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At the close of the current academic year, there will be eight vacancies to be filled in research graduate assistantships which are maintained by the Engineering Experiment Station of the University of Illinois. In addition to these assistantships, there are available two research graduate assistantships in gas engineering, which are supported by the Illinois Gas Association. These assistantships, for each, of which there is an annual stipend of $500 and freedom from all fees except the matriculation and diploma fees, are open to graduates of approved American and foreign universities and technical schools who are prepared to undertake graduate study in engineering, physics, or applied chemistry. An appointment to the position of Research Graduate Assistant is made and must be accepted for two consecutive collegiate years, at the expiration of which period, if all requirements have been met, the degree of Master of Science will be conferred. Not more than. half of the time of a Research Graduate Assistant is required in connection with the work of the department to which he is assigned, the remainder being available for graduate study.

Jan 3, 1919

By Gilbert H. Cody

The present article calls attention to the activities of a committee on coal research of the sister society of Economic Geologists. The field of coal geology crosses the boundary between the two societies and joint meetings are as applicable here as in the metallic and other nonfuel fields of mining and natural resources recovery. The six fields of coal geology are briefly described and some of the ways in which they touch on coal mining, preparation, and recovery briefly indicated.

Jan 2, 1950

By Kenneth J. Kurry

12.2-1. Introduction. Successful management constantly strives to improve its methods and equipment in order to produce a better product at reduced cost. It is not enough that managers be cost conscious and industrious in these days of rapid, dramatic technological development. They must keep abreast of these developments-new or improved methods, machines, and equipment. Most of the machines and equipment have been carefully designed and perfected by reliable companies. However, improvements and progress often evolve from a definite need and are most successful in a particular operation. What may be the "answer" to the requirements of one company may be totally useless or inefficient to those of another. The manager of today must continuously evaluate the myriad proposals for change that result from modern technology-in terms of the particular needs and objectives of his company-to determine correctly which will best satisfy those needs and reach those objectives. Each new method or piece of equipment must receive careful study to make certain it is compatible with the entire operation. It may solve a problem in one department only to create a new problem in another. There are many pitfalls to be avoided in obtaining the necessary facts, and often these problems are unrelated to the actual use of the equipment or method being studied. All facets of the operation being considered must be thoroughly studied to determine if the method is compatible to the entire operation. For example, in considering a possible recommendation that a certain method and type of equipment be used to transport ore, some of the factors that should receive close scrutiny are: blasting procedure, maintenance, turning radius, percent grades, weather extremes, dumping problems, tire problems, length of haul, operator acceptance, or mismatched equipment. Failure to consider every factor-large and small, present and future-in evaluating a proposed change can mean a large investment in a new method or machine that will have to be continued for years at higher-than-antici-

Jan 1, 1968

By Waldemar Lindgren

FIFTEEN years ago, in his presidential address before the Washington Academy of Sciences,1 Alfred H. Brooks said: "Applied geology can only maintain its present high position by continuing the researches which advance the knowledge of basic principles. Future progress in applied geology depends on progress in pure geology." Early in 1927, Dr. David White, then chairman of the Division of Geology and Geography of the National Research Council, appointed a committee "On the Processes of Ore Deposition," which was the first recognition by the Council of this branch of applied geology. This committee will not be able to solve the many complex problems involved; it can only clear the way, survey the field, state the problems and encourage systematic research. This short paper aims to outline and to analyze the present status of this kind of geological research, to ascertain the quality of the work and to suggest lines that might profitably be followed. INCREASING DEMAND FOR GEOLOGISTS Economic geology, or the art of geology, could develop only after the principles of geology and mineralogy had been established. Before that time it was merely a collection of trade rules accompanied by more or less wild speculations. Thus we observe the beginnings of economic geology in the period 1770-1820. Soon afterwards, the State Surveys were established in this country, with the realization that the natural resources should be investigated and described. Geology was hardly yet equal to the task of scientific research in relationships and genesis, however, and there followed a period of discouragement and stagnation. In the meanwhile, pure geology had again registered progress, and, based on its principles and also on the rapid mining development in the Cordilleran region, the present phase of the study of ore deposits began to take form. Raphael Pumpelly, S. F. Emmons and G. F. Becker were among the pioneers in this movement. The United States Geological Survey was organized. Ore deposits were scientifically described and studied along lines of structure and mineralogy; theories of genesis were advanced, not always permanent but based on sound induction.

Jan 1, 1928

By E. P. Pfleider, W. D. Lacabanne

ROTARY-percussive drilling is a new method of drilling hard rock. Designed to give variations in thrust, revolutions per minute, and torque ranges, these drills combine the high efficiency of the rotary system in soft rocks with an increasing amount of percussive action in rocks more difficult to fragment. Fundamentals of the rotary, percussive, and combination systems have been described in detail in various papers-most recently by C. Fairhurst and W. D. Lacabanne1-but there is still much basic work to be done on the interplay of actions in the rotary-percussive system to enable the drill designer to achieve the highest efficiencies. Whereas the original units struck light blows of only 15 to 30 ft-lb, adequate for medium hard rocks, the present trend is to piston blows of 50 to 65 ft-lb in order to cope with the granites and other rocks having Shore hardnesses of 75 or more.

Jan 7, 1957

J. J. RUTLEDGE,* McAlester, Okla. (written discussiont).-Research work has often a more immediate and practical application to the in-dustries than even the investigators themselves realize, but coal mining has not attracted the investigator, except in so far as the mine-accident prevention work and fuel investigations are concerned. In future, the coal geologist will study the subsurface geology of the various coal seams as the petroleum geologist now studies the oil sands, and from the results of these studies the coal operator will be able to locate his shafts to the best possible advantage and to avoid faults that would interfere with underground work. There would have been many thousands of dollars saved, and perhaps some reputations, if a good stratigrapher. had been called into consultation in the southern part of Somerset County, Pa., where a local seam of coal, quite thick, was mistaken for the Pittsburgh seam, which, if ever present at that point, had long since been eroded. Why will the Quemanhoming coal carry more sulfur without injuring the grate bars than George's Creek Big Vein? Only the investigator can answer and yet the fact that the above is true means a greater price for the thinner coal. The owner of the land in Oklahoma receives one-fourth of the cotton crop produced by the tenant who farms his land and one-third of the

Jan 11, 1919

By John A. Mathews

RESEARCH in the steel industry, as in other lines of manufacturing, has for its principal purpose the increasing of profits. That is what manufacturing companies are for, and all departments of the organization must be so coordinated as to lead to profitable operation. To divide a payroll into productive and non-productive labor is misleading. Productive labor, in fact, is necessary labor, and non- productive labor is the labor we can get along without. One might as well say that the steering wheel is not a part of an automobile as to say that the directing minds of an industry are non-productive. Legitimate manufacturing profits in a steel company or any other company are the reward that the public pays for service rendered or risk taken. The desire for profits is the impelling motive that leads investors .to take risks and build up industries that give employment to others. Every department of a company, be it executive, manufacturing, financial, sales, or research, must contribute to the one end which brings success-profits.

Jan 1, 1921

By Gherman Pavlovich Nikonov

Results of preliminary research on the use of small diameter water jets at high pressure for cutting rocks has demonstrated the possibility of effective cutting of anthracite. Detailed research has, therefore, been conducted at the Skotchinsky Institute of Mining to study the dynamics and structure of the small water jets and the mechanism by which they cut coal. One of the objects of this research was to obtain data for the design of a machine for cutting rock, based on the same principles as that for cutting coal. The productivity of water jet mining machines depends on the hydro- dynamic parameters of the jet. Therefore, the research on small diameter water jets was directed, initially to a study of the nature of the variation of these parameters, and to obtain a profile of dynamic pressure distribution over the section of the jet. As has been confirmed previously, the required jet pressure (to cut coal) lies in the range of 100 to 500 atmospheres. These pressures were utilized for the research. The diameter of the nozzle was changed as ~follows; 0.97; 1.24; 1.5; 2.17; 2.87; and 3.57 mm. Graphs showing dynamic pressures for each nozzle diameter and varied axial dynamic pressure were obtained over distances ranging from 2 to 70 cm from the nozzle. One of the most important hydrodynamic parameters of a jet, closely related to the dynamics of jet disturbance in air, is the magnitude of the axial dynhmic pressure. A study of the variation in this pressure with increasing distance from the nozzle led to the separation of the jet into three specific parts, which differ from each other not only in the nature of the change in dynamic pressure, but also in structural properties.

Jan 1, 1971

Jan 1, 1929

By Joseph W. Leonard

The purpose of this paper is to review and discuss some of the less evident and sometimes neglected opportunities for progressive developments in coal research. While a great deal of both promotional and technical information flows from some areas of coal research, output deficiencies in other areas of activity have reached a magnitude where important developments have been, and will increasingly be, unfavorably affected. These areas mainly involve coal mining and preparation. Some recommendations for the intensification of effort in these areas follow: Coal Mining While a huge tonnage of in-the-ground coal is assured, the location and distribution of these tonnages are becoming less favorable. The easy-to-mine coal which is located in or near population centers has been, or is being, mined. The vigor with which the less accessible reserves are recovered by the mining industry depends largely on the condition of the coal market at the time of mining. Hence, during a buyer's market, the commercially oriented mining industry is compelled to mine the easier and less costly reserves. Conversely, during a seller's market, the need to rapidly expand production results in more difficult mining and higher cost coal as few obstacles are encountered in finding markets. Hence, a seller's market tends to enhance the recovery of reserves while a buyer's market does not. One reason for today's fuel supply problems is that the Nation has recently emerged from a long-term coal buyer's market which lasted from about 1950 to 1968. During that period, national policy caused severe production cutbacks which regretably drove the industry to mining only the more accessible and better quality reserves. Often in order to remain in business, many hundreds of millions of tons of more difficult to mine reserves were abandoned and lost behind caved areas. Many of these reserves are close to population areas and would not have been lost in a more stable economic climate. It is difficult to fully account for all the impacts that were caused by the great buyer's market of the 1950s and 1960s. Besides the obvious loss of reserves that were once considered national wealth, the mining of better reserves tended to produce a generation of technically optimistic mining people. Mining people frequently became accustomed to looking at nothing less than outstanding mining conditions as a result of the declining market. Many are now and have long since received a re-education in the other half of mining. Going from many years of mining accessible, select and easy-to-win reserves, to the crash-driving of development entries in reserves that were considered unworthy of mining during 50s and 60s, frequently results in a much higher rate of encounter with in-seam and out-of-seam rock as well as with coal-deficient areas or "washouts." Intensive entry driving activity and compulsory non-selective mining in sometimes lean reserves were brought on by the need to rapidly open up new supplies of coal. Working under these requirements presents a continuing reminder that much more needs to be known about the relatively esoteric art of planning the best direction for driving entries in order to insure that a more consistent and greater supply of coal is available during early mine development. All of the preceding discussion tends to point to a need for a better estimate of those reserves of coal that are likely to be mined in the future. Such estimates should not be limited to the compilation of the amount of coal in the ground; but, where possible, should also include information concerning the capability for producing this coal. After all, a coal seam of ample thickness may have a degree of thickness variability, undulation, bad roof or floor, so as to make what would otherwise appear to be an attractive mining condition untenable. Underlying the problem involving the feasibility of producing known reserves is the need to develop better methods for the characterization of coal seams and associated lithotypes, based on drill core data, once at area is selected for mining. Reserves and their characterization involve aspects of exploration technology that are frequently considered mature. The resulting technological deficiencies may be the main reason why coal exploration frequently does not end with core drilling of a property, as it should, but extends into the mining operation during the driving of development entries. When exploration is extended to the driving of development entries, the near absence of integrated decision-making theory involving mining, geology, mathematics, and economics becomes, once again, all too painfully apparent and frequently results in very costly rationalizations. Hence, by the formal initiation of a concentrated program to combine the cyclical effects of economics with geology and mining, more relevant estimates of reserve distribution, tonnages, and production capability should be forthcoming. Moreover, a similar formal effort is needed to develop a combination of the most advanced concepts of mathematics, geology, and mining to better "see" coal seams as a means to favorably implement many long-range decisions involving mine safety and productivity. Much more applied research needs to be done on coal mining systems for mining in thin seams and/or under bad roof. Current difficulties in both of these areas at recently opened coal mines should provide a sobering glimpse into the future. Full-scale applied research, sponsored by appropriate federal agencies, is urgently needed on a scheme involving a new combination of established mining and preparation elements. The scheme may include: (1) a continuous mining machine remotely operated by a miner stationed at some distance behind the machine using a cord attached control box; (2) hydraulic transport of coal through pipes from the mining machine to a coarse refuse removal grid, crusher, and then on to portable concentrating equipment; (3) the hydraulic transport of clean coal out of the mine in pipes to the surface for thermal dewatering, if neces-

Jan 1, 1974

By Walter Knox, J. D. Doherty

IN 1939, at the request of The Koppers Coal Co., the Koppers Company Research Department established a Stoker Coal Research Laboratory for the purpose of investigating the performance characteristics of stoker coals in typical domestic stoker installations. Fig. I is a photograph of part of the laboratory. The material in this paper deals with the performance of one coal in a single installation. Presented are details of this installation, mechanical characteristics of the stoker, and the results of a series of burning tests in which adjustments were systematically varied. SUMMARY OF RESULTS Mechanical Features I. A large percentage of the total power consumed by a domestic stoker is used to operate the gear case and motor (Fig. 3). 2. The power consumption per ton goes down with an increase in rate of coal feed (Fig. 4). 3. The automatic air control in this stoker showed advantages over manual control (Fig. 5). 4. The air velocities through the retort tuyeres were uniform around the retort, but varied between the rows of tuyere rings (Fig. 6). 5. The crushing of coal with this stoker increased the minus 1/8-in. from 1 1.6 per cent to 19.2 per cent. There was a noticeable segregation of coal as it came from the retort and distribution was not uniform (Fig. 7). 6. Measurement of air entering over the fire showed that with some not uncommon adjustments this air may he a high percentage of the total air supply (Fig. 8 and Table I). Operating Performance I. The removal of clinker was shown to give a period of poor performance characterized by a high fuel-bed resistance and a high percentage of carbon monoxide in the flue gases (Fig. 10). 2. The fuel-bed resistance was found to decrease as the fuel bed built up in a normal response to heat demand after a prolonged hold-fire (Fig. II). 3. With intermittent operation the burning rate was almost always less than the feeding rate. The wide variations were found to be greatly dependent upon the length of the On period and the length of the intervals between On periods (Fig. 12). 4. The maintenance of a low furnace draft led to less fly ash, better clinker formation, and higher efficiencies (Fig. I3). 5. The maintenance of a minimum of excess air also resulted in less fly ash, better clinker formation, and higher efficiencies (Fig. 14). GUIDING PRINCIPLES In planning the investigations, the following principles were adopted: Selection of Healing Equipment.-Use only standard models of stokers and furnaces representative of those widely used.

Jan 1, 1942

By Richard W. Markley

The predominant methods for mining coal in the USA are room and pillar and longwall. Approximately 95 percent of the coal is mined by room and pillar and 5 percent by longwall. The U.S. Department of Energy (DOE) has an ongoing program to improve the rate, quality, and cost effectiveness of stabilizing the roof for both of these mining systems. In room and pillar mining, the installation of permanent roof support is often the task which paces the system operation, and it thus controls the level of production achieved during any mining shift. Two automatic roof bolt insertion equipment developments are discussed, as well as a flexible drill for operation in thinner seams. Progress will be reported on under- ground trials of a particular flexible drill which has been combined with a bolt inserter to form a compact, reliable module for retrofitting to continuous mining machines. In longwall mining, the use of hydraulic supports on the working face provides roof stability. The DOE has several trials ongoing with shield- type supports in difficult strata conditions which are described, as well as a co-funded project with the Bureau of Mines on a resin injection remedial method for consolidating a shear zone at one site. A project to improve the match of strata conditions to shield design is also described, which involves the use of a 1360 tonne vertical load mine roof simulator.

Jan 1, 1983

THE Institute of Metals Division of the American Institute of Mining and Metallurgical Engineers appointed a Research Committee in 1925 to de-termine what could be done by the Division to promote research work in the United States on non-ferrous metals. It was recognized that a considerable volume of use-ful research work in this field was being carried on by individual industrial companies as well as by the uni-versities and other research institutions, such as the Bureau of Standards. One need only refer to the recent research literature on non-ferrous metals in the TRANS-ACTIONS of the A.I.M.E., and elsewhere, to be con-vinced of healthful research activity in this field. The appointment of the Committee, however, voiced the impression that what was being done was, however excellent, inadequate for the needs of the industry. It was felt that the Division could usefully devote some of its time and effort in stimulating activity in this field. The deliberations of the Research Committee have not failed to develop wide differences of opinion even on the simple questions: (1) whether the Division can aid in any practical manner in this cause and (2) what the features of such aid might be. However, it was clear that there was only one type of research activity with which it could be very usefully concerned, viz., that on subjects of fundamental interest and general application. It was obvious that research work having special objects and more immediate commercial appli-cation should best be left to the industry itself.

Jan 1, 1927

By B. H. Sage, W. N. Lacey

The growing background of experimental information concerning the volumetric and phase behavior of binary and ternary hydrocarbon systems is used as the basis for a comparison of these systems with naturally occurring hydrocarbon mixtures under conditions representative of underground petroleum reservoirs. The qualitative and semiquantitative similarities and differences between the two types of systems are considered in reference to the possibilities and limitations of using experimental data on binary and ternary systems for predicting the volumetric and phase behavior of naturally occurring hydrocarbon mixtures of low molecular weight. The possible influence on such phase behavior of water, hydrogen sulphide, nitrogen, and components of relatively high molecular weight is discussed. INTRODUCTION During the past two decades much effort has been devoted to the study of the volumetric and phase behavior of pure paraffin hydrocarbons and of binary and ternary mixtures of these compounds. Many of these studies were carried out with the direct objective of utilizing a knowledge of the detailed characteristics of binary and ternary mixtures of the lighter paraffin hydrocarbons for predicting the behavior of more complex mixtures. The ability to make such predictions with accuracy would be of great value in petroleum production and refining. Although the behavior of the methane-propane system' served at one time as a qualitative illustration of the probable characteristics of the more complex hydrocarbon mixtures found in nature, it' fell far short of requirements for quantitative predictions. The present paper endeavors to indicate the relation of the more recently accumulated information concerning the behavior of binary and ternary hydrocarbons to this problem. In discussing binary and ternary systems as examples pointing toward the behavior of multi-component systems no effort is made to present new methods of predicting the characteristics of natural hydrocarbon mixtures. Preliminary proposals have been made elsewhere for the prediction of volumetric phase equilibrium and thermodynamic data for multicomponent mixtures, utilizing as a basis the behavior of binary and ternary systems. Numerous other proposals have been made. That based upon the concept of a pseudo-critical state" has proved to be of value to the petroleum industry. Concurrently with this study of binary and ternary systems investigations have been made of natural hydrocarbon systems. Of the many publications reporting such experimental information only a few examples will be mentioned. A number of studies of black oil and natural gas have been made and much attention has been directed to extended and detailed investigations of the behavior of fluids in condensate fieldS 16,17,18,19,20. This work has been supplemented by some studies of the separation of bitumen from natural hydrocarbon liquids The over-all behavior of such systems has been used in predicting the volumetric and phase behavior of naturally occurring mixtures This background of experimental and correlated information concerning the behavior of multicomponent hydrocarbon systems also permits a direct comparison of the characteristics of binary and ternary aliphatic systems with those materials produced from underground reservoirs. PRESENTATION OF DATA The primary limitation encountered in using binary and ternary aliphatic hydrocarbon mixtures as examples of the characteristics of the fluids encountered in underground reservoirs lies in the existing lack of knowledge of the quantitative effect upon behavior of the presence of several important constituents, notably hydrocarbons of high molecular weight, water, carbon dioxide, hydrogen sulphide, and nitrogen. The presence of substantial quantities of hydrocarbons of fairly high molecular weight serves to increase the complexity of the phase behavior of natural systems. No simple systems yet studied give adequate guidance in this regard. The influence of such materials of high molecular weight was indicated earlier",?' to an extent which serves to show that definite limitations now exist in the correlation of simple and complex systems. However, significant progress is being made in filling gaps in the information. For example, similarities in the behavior of fluids in condensate fields with that of binary and ternary systems are becoming more systematically evident. A few studies of the behavior of water in paraffin hydrocarbon systems have been made Results of investigations of mixtures of carbon dioxide and the lighter hydrocarbons also are available Limited work has been reported con-

Jan 1, 1949

By W. N. Lacey, B. H. Sage

The growing background of experimental information concerning the volumetric and phase behavior of binary and ternary hydrocarbon systems is used as the basis for a comparison of these systems with naturally occurring hydrocarbon mixtures under conditions representative of underground petroleum reservoirs. The qualitative and semiquantitative similarities and differences between the two types of systems are considered in reference to the possibilities and limitations of using experimental data on binary and ternary systems for predicting the volumetric and phase behavior of naturally occurring hydrocarbon mixtures of low molecular weight. The possible influence on such phase behavior of water, hydrogen sulphide, nitrogen, and components of relatively high molecular weight is discussed. INTRODUCTION During the past two decades much effort has been devoted to the study of the volumetric and phase behavior of pure paraffin hydrocarbons and of binary and ternary mixtures of these compounds. Many of these studies were carried out with the direct objective of utilizing a knowledge of the detailed characteristics of binary and ternary mixtures of the lighter paraffin hydrocarbons for predicting the behavior of more complex mixtures. The ability to make such predictions with accuracy would be of great value in petroleum production and refining. Although the behavior of the methane-propane system' served at one time as a qualitative illustration of the probable characteristics of the more complex hydrocarbon mixtures found in nature, it' fell far short of requirements for quantitative predictions. The present paper endeavors to indicate the relation of the more recently accumulated information concerning the behavior of binary and ternary hydrocarbons to this problem. In discussing binary and ternary systems as examples pointing toward the behavior of multi-component systems no effort is made to present new methods of predicting the characteristics of natural hydrocarbon mixtures. Preliminary proposals have been made elsewhere for the prediction of volumetric phase equilibrium and thermodynamic data for multicomponent mixtures, utilizing as a basis the behavior of binary and ternary systems. Numerous other proposals have been made. That based upon the concept of a pseudo-critical state" has proved to be of value to the petroleum industry. Concurrently with this study of binary and ternary systems investigations have been made of natural hydrocarbon systems. Of the many publications reporting such experimental information only a few examples will be mentioned. A number of studies of black oil and natural gas have been made and much attention has been directed to extended and detailed investigations of the behavior of fluids in condensate fieldS 16,17,18,19,20. This work has been supplemented by some studies of the separation of bitumen from natural hydrocarbon liquids The over-all behavior of such systems has been used in predicting the volumetric and phase behavior of naturally occurring mixtures This background of experimental and correlated information concerning the behavior of multicomponent hydrocarbon systems also permits a direct comparison of the characteristics of binary and ternary aliphatic systems with those materials produced from underground reservoirs. PRESENTATION OF DATA The primary limitation encountered in using binary and ternary aliphatic hydrocarbon mixtures as examples of the characteristics of the fluids encountered in underground reservoirs lies in the existing lack of knowledge of the quantitative effect upon behavior of the presence of several important constituents, notably hydrocarbons of high molecular weight, water, carbon dioxide, hydrogen sulphide, and nitrogen. The presence of substantial quantities of hydrocarbons of fairly high molecular weight serves to increase the complexity of the phase behavior of natural systems. No simple systems yet studied give adequate guidance in this regard. The influence of such materials of high molecular weight was indicated earlier",?' to an extent which serves to show that definite limitations now exist in the correlation of simple and complex systems. However, significant progress is being made in filling gaps in the information. For example, similarities in the behavior of fluids in condensate fields with that of binary and ternary systems are becoming more systematically evident. A few studies of the behavior of water in paraffin hydrocarbon systems have been made Results of investigations of mixtures of carbon dioxide and the lighter hydrocarbons also are available Limited work has been reported con-

Jan 1, 1949

By Carl H. Unruh, D. L. Katz

Experimental data are presented for hydrate formation conditions for gas mixtures of carbon dioxide and methane. Equilibrium constants for carbon dioxide, defined as the mole fraction of carbon dioxide in the gas phase (dry basis) divided by the mole fraction of carhon dioxitle in the hydrate (dry basis)... were calculated usine the equilibrium constants for methane developed in an earlier paper. INTRODUCTION A series of papers have been written on gas hydrates, giving temperatures and pressures at which hydrates would form.2. 3, 4. 5, 6. 9. 12, 13, 15 Vapor-solid equilibrium constants have been developed for methane, ethane, propane and iso-butane' by which it is possible to compute for a specific gas mixture the temperature and pressure at which hydrates will form. Carbon dioxide is present in many natural gases in concentrations usually from 0.1 to 2.0 per cent. It also forms a gas hydrate with water and presumably enters the solid solution when present with a natural gas which is forming a hydrate. The equilibrium constant giving the ratio of the concentration of carbon dioxide in the gas phase to the concentration in the solid phase is required for including the effect of the carbon dioxide when computing the conditions for hydrate formation. Direct determination of the concentration of carbon dioxide in solid hydrate requires a difficult separation to be made. Therefore, this research resorted to the measurement of the temperature and pressure at which specific mixtures of methane and carbon diox- ide would form hydrates. From the equilibrium constants previously mentioned for methane, it is possible to compute the equilibrium constant for carbon dioxide, without measurement of the composition of the solid phase. Fig. 1 shows the conditions at which methane and carbon dioxide form hydrates. The methane curve FG extents to some high pressure while the carbon dioxide curve AB intersects the vapor-liquid water-liquid carbon dioxide

Jan 1, 1949

By Carl H. Unruh, D. L. Katz

Experimental data are presented for hydrate formation conditions for gas mixtures of carbon dioxide and methane. Equilibrium constants for carbon dioxide, defined as the mole fraction of carbon dioxide in the gas phase (dry basis) divided by the mole fraction of carhon dioxitle in the hydrate (dry basis)... were calculated usine the equilibrium constants for methane developed in an earlier paper. INTRODUCTION A series of papers have been written on gas hydrates, giving temperatures and pressures at which hydrates would form.2. 3, 4. 5, 6. 9. 12, 13, 15 Vapor-solid equilibrium constants have been developed for methane, ethane, propane and iso-butane' by which it is possible to compute for a specific gas mixture the temperature and pressure at which hydrates will form. Carbon dioxide is present in many natural gases in concentrations usually from 0.1 to 2.0 per cent. It also forms a gas hydrate with water and presumably enters the solid solution when present with a natural gas which is forming a hydrate. The equilibrium constant giving the ratio of the concentration of carbon dioxide in the gas phase to the concentration in the solid phase is required for including the effect of the carbon dioxide when computing the conditions for hydrate formation. Direct determination of the concentration of carbon dioxide in solid hydrate requires a difficult separation to be made. Therefore, this research resorted to the measurement of the temperature and pressure at which specific mixtures of methane and carbon diox- ide would form hydrates. From the equilibrium constants previously mentioned for methane, it is possible to compute the equilibrium constant for carbon dioxide, without measurement of the composition of the solid phase. Fig. 1 shows the conditions at which methane and carbon dioxide form hydrates. The methane curve FG extents to some high pressure while the carbon dioxide curve AB intersects the vapor-liquid water-liquid carbon dioxide

Jan 1, 1949

By Riki Kobayashi, D. L. Katz

The conditions at which methane and water form solid hydrates have been extended from 4,000 to 11,200 pounds per sq. in. The curve at high pressure had been in doubt because of Villard's report of a critical decomposition temperature. The paper explains the nature of the hydrate curve at high pressure and its dependence on fluid phase behavior. Extropolation of the methane hydrate curve indicates a pressure of 40,000 pounds per sq. in. will cause hydrates to form at a temperature of 100" F. INTRODUCTION The conditions under which natural gases form hydrates when liquid water is present have been studied by several investigators up to pressures of about 4,000 pounds per sq. in. The early work by Villard on hydrates of methane and ethylene13, ethane'', and propane14 included references to critical decomposition temperatures of the hydrates. Villard's work raised the question as to whether the pressure-temperature curve for methane-water hydrate continued above a temperature of 70.7°F. or whether this was the maximum temperature at which hydrates would form. This paper extends the experimental data on methane hydrate to 11,200 pounds per sq. in. A discussion of phase relations in the hydrate region for the hydrocarbons and of the methane-water system at high pressures is included. PREVIOUS WORK Villard suspected that methane hydrates could not be formed at temperatures above 21.5°C. (70.7°F.)la irrespective of the pressure of the liquid-vapor system. However, he was limited in his studies by his apparatus in 1888 to pressures not greater than 300 atmospheres (4,410 pounds per sq. in.) so that there has remained some doubt as to the existence of such a maximum temperature in this region. For the case of ethylene hydrates, however, Villard does specifically state the occurrence of what he terms a "critical temperature for the decomposition of the hydrates"13. Fig. lB shows a pressure-temperature projection of the three-phase locus, hydrate-ethylene rich liquid-vapor (H-L2-V) terminating at the critical locus in which L² and V assume similar properties. Throughout this paper the following phase designations will be used: H for hydrate, Ll for the water rich liquid. L2 for the

Jan 1, 1949

By Riki Kobayashi, D. L. Katz

The conditions at which methane and water form solid hydrates have been extended from 4,000 to 11,200 pounds per sq. in. The curve at high pressure had been in doubt because of Villard's report of a critical decomposition temperature. The paper explains the nature of the hydrate curve at high pressure and its dependence on fluid phase behavior. Extropolation of the methane hydrate curve indicates a pressure of 40,000 pounds per sq. in. will cause hydrates to form at a temperature of 100" F. INTRODUCTION The conditions under which natural gases form hydrates when liquid water is present have been studied by several investigators up to pressures of about 4,000 pounds per sq. in. The early work by Villard on hydrates of methane and ethylene13, ethane'', and propane14 included references to critical decomposition temperatures of the hydrates. Villard's work raised the question as to whether the pressure-temperature curve for methane-water hydrate continued above a temperature of 70.7°F. or whether this was the maximum temperature at which hydrates would form. This paper extends the experimental data on methane hydrate to 11,200 pounds per sq. in. A discussion of phase relations in the hydrate region for the hydrocarbons and of the methane-water system at high pressures is included. PREVIOUS WORK Villard suspected that methane hydrates could not be formed at temperatures above 21.5°C. (70.7°F.)la irrespective of the pressure of the liquid-vapor system. However, he was limited in his studies by his apparatus in 1888 to pressures not greater than 300 atmospheres (4,410 pounds per sq. in.) so that there has remained some doubt as to the existence of such a maximum temperature in this region. For the case of ethylene hydrates, however, Villard does specifically state the occurrence of what he terms a "critical temperature for the decomposition of the hydrates"13. Fig. lB shows a pressure-temperature projection of the three-phase locus, hydrate-ethylene rich liquid-vapor (H-L2-V) terminating at the critical locus in which L² and V assume similar properties. Throughout this paper the following phase designations will be used: H for hydrate, Ll for the water rich liquid. L2 for the

Jan 1, 1949

By J. S. Billheimer, H. H. Reamer, B. H. Sage

Jan 1, 1949