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By F. I. Stalkup

Vapor-liquid phase equilibrium experiments have been conducted in a static equilibrium cell on mixtures of a light, 45 API stock- tank gravity reservoir fluid and a rich hydrocarbon gas containing approximately 55 mole per cent of intermediate hydrocarbons. Both apressure-vs-composition study of the gas and a simulated reservoir fluid, and a multiple-batch contact simulation of the condensing-gas-drive oil recovery process were performed. In the latter experiments equilibrium gas and liquid compositions were analyzed. Also, conventional, "condensing-gas-drive", long-tube displacement experiments of the reservoir fluid and gases of various richness were performed. The results of these experiments could not be satisfactorily interpreted by the conventional pseudo-ternary-diagram representation of multicom-ponent phase behavior. The results seem to be explained better by considering a bubble-point surface and a dew - point surface joined in a plait-point locus. Portions of the plait-point locus cannot be "seen" directly by the rich hydrocarbon gas because of curvature of the dew-point surface. In such a system, continuous injection of the rich gas over stationary reservoir fluid might form a zone of contiguously miscible compositions from pure rich gas to pure reservoir fluid by: (1) saturating the reservoir fluid with injected gas to the bubble-point surface; (2) creating by mass transfer with fresh injected gas a path of contiguously miscible compositions along the bubble - point surface to the plait-point locus; and (3) creating by mass transfer with additional injected gas a path of gas compositions along the dew-point surface up to the point where direct miscibility results between dew-point fluid and the injected rich gas. INTRODUCTION The use of the pseudo-ternary-phase diagram to illustrate miscible displacement phase behavior has been discussed by several authors.5,7 Such a representation of phase behavior is not rigorous, but the ternary diagram nevertheless gives a qualitative picture of what actually occurs in a miscible displacement process. Fig. 1 is a typical illustration of miscible displacement phase behavior by a ternary diagram. The multicomponent hydrocarbon system is divided into three pseudo-components: a light fraction containing methane and nitrogen, an intermediate fraction containing ethane through hexanes plus carbon dioxide, and a heavy fraction containing heptane and heavier components. A two-phase region is bounded by a dew-point curve and a bubble-point curve, which are joined at the critical point. The concept deduced from such a representation for miscible displacement by a condensing-gas-drive process is as follows: a rich gas G, which lies to the right of the limiting tie line through the critical point C, is injected into the reservoir and contacts reservoir fluid L, saturating the reservoir fluid to give bubble-point fluid L1 and equilibrium dew-point gas GI. Continued injection of rich gas changes the composition of the saturated liquid L1 through a series of liquid compositions lying along the bubble-point curve, until the critical composition C is reached, at which point direct miscibility with the rich gas is achieved. Some equilibrium gas with compositions lying along the dew-point curve from G1 to C is also formed in this process. Thus, continuous injection of rich gas forms a

Jan 1, 1966

By Robert F. Mehl

METALLURGISTS are properly interested in papers dealing with subjects ranging from the theories of the metallic state to very practical details on the use of metals. A review of theoretical metallurgy naturally excludes papers concerned with the usefulness of metals and limits itself to those concerned purely with the science of metals. Even in this more limited field the reviewer is confronted with thousands of papers dealing with facts and theories of metallic behavior, from which he can select only a few hundred. The selection is necessarily highly arbitrary. Certain classes of papers definitely fall within the scope of this review. Thus, papers on the deformation of metals, on the structure of alloys, on recrystallization, to select only a few, are fully represented. Other subjects, which verge on what is generally accepted as the science of metals, such as the magnetic properties of metals, the less familiar electrical properties and theories, adsorption of gases by metal surfaces, and the like, are treated scantily. Particular attention is given to reviews of subjects that fall with in the groups chosen; in a summary such as this, which is largely in the nature of a progress report, capably written reviews are of importance, particularly since the monograph and text book literature is so meager in this field. THEORIES OF STATES OF AGGREGATION The electron theory of metals and the relation between possible electron structure and the magnetic properties have been discussed (317.307)† the electron theory of liquid metals, especially with respect to electrical conductivity, has been considered(306).

Jan 1, 1935

By W. S. Weeks

In coursing the ventilating air through a mine it is often necessary to restrict a comparatively open split in order that it may carry exactly the desired quantity of air. Such a restriction is known as a regulator, and usually takes the form of a partition with a hole in it. The quantity of air circulating is controlled by the size of the hole or orifice. For example, it is desired to force a quantity q I cu. ft, per min. through split a (Fig. 1) and the quantity q2 through split b. It requires a pressure of 2 in. water to force the desired quantity through a, and a pressure of 1 in. to force the desired amount through b. The pressure drop between points A and B must be 2 in and a pressure of 1 in. must be destroyed in split b. This is done by inserting a regulator in b, which causes the velocity to increase in the orifice and results in a change from pressure-head to velocity-head. If the air, after passing the orifice, is slowed down in a turbulent manner, all of the velocity-head does not change back into pressure-head, so a permanent loss of static pressure results. A classic formula for computing the area of an orifice to destroy a certain amount of static pressure has been handed down from early days: 0.0004Q a =2 This formula is based on the assumption that all velocity-head in the orifice is "destroyed;" that is, does not reappear again as either velocity-pressure or static pressure. The derivation of the formula is as follows: h = head lost in regulator in fect of air. v = velocity in regulator in fect per second. q = quantity circulating in cubic feet per second. Q = quantity circulating in cubic feet pcr minute. a = area of orifice in square feet.

Jan 1, 1928

By Y. A. Chang

Heat content values of tantalum monocarbide and tungsten monocarbide have been determined from 325" to 985°K by means of a drop-type diphenyl ether calorinzeter. Based on the values obtained in the present study and those available in the literature, best values lected and computed from 298. 15°K to temperatures close to their respectiue melting points. At temperatures higher than 1700°Kfor TaC and 27000 K for WC, values of Cp and related thermodynamic quantities were extrapolated based on the two Debye parameters: one corresponds to the metal sublattice and the other to the carbon sublattice. The contrzbutzon In the total specific heat due to lattice dilation was evaluated using the Nernst-Lindemann relalionship. The calculated values of Cp were in good agreement with the In view of their refractoriness, tantalum monocar-bide (TaC) and tungsten monocarbide (WC) are of con- experimentally determined ualues. Furthermore, the calculated values of the absolute entropies at 298.15"K were 5.03 and 4.15 in comparison to the experimental values of 5.05 and 4.15, all expressed in the unit of cal per degg-atom. Using the same Debye parameters, values of the linear coefficients of ther mal expansion for TaC and WC were calculated from absolute zero to their respective melting points using the Grüneisen equation. The calculated values are in excellent agreement with the experimental values available in the literature. Finally, the values of the bulk modulus of TaC from room tenzperature to temperature near its melting Point were also calculated using the equation recently derived by Anderson. No cot~ipari-son between the calculated and experimental values can be made due to lack of experimental data. siderable practical interest. In order to completely define these materials, it is necessary to know their thermal properties as a function of temperature. Tantalum rnonocarbide having a NaCl structure (B-1 type) melts congruently at 4250PK,1 while tungsten monoearbide with a simple hexagonal structure (Bh type) melts per itectically at 3049°K into melt and graphite.2 In the present study, the heat content values (from which

Jan 1, 1968

By H. M. Davis, T. S. Jones

A methodfor accelerating the reduction of a metal oxide by carbon monoxide is to incorporate in the reduction system a nonreducible oxide which has a strong affinity for carbon dioxide and will remove it from the product gases. The effectiveness of this method was investigated by veduction experiments on specially prepared powder mixtures of SrO-ZnO ("active'.) and SrCO3-ZnO (reference). Measurements at 750o and 677°C showed that the rate of reduction of ZnO by CO was as much as an order of magnitude greater in the presence of SrO. Under the experimental conditions at least as much CO2 as generated by veduction was absorbed when SrO was present. Enlzancernent of the veduction rate by SvO resulted from modification of' gaseous djfitsion processes. THE specific question posed in this investigation was whether the reduction reaction CO + ZnO - Zn(g) + COa [1] could be accelerated by incorporating strontium oxide into the oxide charge undergoing reduction. Provided the strontium oxide was active enough, it could remove carbon dioxide from the product gases of ( 11 and form strontium carbonate, thus modifying Reaction [ 1] to CO + ZnO + SrO = Zn(g) + SrCO3 [ 2] This study of the comparative rates of Reactions [ I] and [2] can be considered as a particular case of a general scheme for increasing the rates of reduction of metal oxides by carbon monoxide. The limits of applicability of this scheme are indicated in the simple thermodynamic analysis presented in the appendix. This analysis primarily dictated the choice of the system, CO-ZnO-SrO, employed in this investigation. In addition, it was thought that a study of this scheme by use of the CO-ZnO-SrO reaction system would be of special interest in view of indications in the literature1-3 that the gaseous reduction of zinc oxide is prone to rate control by diffusion in the gas phase. The distinction should be pointed out between this and other efforts to increase the rates of reduction reactions through the use of addition agents. Additions of a wide range of chemicals have been tried with de- grees of apparent success varying from slightly negative to highly positive. The reasons for making additions have included the use of salts to produce effects akin to catalysis,4, 5 the alteration of the microstruc-tural details of the reduction process (including solid-state diffusion),6-8 and the conversion of an en-dothermic reaction into one that is exothermic or autogenous.9-12 The means used to attempt alteration of the enthalpy change has commonly been to incorporate lime into the charge, so that heat is generated by reaction with either of the reaction products, carbon dioxide or water. The use of lime in this way makes endeavors such as that of Edstrom and Wiberg similar to the present one. Furthermore, the basic principle behind the present work has previously been set forth.13 However, a detailed investigation of the type of reaction described in this work does not appear to have been conducted. EXPERIMENTAL PROCEDURE From both conceptual and physical standpoints, Reaction [2] is to be considered as the sum of two reactions:

Jan 1, 1968

By J. P. Newell, R. W. Storey

AUGER mining is a form of continuous mining in that it completely replaces with a one-cycle operation the older conventional cut, drill, shoot, and load method of mining. Relatively new, having been utilized only within the last few years, it is even more continuous in its production of coal than some other forms of continuous mining being practiced in this country today. There are at present coal recovery .augers in operation working along strip-mined highwalls from the outside. This paper will deal with underground mining, specifically with an experiment which was carried out with a machine developed for this purpose. The location of this experiment was in Pike County in eastern Kentucky in the upper split of the No. 3 Elkhorn seam. Coal height was 32 in. and roof conditions were very bad, with 10 in. of soft draw slate coming down with every cut in conventional mining. The coal is high-grade bituminous, excellent for metallurgical coking. Underground auger mining fills a need for a method of recovering coal in thin seams, under bad roof conditions or in split seams. In many cases it might save money by eliminating the handling of excessive quantities of rock. In fact, if the coal can be recovered, as in the case of this experiment, without mixing with any impurities outside the seam, it may be possible to load or ship a satisfactory product with little or no preparation or cleaning expense. The need for some economical method for recovering coal from thin seams is becoming more pressing as the more profitably mined seams are exhausted. Basic Principles of Auger Mining The principles of the auger, or screw conveyor, have long been used in drilling small diameter holes for blasting and other purposes. These same fundamentals apply to large diameter drilling. However, considerably more attention was given to designing a cutting head that would not pulverize the coal and consequently would require a minimum of power to drive it. The head, as designed for this job, consists of a cylinder 25 in. in diam with steel bits set in 3 positions spaced around the forward rim. A conventional coal drill bit, at the head of a bursting cone in the center of the cylinder, trails the forward rim slightly, see Fig. 1. The bursting cone and auger connections are anchored to the cutter barrel by 3 arms spaced at 120 This head design proved to be very satis-

Jan 1, 1952

By C. H. Fulton

Page Introduction........................... 280 Distillation Products from Reduction of Zinc Ore........... 281 Preliminary Investigations..................... 290 Equilibrium of Reaction Zn + CO2 + ZnO + CO in Temperature Range of Condensation........................ 293 Requisites for Successful Condensation................ 299 Discussion............................ 300 Introduction The study of the condensation of zinc from its vapor was undertaken to shed light on certain problems encountered in large-scale electric zine-furnace work. recently conducted. It is a matter of common knowledge that one of the disadvantages of the arc type, electric zinc furnace, is the production of a large amount of blue powder and proportionately little liquid spelter, for, as stated by Stansfield,l "A notable defect in the electric smelting of zinc ores is the difficulty experienced in obtaining the distilled zinc in the liquid state; ...... when zinc ores are smelted electrically, very little liquid metal is commonly obtained, nearly all of the zinc being in the state of powder." This difficulty was not encountered in the electric furnace used12 the main difficulty being the destruction of the fire-brick lining of the large condenser, in certain parts, and the formation of .some oxide and dross coatings on the condensing surfaces. The reason for these difficulties could readily be explained by the infiltration of air whenever the condenser was changed from one retort base to the other, the zinc absorbed in the fire-brick forming oxide and causing rupture by its expending volume. Two facts, however, tended to disprove this theory for the rupture of the fire-brick lining: first, the large distilling retort, lined with fire-brick, which was shifted from charge to charge on alternate bases at temperatures between 1200 and 1300 C., fully exposed to the air, showed no signs of disintegration whatever; second, marked disintegration in the condenser occurred .only in places that were at tempera-

Jan 1, 1919

By B. G. Agnew

In evaluating fracture treatments, the need to answer such questions as "What zone or zones were actually treated?" and "What was the vertical extent of the treatment" is necessary, since determining effectiveness of the fracture treatwrent depends on knowledge of the reservoir portions stimulated and the vertical extent of the fracture system or systems. Injection of hot or cold fluids during fracturing operations will transfer heat to the surrounding formations and fracture faces mainly by heat conduction. Once injection ceases, temperature anomalies will develop opposite the zone fractured because the rate of temperature decay is less than that opposite zones heated or cooled by flow inside the wellbore or along the cement sheath. Thus, temperature surveys can he used to determine where fractures were generated outside the wellbore and to reasonahly estimate the vertical extent of the fractrires. This technique has been used successfully to evaluate over 344 fracture treatments at depths ranging from 1,500 to 15,700 ft. Examples of actual temperature surveys are presented to show how this method of fracture treatment evaluation can be used effectively and beneficially. INTRODUCTION Stimulation of producing or injection wells by fracturing is commonplace in the industry today. In evaluating these treatments, two basic questions which arise are "What zone or zones were actually stimulated?" and "What was the vertical extent of the treatment?". Knowledge of the reservoir portions stimulated and vertical extent of the fracture system or systems is vital to effect efficient and economical well completions and to assure maximum recovery from reservoirs. Not all fracture treatments are successful and many times the desired or anticipated results are not achieved. When this occurs, it is in most cases the engineer's job to determine why. The answer to this problem forms the primary basis for deciding whether to spend more money for development drilling and/or completion attempts or to forego additional expenditures to improve the particular zone. Also, knowledge of the reservoir portion actually stimulated is invaluable in planning future workovers. This is especially true in wells producing from reservoirs containing multiple porosity stringers or zones. For various reasons, all zones within a reservoir may not be perforated on initial completion with the thought of developing remaining zones through future workover operations. Because particular zones are perforated and fracturing fluid pumped down the wellbore, it cannot be assumed that all perforated zones are stimulated, and in turn drained. Occasionally, unperforated zones which are planned for future development are actually stimulated on initial completion. eliminating the need for future recompletion attempts or all zones perforated initially are not stimulated, thus requiring additional completion work to insure that these zones are adequately drained. In most cases, it is costly. if not impossible, to determine with assurance why a fracture treatment is unsuccessful after the job has been completed and the results tested. Further, unpredictable upper and lower fracture barriers. as well as possible borehole communications (cement channels), do not permit it to be taken for granted that the formation opposite the perforations is the only zone receiving the fracture treatment. Thus. evaluation of fracture treatments is necessary for efficient and prudent well completion practices and should be done simultaneously with the fracture job. Several methods have been used to locate fractured zones, all of which are based on detection of radioactive tracer materials added to either the fracturing fluid or the propping agent. These methods have been helpful in increasing knowledge of fracturing operations; however, they are seriously limited because of cost and inability to detect accurately radioactive tracer material more than a few inches away from the borehole. To develop a better diagnostic tool to pinpoint which zone or zones had actually been fractured, temperature surveys were run after fracturing with heated and cooled fluids. Significant temperature anomalies were found to exist opposite zones suspected of receiving the fracture treatment. From the analysis and examples to be shown, it can be seen that temperature surveys run in a stabilized wellbore several hours after a fracture treatment using hot or cold fluid will yield temperature anomalies which show the actual reservoir portion stimulated, the vertical extent of the fracture system or systems and a qualitative indication of the portion of fracture-fluid volume entering a given depth interval. The experience and illustrations used in this paper are based on evaluation of over 344 fracture treatments during the past three years using this diagnostic tool at depths ranging from 1.500 to 15,700 ft and fracture volumes ranging from 2.000 to 110.000 gal. Based on analyses of these temperature surveys, analyses of fracture gradients and evaluation of several open-hole packer impressions in the West Texas area,' vertical fracturing is the predominant mechanism and horizontal fractures occurred frequently, if at all.

Jan 1, 1967

By B. S. Gottfried

A generalized mathematical model is presented, which describes the thermal recovery of oil in linear systems with convective external heat loss. Three-phase fluid flow, conduction-convection heat transfer, chemical reaction between oxygen and oil and aqueous phase change are included, making the model applicable to a variety of thermal recovery processes. The complexity of the model requires that numerical solutions be obtained with a digital computer. The numerical approximations of the partial differential equations are presented and the algorithm is discussed in detail. The analysis is applied to the detailed simulation of a forward-combustion laboratory tube experiment. The results of the simulation exhibit with reasonable accuracy all of the principal thermal and bydrodynamic characteristics observed in the laboratory (i.e., the propagation of a combustion zone, a steam plateau, and oil and water banks). Numerical variations in the parameters appearing in the external heat-loss term, the aqueous phase-change term, and the Arrhenius combustion term are examined, and their effects on the predicted temperature profiles, oil and water production histories, and the air-oil ratio are presented. In spite of an oversimplification in the chemical reaction mechanism and the considerable computer time required to obtain solutions, the model represents a major advance in the ability to simulate the phenomena observed in thermal recovery experiments. INTRODUCTION Thermal oil recovery refers to a class of recovery processes where heat is supplied to a reservoir to provide the necessary expulsive energy. This thermal energy can be supplied externally as steam or hot water, or it can be generated in situ by forward or reverse combustion. In either case, however, thermal recovery processes are charac- terized by the simultaneous flow of two or three fluid phases in a variable - temperature field, accompanied by possible chemical reaction or phase-change effects.2-5, 7- 10, 14,16-18,20-22 Although a physical understanding of the thermal recovery processes is far from complete, it is possible to construct mathematical models which describe approximately all of the principal physical and chemical phenomena. However, attempts to solve such models, even with high-speed computers, involve formidable mathematical difficulties. Consequently, theoretical solutions have been obtained only for idealized cases in which important physical phenomena are neglected. For example, consider the process of forward in situ combustion. All such theories which have been developed consider only certain aspects of the process, such as heat transfer, 2-4,8,9,l6,l8 heat transfer with phase change,10 heat transfer with chemical reaction,7 or the hydrodynamics of three-phase flow.21 A general theory including all of the above phenomena has not been developed to date. This paper presents a unified theory of thermal recovery processes in linear systems. A mathematical model is developed which explicitly includes conduction-convection heat transfer with convective external heat loss, chemical reaction between air and oil, aqueous phase change, and the hydrodynamics of three-phase flow. A system of equations is developed which can be solved numerically on a high-speed digital computer, resulting in predicted temperature, pressure, and saturation histories in space and time. The model allows a more detailed simulation of thermal recovery tube experiments than had previously been possible. THEORETICAL DEVELOPMENT Consider the linear flow of gas, water and oil in a homogeneous porous medium. Assume that the oil will react with gaseous oxygen, and that mass is transferred between the water and gas phase by evaporation or condensation. In the absence of hydrocarbon phase change, intraphase diffusion,

Jan 1, 1966

By P. S. Rudman

The solubility limit and the diffusivity of carbon in molybdenum have been obtained by duffising carbon into molybdenum rods from a Mo + Mo2C powder mixture. The solubility limit was taken as the long-time asymptotic limit of the rod composition. The diffusiv-ity was obtained from fractionally saturated rods from the rate of change of the average composition. Compositions were determined by chemical analysis. The solubility limit obtained is: WhILE the Mo-C system is important in refractory alloy technology neither the solubility limit nor the diffusivity of carbon in molybdenum is unambiguously known. In Fig. 1 the Mo-C phase diagram is presented. The heavy lines, the terminal solution solubility limit, and the eutectic temperature are results of the present investigation and will be discussed in detail later. However, it is readily seen that the previously published solubility limit determinations, Few and Manning1 and Fromm and ROy2 differ by up to an order of magnitude. The general form of Fig. 1, the Mo2C field, and a eu- tectic temperature -2200°C are due to an early Investigation by Sykes et a1.3 Although they did not determine the solubility limit, they did establish that the maximum at the eutectic temperature was about 1000 ppm. The only other prior data found on the solubility limit is from a lattice-parameter study by Speiser et a1 .,4 from which it can be concluded that the maximum solubility is greater than 1800 ppm. There does not appear to be any data oh the diffusivity of carbon in molybdenum. However, Samsonov and Epik5 have determined, from the rate of growth of an MozC layer, the diffusivity of carbon in Mo2C, and this has been erroneously interpreted, for example by ~c~eil,' as applicable to diffusion of carbon in molybdenum.

Jan 1, 1968

By Dr. O’Neil Thomas J., Donald W. Gentry

"There is nothing so disastrous as a rational investment policy in an irrational world. " John Maynard Keynes INTRODUCTION The principles of time value of money concepts were discussed and illustrated in Chapter 3. The importance of time value of money and the role it plays in the discipline of engineering economy have been well established. Chapter 9 further illustrates that project evaluation criteria that fail to consider this aspect are seriously deficient in providing appropriate capital budgeting decisions. Obviously future project receipts and expenditures must be discounted to permit valid comparisons with current cash flows. Although the concept of discounting is widely accepted, the selection of the appropriate discount rate has been the source of considerable debate and much disagreement. This chapter, then, provides an overview of the theoretical and practical considerations for determining or calculating the appropriate rate for discounting, the corporate cost of capital. Note specifically that the assumption of constant business risk among the various investment alternatives is maintained throughout this chapter. THE INTUITIVE APPROACH The fact that interest exists suggests that all money has a cost associated with its use. The cost of this money may be the result of either explicit or implicit charges or some combination of the two. Any time an individual or a firm consumes less than the total earnings generated in a given time period that individual or corporation has either consciously or unconsciously decided to "invest" these excess funds in some type of activity. For instance, the individual or corporation may decide to invest the excess funds in tangible property, place the funds in a money market account, or simply keep these funds in cash. In any case, these funds have been invested in some type of activity which promises the investor some return on the invested capital. Remembering that the firm's primary objective should be the maximization of shareholder wealth, then intuitively it seems reasonable to suggest that the firm should not invest in any project where the anticipated return does not exceed the cost of funds (capital) committed to the project. Indeed, if the firm always invests in projects having returns in excess of the cost of capital committed to them, then the wealth of the firm (as measured by the price of common stock) should be in-

Jan 1, 1984

By Noel H. Stearn

When the Age of Machinery was suddenly thrust upon civilization about the beginning of the 19th century, an unprecedented demand for mineral resources sprang up. This demand brought about the rapid development of the known ore deposits and the discovery of such other deposits as could be encountered by energetic and canny prospectors. Thus in the countries now reasonably accessible nearly all orebodies have been located except those which are totally concealed even from the eyes and "senses " of experienced and expert prospectors. The high rate of exhaustion of known ore deposits and the necessity of looking farther and farther ahead for raw materials as a matter of insurance on the stupendous capital outlays involved in mining, development, and conversion operations, have resulted in exceptional activity in three different fields of effort. The first is purely geographic. Prospectors are now penetrating the few hitherto inaccessible regions in the hope of stumbling upon exposed ore deposits or locating visible indications of their presence. The second is chemical. Industrial chemists and metallurgists are seeking to facilitate the exploitation of lower grade ores or to find methods of recovering valuable metals from common substances. In the third field of effort lie the activities of the economic geologist and the mining engineer, who endeavor to locate concealed ore deposits which would remain hidden from the prospector no matter how expert or conscientious he might be. Obviously the task which such a man must face is both exacting and indefinite, and the tools which he has heretofore been permitted to bring to it are, for the most part, abstract—a knowledge of certain fundamental principles and processes involved in the origin, occurrence, structure, and distribution of deposits of natural resources and of the rocks which form the environments of those deposits; and a process of reasoning by analogy supplemented by the use of the diamond drill, or such artificial exposure as the test pit, trench, shaft, or tunnel.

Jan 1, 1929

By J. R. Elenbaas, J. A. Vary, D. L. Katz

The development of gas fields, oil fields and aquifers for storing natural gas is treated from two main vieu.-points: (I) the volumetric storage capacity for gas in a given situation and (2) the prediction of the number of wells required for the delivery of gas. Other experiences in the design and operation of storagc fields are incluclerl INTRODUC TION Storage of natural gas in underground reservoirs near the terminus of long distance pipelines has been the prime factor in opening the space heating market to the natural gas industry. Storagc has permitted a major. increase in both the load and the load factor of pipe-lines; some are now operating at steady load throughout the year. Thus, underground storage has been responsible for the rapid increase in demand for natural gas in recent years. Three types of reservoirs have been used for gas storage: natural gas reservoirs, oil reservoirs, and waterbearing sands or aquifers. This paper presents the factors to be considered when developing gas storage reservoirs of these three categories. There are two prime considerations tor any storage reservoir: (1) the volume of gas which a given reservoir will store advantageously and (2) the number 01 wells needed to provide the required peak deliverability. These two problems will be considered for the three types of reservoirs just noted STORAGE IN PARTIALLY DEPLETED GAS FIELDS Early storage operations consisted of replenishing the natural gas in a depleted gas field situated adjacent to the market. Today, newly discovered fields near the market may be considered for storage, and this discussion applies equally to both types of reservoirs. For reservoirs originally containing gas or oil, the question of the impermeability of the cap rock nor-mally does not arise. However, such fields are likely to have many wells drilled either to or through the reservoir under consideration. Positive assurance must be obtained that such wells are or can be made mechanically tight. Corroded casings may need to be lined or permanently plugged. Abandoned wells should bc reopened and properly cemented. The volumetric capacity for gas storage depends upon space available in the porous rock as well as pressure and temperature of the gas in the reservoir. The production-pressure decline data on partially depleted gas reservoirs without water drive permit calculation of the reservoir space for gas. Isopachous maps of sand volume and porosity data for the reservoir rock provide an alternate method of calculating the pore volume for water-drive reservoirs. The pressure range selected for the storage cycle depends upon ()) the safe upper limit of pressure. 2) the flow capacity of wells and (3) compression requirements when injecting gas into the reservoir or delivering to market. Normally, gas and oil fields have pressures at discovery in the range of 0.43 to 0.52 psi/ft of depth. Pressures of around 1.0 to 1.2 psi/ft of depth appear to lift the overburden1-3 and invite uncontrolled movement of fluids in the porous rock. Some top pressure is normally selected for a storage reservoir ranging from below discovery pressure for deeper reservoirs to 0.65 psi/ft of depth for shallower reservoirs. Pressures to 0.66 psi/ft have been experienced without difficulty. The lower pressure limit is set by water intrusion accompanying low pressures, reduced flow capacity for wells at lower pressures and compression requirements. Depletion-type gas reservoirs often encounter water problems in the later stages of gas production. Such water intrusion may be due to movement from the surrounding aquifer. Accordingly, displacement of this water back into the aquifer by gas pressure and subsequent surges of water corresponding to the gas storage pressure cycle must be considered. Storage fields often produce in four months a volume of gas equal to its initial content. Rapid decreases in reservoir pressure occur, such as 20 psi/day. Accordingly, closed-in pressure observation wells which reflect the pressure in the bulk of the reservoir are required for following the operation of the reservoir. It has been found that a plot of observation wellhead pressures against gas content, Fig. 1, is very useful in observing operation of the field, checking the inventory and predicting future behavior. The plot is based on a given quantity of base or cushion gas in place. The injection and withdrawal curves may spread depending upon the homogeneity of the reservoir rock. permeability of the rock, well spacing and flow rates.

By D. M. Waldorf

Steam permeability measurements have been made in the laboratory on several samples of natural reservoir materials. The steam temperatures and pressures were selected to simulate conditions which might exist in a reservoir during the injection of steam. For each sample tested, the experimental permeability to superheated steam was comparable to that measured with air and no evidence of plugging was detected. Some samples were exposed to water at various temperatures and plugging was found to occur in materials which contained significant quantities of monmorillonite clay. Temperature had little effect on the degree of plug-ning between 75 and 325 F. The measured pemeabilities tended to increase slightly with temperature, but the changes were small compared with the initial loss of per~neability on wetting. Sequential pemzeability measurements were made on two samples using air, water, steam, water and air, in that order. Both samples were water-sensitive and plugged extensively after the initial injection of water. Upon exposure to superheated steatm the samples dehydrated and their permenbilities to superheated steam were comparable to those initially measured with air. The remaining measuretnetzts with water and air confirmed that the water plugging was reversible and that the samples were not seriorrsly damaged during the tests. INTRODUCTION The swelling of water-sensitive clays during water floods has long been recognized as a potential source of reservoir damage. The recent extensive application of steam injection and stimulation has compounded this problem since both hot water and steam (as well as fresh water at reservoir temperatures) are, at sume time, in contact with the producing zone adjacent to the bore of a steam injection well. The purpose of this paper is to present data which compare the sensitivity of some natural sedimentary rock samples to water at various temperatures, and to super-heated steam. Some properties of montmorillonite clay are briefly reviewed, and comparisons are drawn between empirical data and the predicted behavior of the montmorillonite known to be present in the samples. PROPERTIES OF MONTMORILLONIT E CLAY Water initially adsorbs on dry N a -montmorillonite clay in discrete layers in the interlaminar space between clal platelets. The platelet spacing, which is 9.6 A (angstroms) for a dehydrated clay, has been observed to expand in discrete steps to 12.4, 15.5, 18.4 and 21.4 A spacings, indicating the formation of four discrete layers of regularly oriented water molecules.' The first two layers are easily formed by hydrating a dry sample to equilibrium in an atmosphere with carefully controlled humidity. The formation of the higher layers is more difficult. The usual X-ray diffraction patterns of the more highly hydrated samples indicate a gradual increase in the average spacing betwcen 15.5 and 19.2 A, followed by a discontinuous expansion to 31 A when the weight ratio of water to dry clay is between 0.5 and 1.2.' Platelet expansion above 31 A proceeds monotonically as the moisture is increased and no regular arrangement of the platelets ib observed. Water-sensitivity in sedimentary rocks is usually associated with Na-montmorillonite clay when it is in the noncrystal-line state. Mering3 found that the average lattice spacing of sodium montmorillonite hydrated at 68 F and 70 per cent relative humidity was 15.5 A, and that the spacing, at 92 per cent humidity was 16.5 A. The water adsorbed at the higher humidity has the same free energy as liquid water at 65.6 F. Kolaian and Low' used a tensiometer to measure the thermodynamic properties of water in diffuse suspensions of montmorillonite clays relative to pure water. They observed that water in suspensions as dilute as 6 per cent clay became partially oriented when left undisturbed. The bonding associated with this orientation was not extensive because the free energy difference between the water in suspension and pure water was only a few millicalories per mole. They also found that the measured free energy difference decreased rapidly with temperature and became negligible above 100 F. This evidence indicates that montmorillonites contained in sedimentary rocks would dehydrate to a crystalline structure when exposed to superheated steam, and that the rock permeability measured with steam would be equivalent to that measured with air. The effect of elevated temperatures on the swelline of montmorillonite clays in aqueous suspensions has not been investigated. The Gouy-Chapman diffuse-ion-layer theory has been used to predict the swelling pressure of clay suspensions in dilute salt solutions at room temperature with reasonable success. theory also correctly predicts the direction of the thermal response of Na-mont-morillonite swelling pressures in dilute salt suspensions, 9 Over the temperature range of 33 to 68 F, an increase in

Jan 1, 1966

By Charles C. Peterson, Ronald E. Enstrom

Significant improvements have been made in the ursine systern for epitaxial vapor gvowtlz of Gds. The electron concentration has been reduced to below 1015 cm-3 with electron-mobility values as high as 7200 sq on per v-sec at 30PK and 60,000 sq cw7 per v-sec at 77°K. These high-purity layers have been successfully gvown on n&apos; layers with thicknesses as snzall as 1 p and as large as 125 p. Furthermore, high-purity layers have been incorporated into an structure without degradation of electrical properties. Different impurity gradients at the n&apos; to n interface were achieved. Using these structures, Gunn oscillators have been operated at frequencies as low as 0.4 GHz and as high as 40 GHz, which equals the highest valzle yet reported. The frequencies nleasured are in reasonable apeenlent with those calculated fron7 the n-layer widths and the transit times. CW operatiolz has been achieved from 3 to 20 GHz. In Gunn devices for >40 GHz operation (i.e., witk an n-layer tkickness below 2.5p), the n layer has been generally too pure to permit oscillations to occuv. ThE mechanism of the Gunn oscillator&apos; is now generally understood.2-5 Electron transfer from the (000) minimum to the ( 100) minima leads to a voltage-controlled negative resistance, which results in the formation of domains of high and low electric fields which travel through the crystal with a characteristic velocity of about 107 cm per sec. When a constant voltage is applied to the sample, this domain motion generaliy leads to oscillations at the transit time frequency, fT = 107/L, where L is the thickness of the active n layer.&apos; In this case, a single high-field domain is nucleated at the cathode and grows until it reaches the anode, where it is absorbed; a new domain then forms at the cathode.5 There are related modes of oscillation of the same device in which a tuned circuit causes a periodic variation of the voltage across the device. The frequency then may be either above or below fT. It has been shown that oscillations will occur when n • L 2 1012 cm"2, where n is the carrier concentration in the active region. At lower doping densities, 10" 5 n . L 5 lo&apos;&apos;, the doping is said to be subcritical for oscillation and the description of the device operation changes since the domains become comparable in thickness to the device thickness, L. Nevertheless, such devices have been found to be "active" and, in fact, are useful as amplifiers.778 For CW operation, one wishes to minimize the power dissipation, which is related to the electric field, E, and the low-field resistivity, p. Below threshold, the power dissipation density is approximately Typically, at threshold where E -- 3 x 103 v per cm, the dissipation density is 107/p watts per cu cm, p in ohm-cm. Furthermore, it is desirable to provide good conduction of the heat generated in the active region. The temperature rise, AT, across the active layer of a sandwich structure, with a heat sink on one side, is given by AT = (E&apos;/P)(L~/~~) where it is assumed that the thermal conductivity, u, and resistivity, p, of GaAs do not vary appreciably over the range of temperature and electric fields existing in the layer. This expression shows that, subject to maintaining an appropriate (n . L) product, CW operation is favored by a higher resistivity, a lower threshold field, and a thinner device. The above device requirements place some severe restrictions on the materials to be used, especially for high-frequency (>10 GHz) operation. Here, it is necessary to prepare very thin (<10 µ) layers of GaAs, in a state of high purity (-1 ohm-cm), complete with very low-resistance ohmic contacts. Problems of handling such thin and fragile samples become inereasingly severe as the frequency is raised. Furthermore, while good low-resistance ohmic contacts are easily applied to low-resistivity GaAs, contacting difficulties are encountered for these higher-resistivity materials.

Jan 1, 1968

By G. D. Boozer, W. H. Somerton

RESEARCH CORP., LA HABRA, CALIF. Thermal diffusivities of some typical sedimentary rocks have been measured by a rapid unsteady-state technique. Thermal data including diffusivity and conductivity are presented for the temperature range of 200" to 1,800°F. Diffusivities calculated from steady-state conductivity rneasurernents compared favorably with unsteady-state data at the lower temperatures. Unsteady-state data are less reliable at higher temperatures; reported values may be as much as 20 per cent high at temperatures in excess of 1,500°F. This is caused partly by the simplified method used in calculating diffusivity from experimental data and partly by the many thermal reactions which occur at the higher temperatures. The marked decrease in thermal diffusivity and conductivity at elevated temperatures indicates the importance of considering the temperature dependence of thermal properties in subsurface heat-transfer calculntions. Knowledge of the effects of liquid saturation, overburden and pore pressures, and heats of reaction of reservoir materials will be required before complete subsurface thermal analyses may be made. INTRODUCTION Heat-transfer calculations are becoming increasingly important in the analysis of in situ combustion and underground nuclear explosions. Thermal data for natural rock materials at elevated temperatures are generally unavailable. Calculations at high temperatures may be grossly inaccurate if temperature-dependent thermal properties of rocks are not considered. It is known that the heat capacities of rocks increase with temperature. Heat capacities may be calculated from chemical or mineralogica1 analyses of the rock system. Thermal bulk expansion of rocks is believed to be small, although few data are available. Thermal conductivities of most natural rock materials decrease with increased temperature. Thermal diffusivity, defined as the thermal conductivity divided by the product of the heat capacity and the bulk density of the material, is used in unsteadv-state heat-transfer calculations. It is apparent that thermal diffusivity decreases markedly with increased temperature. A new method, which gives a nearly continuous record of thermal diffusivity within the temperature range of 200° to 1,800°F and requires less than 1.5 hours for the run,&apos; was used to measure the diffusivity of several sedimentary rocks. Thermal conductivities were calculated from measured bulk densities, heat capacities calculated from chemical analysis and the measured diffusivity values. Thermal conductivities were measured at lower temperatures by a steady-state technique1 to test the agreement of data obtained by the two methods.

By Joseph W. Murray

Prior to 1950 Magma&apos;s ore production came from two parallel, steeply dipping, east-west striking mineralized faults, one called the Main or Magma vein and the other the Koerner vein, which lay about 1100 ft to the south. This vein system has been explored and mined over 9000 ft horizontally and 4800 ft vertically. In 1950 continued exploration led to the discovery and development of replacement orebodies in the Devonian limestone zones adjacent to the veins. These replacement deposits occur in the eastern part of the Magma mine and follow the strike and the 30º east dip of the host limestone. Strike length of the ore bodies varies from 250- 500 ft and thickness from 15-125 ft. The orebodies are large tabular masses with chalcopyrite and bornite being the dominant ore minerals. Hematite and pyrite are the most abundant gangue minerals. Incompetent limestone, shale, or a porphyry sill hanging wall is characteristic of portions of the replacement beds. In many instances the ore is blocky, badly fractured and intermixed with layers of limestone gouge, pyrite and hematite.

Jan 6, 1973

By Wilson Blake

Rock deformation and failure taking place around underground openings is usually both accompanied and preceded by the phenomena of rock noise or microseismic activity. These small-scale releases of seismic and acoustic energy can be detected with special geophysical monitoring equipment. Use of this equipment allows one to look inside a rock mass to determine how an opening is behaving under the applied loading system. Microseismic equipment and monitoring techniques are briefly reviewed, and use of the microseismic method as an engineering tool in monitoring rock structure stability is illustrated by case histories. Examples cited range from evaluating roof stability using single-channel portable equipment, to rock burst monitoring using sophisticated computer controlled, multichannel monitoring systems.

Jan 1, 1983

By Michael E. Zellars

The environment for deposition of marine phosphorite is controlled by the relationship of prevailing climatic, oceanographic, structural, and sedimentary conditions. The set, or sets, of conditions that has evoked the accumulation of economic concentrations of phosphorite has been the subject of a number of previous works. Phosphorite presently considered ore is generally in excess of 10% P205 with an extractable phosphate product in excess of 30% P2O5. The concentration of the product in the ore, its amenability to state-of-the-art extraction, and thickness of the overburden are major controlling factors in determining its mineability. A recent survey of phosphorite deposits in the south-eastern United States included a review of the depositional and structural setting for the major areas of occurrence. The application of previous work regarding phosphorogenesis has led to the establishment of a general depositional model for most mid-Miocene primary phosphorites, and, is also possibly applicable to the Bone Valley (Pliocene-Miocene) district of central Florida.

Jan 12, 1978

By Robert M. Lewis

Silica sand deposits are usually contaminated with various heavy minerals which must be removed to make the silica useful for flat-glass production. Research was undertaken to develop a better procedure for producing flat-glass-grade silica. Batch tests revealed that anionic detergent-type reagents had considerable promise. Pilot plant tests were run to compare the effectiveness of anionic detergent-type reagents with petroleum sulfonate in the removal of heavy minerals from a potential glass sand. Another slightly modified commercial procedure also was evaluated for comparison. In the pilot plant trials, utilization of the anionic detergent potation reagents did not produce quite as good results as petroleum sulfonate. It is likely that flat glass-grade sand could be produced with the anionic detergent reagents if more extensive pilot plant tests were conducted.

Jan 1, 1977