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By Wido Tilmann

13.6-1. Importance. In Germany there are large tertiary brown coal reserves, most of which are located close to the surface. Therefore, brown coal has been recovered for many years by means of opencast methods. By utilizing a high degree of technology, a rational operation has been achieved, and as a result, the mining techniques have become renowned all over the world. After the war, all the dredgers and overburden spreaders, as well as the means of conveyance, had to be redeveloped for adapting this equipment to the changing conditions of the deposits. Numerous auxiliary machines were adopted from the American earth moving industry and altered according to the different requirements. As a result of such technical developments, the output per man and per shift was increased remarkably in spite of the deterioration of the geological conditions. In the whole of Germany, the total reserves of brown coal amount to 100 billion metric tons, of which 60 billion tons are situated in the Federal Republic of Germany. In the latter area, 8.5 billion tons will be recover- able by opencast means, of which 3.5 billion tons are already developed. The annual output reached 102 million tons in 1965. This total figure comes from four different mining districts: Rhineland, Helmstedt (town at the border of the Soviet occupied zone), Hesse, and Bavaria. The production figures (1965) are as follows: [ ]

Jan 1, 1968

In late May, at its final session in Nairobi, Kenya, the UN Conference on Trade and Development (UNCTAD) narrowly rejected the US proposal for a new International Resources Bank suggested by Secretary of State Henry Kissinger. The proposal was defeated by a roll-call vote of 33 to 31, with most of the nay votes cast by communist countries, and with 89 of the less-developed countries abstaining or absent.

Jan 7, 1976

By Arne Westgren

ONLY in exceptional cases can the ordinary methods of chemistry be used for determining the constitution of compound metallic substances. Recourse has therefore been taken to special methods, the main expedients of which are, as we know, thermal analysis and metal microscopy. To these may be added-though more accessory-the determination of electric conductivity, specific volume, hardness or other properties. The information obtained by these methods has been compiled in equilibrium diagrams. Naturally, the technically most important alloys, such as steel, bronze and some others, have been subjected to very close study, and many investigators have devoted themselves to the solving of their problems of constitution. The equilibrium diagrams of these systems are therefore known today with a comparatively high degree of accuracy, even though it must be admitted that many details regarding their transformation reactions still remain to be completely explained. The equilibrium diagrams of the other alloys as a rule have not been determined so accurately. Most of them are based only on approximate determinations of the homogeneity ranges of the various phases. Thus extensive, detailed studies remain before these diagrams may be considered as established. Unfortunately, it must also be admitted that many of the alloy diagrams given in the present handbooks are as a whole very dubious. As a matter of fact, many of them may really only be viewed as the results of rather superficial, orientating investigations. In fact, there also seems to be a general opinion prevailing in our day that much work still remains to be done before the equilibrium conditions of the alloys may be considered as fully explained. At present, in almost all institutes for research on metals, as well as in many university laboratories, investigations to this effect are being carried out. As a rule, the classical methods of metallography, the thermal analysis and metal microscopy are applied.

Jan 1, 1931

By A. M. Ross

DEURING the past year the uranium milling industry has seen the installation and initial operation of solvent extraction circuits in the Climax Uranium Co. mill at Grand Junction, Colo.; the Kerr-McGee Oil Industries mill at Shiprock, N. M.; and the AEC pilot plant at Grand Junction, operated by National Lead Co. Inc. The Vitro Uranium Co. mill in Salt Lake City is converting to solvent extraction, and the new Union Carbide Nuclear Co. mill to be constructed at Rifle, Colo., will also employ this method. Solvent extraction circuits will be incorporated in two mills now under construction -the Texas Zinc Minerals Co. mill at Mexican Hat, Utah, and the Gunnison Mining Co. mill at Gunnison, Colo. In Canada the expansion of the Eldorado mill at Port Radium includes installation of a solvent extraction circuit. Solvent Extraction Process: In simplest terms, the organic solvent is mixed with leach liquor and then the organic and aqueous phases are allowed to separate. By this contact the solvent selectively extracts uranium from the liquor, leaving a raffinate, or barren leach liquor, which may be discarded. The pregnant solvent is stripped of its uranium by con- tact with a stripping solution, such as aqueous sodium carbonate, which has a greater affinity for uranium than the solvent does. The barren solvent from the stripping step is available for further leach liquor extraction, and the pregnant stripping solution, which usually contains 30 to 60 g U3O8 per liter, is ready for precipitation of a final product, or uranium concentrate.

Jan 9, 1957

By J. R. Ross, J. B. Rosenbaum

Bureau of Mines research has resulted in the development of fluid- bed ion-exchange columns for recovering uranium from slime pulps. In pilot plant tests, slime slurries containing up to 6 percent solids were processed at flow rates of 10 gallons per square foot per minute with high uranium recoveries and efficient resin loadings. Uranium was effectively eluted in a laboratory fluid-bed elution column at eluate-to-resin ratios of less than 5:1 and eluate flow rates of 3 gallons per square foot per minute. Construction costs of mills using these improved ion exchange techniques are estimated to be 25 percent less than for mills using solvent extraction of clear solutions. For mills having a capacity of 2,000 to 2,500 tons of ore per day, the saving would be in the range of $2.5 million. In addition, a saving of about $0.80 per ton of ore in total operating costs is indicated.

Jan 1, 1973

On the following pages are abstracts of papers published by the Institute during the year 1936 as TECHNICAL PUBLICATIONS and CONTRIBUTIONS, papers in bound volumes appearing for the first time, and papers in MINING AND METALLURGY For abstracts of papers that appeared in bound volumes in 1936 but that were published as TECHNICAL PUBLICATIONS in 1935, see the YEAR BOOK dated January 1936.

Jan 1, 1937

By C. Dinis da Gama

In mining, all unit operations are closely interrelated, and the results of blasting are probably the key factor within that sequence. The drilling program prior to blasting is just as dependent upon the desired rock fragmentation as are the loading, hauling, and mechanical crushing operations which are economically and technically influenced by the results of blasting, namely, the size and scatter of the product. What is known today as optimum blasting is the process of designing a blast in order to obtain a certain degree of fragmentation so that overall mining costs are minimized. Applying this criterion often results in a different program than when an individual blasting pattern is chosen only on the basis of the lowest operational cost for that pattern, disregarding what comes before or after the blast. [Fig. 1] shows the characteristic variation of mining unit costs with the degree of fragmentation, or the maximum size of blocks obtained from blasting. From the figure, it can be seen that optimum breakage must correspond to the lowest total costs, but reducing drilling-blasting costs only does not achieve such an optimum solution. Methods of designing surface or underground blasting operations should comply with the optimization criterion, but this compliance is feasible only if a detailed mining system analysis is available. Therefore, predictions of costs of loading, transporting, and mechanical breakage of ore as a function of its size will define a narrow range of variation for drilling and blasting parameters in order to get the minimum total costs.

Jan 1, 1972

By J. E. Flinn, E. R. Gilbert

Recently, Green reported some high-temperature, 0.60 to 0.89 T3, creep results on unalloyed tantalum. From his study he determined an activation energy of 114 kcal per mole for steady-state creep using the T, differential-temperature method25 for testing. He accounted for the difference between this value and 110 kcal per mole for self-diffusion by the temperature dependence of the elastic modulus, 4 kcal per mole. This reported activation energy is in apparent disagreement with that which can be determined from Green's isothermal data, which we have plotted as log creep rate vs 1/T in Fig. 15. From this figure, it appears that there are two activation energies of -185 kcal per mole at the higher temperatures and -75 kcal per mole at the lower temperatures. It is not obvious that the data can be fitted to a straight line corresponding to an activation energy of 114 kcal per mole. One is led to two possible conclusions regarding Green's study: there are two discrete processes controlling the creep rate from 0.60 to 0.89 Tm or the apparent activation energy is not discrete but continuously increases with increasing temperature. The former speculation would be in closer agreement with the high-temperature creep behavior of tungsten.28 The apparent disagreement between the activation energies determined by the AT and isothermal methods certainly suggests that further study on the high-temperature creep of tantalum is needed.

Jan 1, 1967

By F. C. Blare

THE best method for the estimation of copper in ores and secondary products is that proposed by Dr. Steinbeck* for the award offered by the Mansfeld'schen Ober-Berg-und Hutten-Direction. It is based upon the decolorization of the blue ammonia solution of copper by potassic cyanide,† It is necessary for the accurate estimation of copper in arsenides that the arsenic be separated from the copper before the ammonia solution is made. The presence of a notable amount of arsenic renders the titration by potassic cyanide inaccurate, the end reaction being obscured by the appearance of a yellowish-green tint towards the end of the titration. The change of the color of the ammonia solution from blue to the tint caused by the presence of arsenic cannot be used for an end reaction, for the intensity and quick appearance of the latter-color depend upon the amount of arsenic present in the solution. In the analysis of speise, the method of separating the copper by an oxidizing and reducing treatment in the muffle, to volatilize the arsenic, gives poor results, and there may easily be some loss of the weighed sample. The separation of the precipitated sulphides of arsenic and copper by treating with sodic sulphide, gives good results, but the process is tedious. I have used the two following methods, which are simpler and more expeditious than those mentioned, with good results. * Fresenius, Zeitschrift Air Anal. Chemie., viii, 1. †First noted by Parkes in the Mining Journal for 1861.

Jan 1, 1881

By Philip McKenna

WHEN a new material becomes available to industry, it is useful to describe its properties as a guide to its most effective application; and when the new material may be produced in compositions having a series of graded properties, tests to select the combination of properties best adapted for various uses are helpful. The class of materials to be con-sidered in this paper are hard tool materials produced by processes of powder metallurgy from hard carbide constituents and various matrices of iron, nickel or cobalt, or alloys of them with tungsten, or tungsten and carbon. The customary use of carbide hard alloys is for metal-cutting tools; although wire-drawing dies, lathe centers, follow rests, grinding rests, burnishers, rolls, extrusion dies, measuring gauges and micrometers, and a number of other tools are also made with these hard alloys as the essen-tial wear-resisting parts. The properties and tests to be considered are those affecting these uses. In the development of tool, materials since the industrial revolution we have had carbon tool steels, Mushet steel, high-speed steels, stellites, and now cemented carbide compositions. For an understanding of the latter category of materials their properties and uses relative to the older and more familiar tool materials will be considered.

Jan 1, 1938

By Albert D. Brokaw

The accompanying charts are presented to extend and improve a chart published under the title "A Chart to Provide Approximate Correction for Temperature and Deviation from Boyle's Law."' The applicability of this earlier chart was limited by the fact that it was based on the work of Burke and Keyes² and Kvalnes and Gaddy3 whose experiments were conducted with pure methane, the adjustments suggested for natural gases of higher specific gravity were unsatisfactory except within limited ranges of temperatures and pressures, and precise interpolation was difficult. The extensive work of G. G. Brown, D. L. Katz and their associates on the heavier natural gases has provided better bases for the needed corrections, and the present charts. which are based largely on their work, are intended to simplify the computations involved. The design of the charts has been changed by plotting temperatures as a function of pressure and correction factor, on a semilogarithmic or "ratio" grid, which gives fairly even spacing of the graphs and simplifies interpolation. Charts have been prepared for natural gas with specific gravities of .60, .65, .70, .75 and .80. The standard computation for use in estimating the quantity of gas in a reservoir may be expressed as follows: _ PA X 520 X VR ZT where: Q is the volume of gas at 60°F and one atmosphere pressure PA is the absolute formation pressure in atmospheres

Jan 1, 1949

By Albert D. Brokaw

The accompanying charts are presented to extend and improve a chart published under the title "A Chart to Provide Approximate Correction for Temperature and Deviation from Boyle's Law."' The applicability of this earlier chart was limited by the fact that it was based on the work of Burke and Keyes² and Kvalnes and Gaddy3 whose experiments were conducted with pure methane, the adjustments suggested for natural gases of higher specific gravity were unsatisfactory except within limited ranges of temperatures and pressures, and precise interpolation was difficult. The extensive work of G. G. Brown, D. L. Katz and their associates on the heavier natural gases has provided better bases for the needed corrections, and the present charts. which are based largely on their work, are intended to simplify the computations involved. The design of the charts has been changed by plotting temperatures as a function of pressure and correction factor, on a semilogarithmic or "ratio" grid, which gives fairly even spacing of the graphs and simplifies interpolation. Charts have been prepared for natural gas with specific gravities of .60, .65, .70, .75 and .80. The standard computation for use in estimating the quantity of gas in a reservoir may be expressed as follows: _ PA X 520 X VR ZT where: Q is the volume of gas at 60°F and one atmosphere pressure PA is the absolute formation pressure in atmospheres

Jan 1, 1949

By Paul G. Shewmon

The migration of slightly solzrhle spherical particles through a solid under the infllrence of a temperature gradient is analylzed for the cases of various transport mechanisms. It is shown that the variation of the velocity of the particles with radius, r, depends on the dominant mechanism of matter transport around or through the inclusion. Thus the velocity varies as r-1 jor surface-dijf1~sion controlled migratzon. is independent of r for volume diffusion in either phase, and varies as if the rate is determined by an interfacial reaction (n is the order of the interfacia1 reaction). These same results hold tor the migration of a cvlinder of length much greater than its radius. and .for other types of potential gradients, e.g., an electrical field. These equations are combined with recent electron-microscopic ohservations to show that the rate of migratzolz of small helium-silled bubbles through copper is determined by surface diffusion of the metal atoms. With these equations and the temperature gradients attainahle in an electron-microscope joil, the dominant transpar/ mechanism (or any migrating pnrtzclos can he determined. AS a result of fission, rare-gas atoms are created in the hot fuel element of a nuclear reactor. These insoluble atoms precipitate to form bubbles of the gas in the fuel. The subsequent migration and coalescence of these bubbles is thought to play a dominant role in the swelling of fuel elements which in turn can limit the fuel-element life. As a result of this practical problem and because of the relative simplicity of the system, workers in several laboratories have imbedded rare-gas atoms in metals with the aid of an accelerator and studied the formation and behavior of the bubbles that form on annealing. Recently Barnes and Mazey have studied the migration of such helium-filled bubbles in copper foils using the electron microscope and the temperature gradient that can be induced in the foil by the electron beam. They found that the smaller bubbles moved faster than the larger ones. It is shown below that, if this is true, the rate-controlling step in their migration is surface diffusion of metal atoms instead of volume diffusion, vapor transport, or an interfacial reaction. The analysis given is in no way limited to gaseous inclusions so the variation of velocity with particle size for any relatively insoluble precipitate particles could be used to obtain information about the relative importance of surface diffusion, volume diffusion, and interfacial reaction in such two-phase systems. VOID MIGRATION IN A TEMPERATURE-GRADIENT ANALYSIS Barnes' studies indicate that helium does not dissolve or diffuse in metals to a measurable extent, so that when the voids move they must do so through the movement of metal atoms from the leading to the trailing sides of the void.' Thus voids might move by surface diffusion, diffusion of vacancies in the surrounding lattice, or vapor transport. We consider first the case of flow by surface diffusion alone. We assume that there is a force, in the sense of irreversible thermodynamics, tending to move the atoms around the bubble in a given direction. We designate this direction as the x axis and the force per atom as Fa. The net rate of flow of atoms from one side of the bubble to the other, under the influence of this force, is the surface flux, Js, times the cross-sectional area available for flow, A,. A, is taken as the circumference times the thickness of the high-diffusivity surface layer 6. Thus where 51 is the atomic volume. For bubbles to advance a distance dx, a volume equal to nr : dx must flow around the void so that The minus sign enters because the bubble moves in the direction opposite to that of the force on the atoms. Equations for volume diffusion and diffusion through the vapor can be obtained in the same manner. For vapor transport we have Ag = and the ratio of the densities of metal atoms in the gas and the solid (pg/pl) enters so that

Jan 1, 1964

By John A. Prof. Church

ONE of the most striking phenomena connected with the mines on the Comstock lode is the extreme heat encountered in the lower levels. This heat is not due to the burning of candles, heat of the men, and decomposition of timbers, all intensified by bad ventilation, as was the case nearer the surface. It proceeds from the rock, which maintains constantly a temperature very much higher than the average of the atmosphere in Nevada. The heat of these mines is a matter of more than usual interest, for they are the only hot ones now worked in the United States, and both in the present temperature encountered and in the increase which is to be expected as greater depths are reached, they appear to surpass any foreign mines of which we have a record. Hot mines are known also in other countries, as in the tin and copper lodes of Wales, where one of the veins worked by the United Mines is known as the hot lode. It has springs which discharge water at a temperature of 116° Fahrenheit, the depth being 220 fathoms, or 1320 feet. The heat of the air in these workings is given at 100° to 113° Fahrenheit. The air is bad, and the heat in the drifts seems to be traceable to defective ventilation rather than to the real necessities of the case. Air is supplied through a small pipe, and is drawn from a place where the temperature is 95° Fahrenheit. Under such circumstances it is not surprising to read that in this hot mine the air is hotter than the rock, a state of things which I have never observed in the Comstock. Other mines have been reported to the British Coal Committee as having temperatures of 106° Fahrenheit and thereabouts, but the only positive comparisons that are available at this writing are the following, all from Cornish mines * Read by permission of Lieut. Geo. M. Wheeler, Corps of Enginerrs, U. S. Arm J, in charge of U. S. Geographical and Geological Surveys, west of the 100th meridian.

Jan 1, 1879

By O. C. Wheeler

The production of oil in Colombia during 1933 was at the lowest level since the completion of the loop of the Andian pipe line in 1927. The commercial production amounted to 13,157,641 bbl., all of which was produced from the Infantas and La Cira structures of the Tropical Oil Company. One of the most important developments was the discovery of what may be commercial production on the Colombian Petroleum (Gulf) Company's Tarra anticline on the Barco Concession in eastern Colombia near the Venezuelan border. This promises to become the second commercially productive area developed in Colombia and, perhaps, one of major importance. Applications made in 1931 for concessions under the new Colombian petroleum law were ratified covering the Putana application of the Tropical Oil Co. and others of local Colombian and French interests west of the Carare River. On none of these concessions has any development work yet been initiated. South American Gulf Oil Company The following information covering the activities of the South American Gulf Oil Co. was furnished by E. S. Bleecker, chief geologist of the company. Magdalena Valley.—No development work was undertaken during the year either on the Valenzuela property acquired from the Colombian Syndicate or on the lands obtained from the Leonard Oil Development Co. near the Sogamoso River. The Valenzuela property was relinquished and a portion of the material was removed therefrom to the Leonard property near by. Colombian Petroleum Co.—The Colombian Petroleum Co., controlled by the Gulf interests, pursued an active development campaign on the Chaux-Folsom or so-called Barco Concession in the Department of North Santander. The drilling of the first well was begun early in the year on the north Petrolea dome of the Tarra anticline and at 490 ft. a heavy flow of oil, gas and salt water was encountered. On blowing in unexpectedly, the well caught fire, and after being extinguished was controlled only by pumping large quantities of cement into the formation and plugging the well. The drilling of the second test, No. 1-A, approximately one kilo-

Jan 1, 1934

By A. J. Nicol

Field experience in uranium has shown it is most economical to ram through a drilling program to obtain maximum footage per drill hour. Drift surveys can then determine the course of the holes. Using this method is generally cheaper than paying the additional cost involved in using the drilling technique and equipment necessary to maintain straight holes. Factors Affecting Direction of Bit Travel: In all rotary-drilled holes there is an interplay of forces or conditions affecting the direction of bit travel. Rarely is a straight vertical hole obtained. One of the major factors is weight on a drill string. In looking at a joint of drill stem it is hard to imagine its being quite flexible, but flexing of the steel increases when many joints are made up together, and even a slight weight added to the upper portion causes a buckling or spiraling effect in the hole. The result is that the bit deviates from the vertical.

Jan 1, 1959

By A. Lubinski, J. L. Logan, W. S. Althouse

A4ost gas twells and flowing oil wells are completed and treated through a string of tubing and a packer. Changes in temperature and in pressure inside or outside the tubing will: (I) if free motion of the tubing inside the packer is permitted, increase or decrease the length of the rubing; or (2) if free motion is prevented, induce forces in the tubing and on the packer. If pressure inside the tubing is greater than outside, the tubing may buckle helically even in the presence of a packer-to-tubing tension. The tubing will always buckle, and much more severely, if free motion is permitted. The buckling may be prevented by pulling the tubing in sufficient tension. The prediction of these forces and tubing movement has here to fore been based upon calculations that did not inciude helical buckling. This paper preseitts means with which these length or force changes can be calculated while taking into account the effect of helical buckling. To avoid damaging formations, failure of remedial operations, or damage to the tubing or packer, application is made to practical problems involving calculations of the required length of seals, amount of sluckoff or tension, and prevention of permanent corkscrewing. INTRODUCTION Leakage of a packer may result in costly failures of such operations as squeeze cementing, hydraulic fracturing, etc. To avoid such failures, the authors are often asked questions pertaining to the length of necessary seals, the amount of necessary slackoff, etc. Published work' does not take into account helical buckling of tubing. Investigation of helical buckling was prompted by the fact that allowance must be made for this phenomenon in order to provide relevant answers. In the past, theoretical work on helical buckling was confined to conditions for which such buckling does not The mathematical treatment of behavior in a buckled condition, given in the Appendix, is novel. Assumptions upon which this investigation is based are listed and discussed in a special section. The following are a few of the many kinds of problems which may be solved with this paper. 1. Consider a packer in which tubing may move. Such movement will occur after pressures and temperature are changed. The paper provides means for: (a) calculating the amount of such movement and, therefore. the required length of seals; and (b) calculating the necessary amount of initial slackoff, for which there is no danger of unsealing the packer, if the length of seals is given. Such calculations, as well as those which follow, tully take into account the fact that part of the movement ib due to elastic helical buckling of the lower part of the string. This buckling may occur even in tubing under tension. Insufficient initial slackoff for a given length of seals, or insufficient length of seals for a given slackoff, may result in costly failures. A field case of such a failure will be given further in this paper. 2. In the case in which tubing cannot move in the packer, changes of pressure and temperature result in tubing-to-packer forces and forces in the tubing above the packer, both of which may be calculated. This knowledge is important because, if these forces are too large, the) could damage the packer or the tubing. 3. For wells in which wireline tools are to be run through the tubing, the paper provides means to keep the tubing from buckling, thereby permitting free passage of tools. 4. In deep wells, mainly in the presence of large casing, tubing may become "corkscrewed", i.e., take a permanent helical set. A field case is described further in the text. Using this paper, one may calculate in advance conditions under which permanent corkscrewing would occur, and then take preventive steps. HELICAL BUCKLING Consider a string of tubing, freely suspended in the absence of any fluid inside casing, as shown in Fig. I(a). Now consider an upward force F applied at the lower end of this tubing. This force compresses the string; and if the compression is large enough (which is always the case in actual problems), the lower portion of the string will buckle into a helix, as shown in Fig. 1 (b). The lower end of the tubing is subjected to a compression F. This compression decreases with the distance from the bottom and becomes nil (neither compression nor ten-

By A. Brown

RAPIDLY rising world demand for mineral pro- ducts has accelerated depletion of the more readily accessible ores, particularly those of premium grade. Operations must proceed at a faster rate to deeper horizons, where there are problems of ground control that restrict economic recovery of the mineral and introduce new hazards to mine personnel. For some of the new Canadian mining fields severe problems of ground stress are still in the future, but much of Canada's mineral output comes from well established mines that have reached considerable depths. It must also be anticipated that the depletion of premium grade ores will eventually necessitate mining low grade material at competitive cost, and unsolved problems of ground control can materially increase costs. Studies of ground stress phenomena in underground workings are therefore considered a present-day necessity, especially since these investigations must be a long-term effort owing to the highly complex nature of the problem and the difficulty of making full-scale observations.

Jan 8, 1958

By Harrison A. Schmitt

One of the great copper-producing areas of the world is comprised of five U. S. western states and northern Sonora, Mexico. The Southwest province of this area, covering southern Arizona, south- western New Mexico, and northern Sonora, produces some 55 pct of U. S. copper output and the equivalent of 15 pct of world production. In 1956 the area produced about 550,000 tons. Tucson is approximately the center of the oval- shaped province, which measures only 300 miles on its east-west axis and about 200 miles on its short axis. Northwest of the oval, and forming a tenuous connection with the Utah and Nevada copper fields, is an important operating mine, Bagdad, and also the now inactive United Verde. Along its north- south axis, running from Globe, through Tucson, to Nogales, ten moderate to major copper properties have been discovered or revived during the past 15 years, and five of these in only the past seven years. The latter five properties lie in an area 25 miles in diameter, centering 20 miles south of Tucson. In order of discovery, or revival, they are: Banner's Mineral Hill and Daisy; Cyprus et al's Pima; Duval's Esperanza; Asarco's East Pima (now called Mission mine) ; and Lewisohn's Peach. Total tonnage is estimated at about 250 million tons averaging some 0.90 pct Cu, but ultimate production may exceed this amount since some of the reserve is open ended.

Jan 6, 1959

By Harold Vagtborg

Equilibrium vaporization ratios were obtained for light hydrocarbons, nitrogen, carbon dioxide, and hydrogen sulfide in a reservoir fluid containing 35 mole per cent hydrogen sulfide. The data cover the range from 700 to 2500 psia at 154°F. The results of this study are compared with results obtained by other investigators on systems containing less hydrogen sulfide. When large amounts of hydrogen sulfide are present, the equilibrium vaporization ratios for ethane and heavier hydrocarbons are greater than the ratios for systems containing little or no hydrogen sulfide. Large amounts of hydrogen sulfide have the reverse effect on the ratios for methane. Routine PVT studies were performed on the reservoir fluid including flash and differential liberations of the dissolved gas. The pressure-volume relationships of the saturated fluid were also determined. It is shown that the use of published correlations on physical properties of reservoir .fluids can lead to gross errors when applied to systems containing large amounts of hydrogen sulfide. INTRODUCTION Equilibrium vaporization ratios for various components in naturally occurring crude oil and condensate systems have been reported in the literature.1,2,3,4 Recently, several papers have been published with emphasis on non-hydrocarbon components such as nitro- gen, carbon dioxide and hydrogen sulfide.5,6,7,8,9 The increased discovery of reservoir fluids having high concentrations of these non-hydrocarbon components, particularly hydrogen sulfide, has created a need for a further study of their phase behavior. Equilibrium vaporization ratios are known to vary with pressure, temperature, and overall composition of the system.'" It was anticipated that ratios for systems containing large amounts of hydrogen sulfide would differ from the ratios for systems containing small amounts of hydrogen sulfide. Therefore, the present work was undertaken in order to obtain reliable equilibrium vaporization ratios for the reservoir-fluid in question. PROCEDURE The procedure followed was evolved after considerable experimentation on methods of handling the very sour crude. It was found that drying agents (e.g. CaCl2 and CaSO4) absorbed an appreciable amount of hydrogen sulfide from the gas used to prepare the recombined samples. The concentration of hydrogen sulfide dropped as much as 10 mole per cent in a single pass through a 3-ft drying tube. It was also found that when undried gas was agitated with mercury in the PVT cell, a black scum, believed to be mercuric sulfide, was formed and the hydrogen sulfide content of the gas dropped several mole per cent. Because composition changes during a run could not be tolerated, separation of the mercury and sour fluid was necessary. In order to effect this separation, a stainless steel piston, equipped with Teflon O-rings, was placed in the PVT cell between the mercury and the sour fluid. This piston had to be constructed in three parts because

Jan 1, 1955