 74o28'W, just south and east of the town of Green Pond, N. J. The outstanding topographic feature of the region is Copperas Mountain, a well defined ridge, maximum elevation 1222 ft, which runs the entire length of the survey. The lowest point in the survey, 810 ft, is in the extreme eastern corner. Topography of the area is shown in Fig. 1. The three major rock units outcropping in the area are all metamorphic: the Pochuck gneiss, which has been divided into two metamorphic facies; the Byram gneiss; and the Green Pond conglomerate. The relative ages of the Pochuck and Byram formations, both pre-Cambrian, are in doubt, but it is believed that the Pochuck is the older of the two.' The Green Pond conglomerate is Silurian.' Distribution of the outcrops and mine locations is shown in Fig. 1. Two facies of the Pochuck gneiss can be distinguished locally—the Copperas Mountain and Kitchell members. The Copperas Mountain member is a hornblende gneiss, and all the mines and prospects in the area are in this unit. The Kitchell is a quartz-plagioclase feldspar gneiss. The Byram gneiss is a relatively nonresistant valley formation which is high in the potash feldspar. The Green Pond conglomerate is a well indurated quartzite-conglomerate which forms the Copperas Mountain and the Green Pond Mountain's ridge to the north. It overlies the gneisses with a strong angular discordance that may be a fault. The geologic structure of the Green Pond area is relatively uncomplicated. The foliation planes of the gneisses dip steeply to the southeast, and the Green Pond conglomerate dips steeply to the northwest. Additional faulting in the area is indicated at the contact between the Kitchell member of the Pochuck and the Byram along the base of the topographic spur extending to the southeast from Copperas Mountain. The magnetite mines of Pardee, Winter, Davenport, Green Pond, Copperas, and the Bancroft shaft are described by Bayleyl and Stampe2.' The ore is in the Copperas Mountain member of the Pochuck gneiss. The magnetite veins are 10 to 50 ft wide and up to 300 ft long, dipping to the southeast at angles ranging from 40" to 75". The locations of these mines are shown in Fig. 1. Dip Needle Survey: The dip needle survey shown in Fig. 2 was taken from a U. S. Bureau of Mines Report of Investigations." The figure numbers below the local, individual map area outlines refer to the figures in the aforementioned reports which were not contoured. The area of the dip needle survey was confined almost exclusively to the outcrops of the Pochuck gneiss. The separation between survey profiles was 100 ft and the distance between stations on the profiles was 25 ft in highly anomalous zones to 100 ft in magnetically flat areas. A total of 16 1/2 miles of traverse was surveyed over an area of approximately 1/2 sq mile with 2050 stations. The magnitude of the magnetic anomalies is difficult to determine due to the lack of information concerning the type of dip needle used and the procedure followed in making the dip needle survey. This latter would include the method of "zeroing" the dip needle and the procedure of reading at the stations, whether on the swing or statically. Calibrations made of the Gurley dip needle, Lake Superior type, show a static sensitivity of 385 gamma per degree in the range from —25" to +35o, corresponding to a variation in the total field of —9600 gamma to +13500 gamma in a total field of 57000 gamma, inclination 72". The sensitivity increases to 16 gamma per degree from a deflection of 60" to 76", and from 76" to 172" the sensitivity decreases continuously to a low of 260 gamma per degree. From the above it may be seen that it is difficult to assign an arbitrary sensitivity for the dip needle used on this survey. However, an estimated value of 100 gamma per degree may be assigned. On this basis, the majority of the magnetic anomalies, whose deviation is +20°, would be 2000 gamma. Locally, west and northwest of the Pardee mine the magnetic anomaly is +50°, or 5000 gamma; in the Green Pond mine area deviations of +75" are observed that would correspond to anomalies of 7500 gamma. The areal extent and width of the dip needle magnetic anomalies is comparable to profile and station spacing. Hence it is concluded that part of the detail may be due to control, and the probable cause of the magnetic anomalies is at or near surface exposures of magnetite concentrations in the form of veinlets and disseminations whose locations correspond to the local magnetic anomalies. On the basis of the magnetics, none of the magnetite concentra-

Jan 1, 1956

By Donald L. Katz, Leslie J. Noaker

Experimental data are presented for hydrate formation conditions for mixtures of hydrogen sulfide and methane. Vapor-solid equilibrium constants for hydrogen sulfide are also presented. Equilibrium constants, defined here as the ratio of the mole fraction of hydrogen sulfide in the vapor phase (dry basis) to the mole fraction of hydrogen sulfide in the solid phase (dry basis), were calculated using the vapor-solid equilibrium constants for methane presented in an earlier paper. The conditions at which a natural gas will form gas hydrates with water may be computed from its composition, when hydrogen sulfide is present in addition to carbon dioxide and the paraffin hydrocarbons. INTRODUCTION Many gases are known to form solid hydrates in the presence of liquid water at temperatures above 32°F. This hydrate formation is of importance to the natural gas industry inasmuch as most of the constituents found in natural gases will form hydrates. The attention of the industry was called to hydrates by Hammer-schmidtl0 in 1934. A number of papers have been written giving the temperatures and pressures at which these hydrates will form3,4,5,6,7,8,9,10,13,14,15,18,19 and a bibliography on the subject has been compiled13. Deaton and Frost4,5,6,7,8 report work for various pure gases and for some natural gases. Katz and co-workers3,4,13,14,18,19 have reported data for various gases at high pressure. They developed a method of predicting conditions for hydrate formation from equilibrium constants3,19 and from gab gravity." The effects of anti-freeze agents on the formation of hydrogen sulfide hydrate were reported by Bond and Nelson.' The hydrogen sulfide-water system, including hydrate, has been the subject of recent investigation by Sage and co-workers." Mixtures of hydrates behave as solid solutions and an equilibrium exists between the vapor phase and the solid phase that appears to be comparable to the equilibrium between vapor and liquid phases.3,10 By means of the vapor-solid equilibrium constants which have been published for methane, ethane, propane, iso-butane, and carbon dioxidel6 it is possible to determine the temperature and pressure at which hydrates will form for a specific gas mixture when water is present. Hydrogen sulfide which is frequently found in natural gases has a very strong tendency to form hydrate and must enter the solid solution when present in a natural gas forming a hydrate. To determine the effect of hydrogen sulfide when computing the conditions for gas hydrate formation, it is necessary to have the equilibrium constant giving the ratio of the concentration of hydrogen sulfide in the gas phase to the concentration in the solid phase. This paper presents data on hydrate formation for mixtures of hydrogen sulfide and methane and presents the equilibrium constants which were calculated from these data. EXPERIMENTAL PROCEDURE The apparatus used to determine the conditions of hydrate formation for the methane-hydrogen sulfide system was similar to that employed by previous investigators.3,18,19 A charge gas cylinder was used to supply the hydrogen sulfide-methane mixtures, called the charge gas, and to supply the pressure up to 1.000 psia. This

Jan 1, 1955

PRESIDENT WILLIAM L. SAUNDERS,1 NEW YORK, N. Y. PAST PRESIDENTS CHARLES F. RAID;1 NEW YORK N. Y. BENJAMIN B. THAYER,2 NEW YORK, N. Y. FIRST VICE-PRESIDENT PHILIP N. MOORE,1 ST. Louis, Mo. TREASURER GEORGE C. STONE,1 NEW YORK, N. Y. SECRETARY EMERITUS ROSSITER W. RAYMOND NEW YORK, N. Y. SECRETARY BRADLEY STOUGHTON, NEW YORK, N. Y.

Jan 3, 1915

Jan 1, 1902

[EXECUTIVE COMMITTEE OF THE BOARD OF DIRECTORS LOUIS S. CATES, Chairman DONALD H. NCLAUGHLIN, Vice-Chairman JOHN L. CHRISTIE JOHN R. SUMAN CLYDE E. WEED]

Jan 1, 1946

Aaby, Alton O , (S'47) Univ of Minnesota, Mimeapolis, Minn Aaby, Waldo S , (S?48) Univ of Minnesota, Minneapolis Minn Aalde, Kaare, (S'48) Univ of Nevada, Reno, Nev Aaring, Floyd D , (S'48) Univ of Oklahoma, Nor man, Oka Aaronson, Hubert I , (S'47) Carnegie Inst of Technology, Pittsburgh, Pa Abbott, Peyton Osborn, (S'46) 1502 Westover, Austin 21, Texas Abel, Malcolm D , (S'47) Univ of Texas, Austin, Texas Aberg, Richard S , (S'47) Univ of Minnesota, Minneipolis, Minn Abrahamson, Guy C , (S'43) 420 W Dennis St , Wilmington, Calif Abrahao, Benjamin, (S'46) Escola Politeenica da Unnersidade, de Sin Piulo, Braizil Achter, Meyer R , (S'46) Carnegie Inst of Tech , Pittsburgh, Pa

Jan 1, 1952