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By David E. Jones, Dean K. Hunt, C. Y. Chen

INTRODUCTION Of all the numerous geological hazards that threaten the well-being of urban areas in the United States, probably none is so widespread, persistent, and diversified as surface subsidence (HRB-Singer, Inc., 1977). Simply defined, subsidence is the vertical displacement or sinking of the ground surface caused by either natural phenomena or man's activities. The downward movement, however, can be accompanied by horizontal movement, strain, tilt and even by a locally upward movement. Damage to structures and the environment can result from any of these movements. Extracting subsurface materials, fluids and solids, accounts for most man-induced subsidence in the United States. Among all the mining-related subsidences, the collapse of voids created by underground coal mining has been the major cause in inflicting surface damage (Comptroller General of the United States, 1979). Subsidence from coal mining may occur within a few weeks or be delayed for years, depending upon the mineral layer's depth below the surface, the overlying rock strata's characteristics, the extent and methods of mining that were employed, and the time deterioration of pillar and mine structure. Unless underground resources are not mined or control measures are implemented to prevent or minimize damage, some degree of surface subsidence and its accompanied deleterious effects are often inevitable. The ways to control the subsidence and minimize surface damage may include: 1. Precautionary measures built into new structures or surface features. 2. Preventive works applied to existing structures or surface features. 3. Mine design incorporating special underground layouts. 4. Any combination of the above measures. Upon the enactment of Public Law 95-87, the Secretary of the Interior, through the recently created Office of Surface Mining (OSM), was authorized to promulgate rules to regulate mining reclamation including subsidence control. Proposed on September 18, 1978, these rules were finalized, following public comment and hearings, on March 13, 1979, as part of the permanent regulatory program for the regulation of surface mining and reclamation operations which include the surface effects of underground mining. On January 28, 1981, Secretary Watt of the Department of the Interior issued an order to re- quire all agencies to identify with recommendations all regulations which are believed to be excessive, burdensome or counterproductive. Also on February 17, 1981. President Reagan issued Executive Order No. 12291 requiring all Federal agencies to conduct a regulatory review to make a determination that each promulgation of a regulation is clearly within the authority delegated by law and consistent with Congressional intent (Federal Register, 1981). As a result, OSM initiated the regulatory reform to revise the permanent regulatory program. Following a brief discussion of the technical aspects and the effects of subsidence on man and his environment, this paper presents a historical overview of how rules and regulations are used to govern the subsidence related problems. The development of the regulation of subsidence under Public Law 95-87, the Surface Mining Control and Reclamation Act of 1977 (SMCRA or the Act) are also discussed, including the new regulations being developed under the regulatory reform program. SOME TECHNICAL ASPECTS Am EFFECTS OF FINE SUBSIDENCE An extensive historical review of mining subsidence is given by Zwartendyk (1971) and Shadbolt (1978). Comprehensive technical presentations have been given by Henry (1956), King and Whetton (1957), Hall and Orchard (1963). Muller, et al. (1968). Grard (1969), Voight and Pariseau (1970). Kapp and Williams (1972), Cummins and Given (1973), Brauner (1973) , and NCB (1975). A theory of surface subsidence due to underground mining was perhaps first fundamentally stated by a French engineer, Toillez, in 1838, and formulated by a Belgian engineer, Gonot, in 1839 (Goldreich, 1913, cited by Zwartendyk, 1971). Since that time,

Jan 1, 1982

By A. Weiss, W. A. Coster

The search for ore is characterized by a great variety of uncertainties, each of which can be resolved by obtaining information at a cost. Three exploration stages may be distinguished in which information can be obtained, based on inherently different cost structure: 1) the reconnaissance or scanning stage, 2) the examination or screening stage and 3) the project stage. This exploration sequence would roughly coincide with replies to questions as to: where, how, why and how much. As complete information in each stage is too costly to acquire, we must assess the probability that adequate information will be furnished by a limited amount of effort and attempt to maximize the expected value of ore to be found for a given exploration expenditure. Several problems are discussed relative to the mathematical formulation and possible computer procedures for determining the optimum allocation of a total exploration effort. Based on the available literature possible solutions to this problem are indicated. When scanning through published literature on mineral exploration, it seems at first that there is little room for substantial and systematic improvements in the efficiency with which the problem of discovery of new ore deposits is presently being handled by large organizations active in exploration. It appears equally difficult to offer something relevantly new which could generate a break-through in exploration thinking and cause a marked improvement in the ratio of successful undertakings to the total exploration projects started. On the other hand, a number of experts in recent years have urged that the problems in prospecting be analyzed in a more skillful and sophisticated manner than in the past. Their thesis is based mainly on the premise that the cost of finding mineral deposits will increase with increasing technical difficulties. In present large-scale exploration ventures, especially in those regions where outcrops and immediately visible geologic evidence are scarce, older methods of prospecting are increasingly being replaced by more indirect and systematic geophysical and geochemical methods with more emphasis on correct statistical design of exploration patterns. It is perhaps the oil industry which has made the greatest strides in developing statistically, well justified patterns in its search for oil; possibly because oil seepages, as indicators of the presence of oil, left off at an earlier point in time than did outcrops as indicators of base metals. Among the pioneers in the field of statistics and operations research, as applied to mineral exploration, the excellent works of Allais, Slichter, Koop-man, Mickey, de Guhnin, Krumbein, Griffith, Sichel, Krige, de Wijs, and Matheron may be mentioned. It should, however, be pointed out that three subjects of basic importance to the allocation of exploration efforts have so far received only scant attention in published literature, even by the aforementioned authors. In the first place, a more precise definition of the object of the search, i.e., a minimum-size orebody, seems to be outstanding. Secondly, a decision model is not a widely-discussed subject. Thirdly, no concentrated attempt so far seems to have been made to establish probabilities of the occurrence of economic deposits on a regional scale and to arrive at a slightly more accurate knowledge of the probability laws governing the deposition of ore. It is not the purpose of this paper to create new order in the complexity of uncertainties in which our decision processes in exploration necessarily have to be conducted. Rather, we intend to highlight some of the outstanding, hitherto unmapped territory, where diligent compilation and a utilization of present and historic data may statistically improve our chances of success. We hope that the contribution of this paper will lie in bringing allocation problems into better focus and in increasing the mineral industry's realization of the magnitude of the factors involved. THE MINIMUM-SIZE OREBODY The concept of target specifications for what constitute a minimum-size orebody in exploration is a rather variable one and depends to some extent on

Jan 1, 1963

By C. O. Lee, R. H. Feierabend, Z. W. Bartlett

DESPITE the fact that American brimstone production has increased 2 times since the prewar period 1935-1939, the demand for sulphur exceeds the supply. To alleviate this situation efforts are being made to increase the production of sulphur and bring the shortage to an end. The most important developments are being undertaken on the Gulf Coast. One new brimstone mine has been put into operation and three others are being developed. These projects are expected to account for a large part of the additional sulphur production now anticipated for the free world.'.' Except for a small amount of byproduct sulphur from sour natural gas and refinery gases, American brimstone is produced by the same process devised by Frasch 60 years ago, consisting essentially of the injection of superheated water at about 325°F into sulphur-bearing formations through wells which are drilled from the surface by standard oilfield methods. Sulphur deposits vary in depth from a few hundred feet to 2500 ft from the surface; in a typical deposit the sulphur occurs as crystalline aggregates in porous limestone and gypsum in concentrations varying from 5 to 40 pct, the thickness of the formation ranging from a few feet to several hundred.3 The deposits are usually surrounded by formations impermeable to the flow of hot water, the top and sides being enclosed by impermeable sediments and the bottom by dense impermeable anhydrite. As the hot water leaves the well bore, it percolates through the formation and transmits its heat to the rock and sulphur. When the sulphur reaches 240°F it melts, separates from the rock, and flows through the hot channels downward to the bottom of the well. Here it is freed from incoming water and from formation water, which saturates the porous rock, by gravity separation, liquid sulphur being 1.8 times as heavy as water. It then is pumped to the surface in a relatively pure state, 99.5 pct or better. Chief contaminants are organic impurities, such as petroleum residues, which are soluble in sulphur and tend to discolor it.' Sixteen deposits of commercial magnitude have been discovered in the Gulf Coast area. Five of these deposits have been depleted and abandoned with production totalling more than 26,886,000 tons. Eight properties are operating and have produced 65,875,-000 tons to Jan. 1, 1952, for a total Frasch-type production of 92,761,000 tons. Three new deposits are under development. Aforementioned deposits are listed in Table I. Each of these deposits has been found in the cap-rock overlying shallow intrusive salt plugs or domes and buried in several hundred to as much as 2500 ft of sediments. All salt domes do .not contain sulphur; only 16 sulphur deposits have been found in a total of 231 salt domes which are known to exist in the Gulf Coastal states of Texas, Louisiana, Mississippi, and Alabama. Ten of the salt domes lie in the Gulf of Mexico offshore from the Texas and Louisiana coasts. Additional offshore domes may be found, but their value as a sulphur potential is questionable owing to the great hazard and high cost that can be visualized at these exposed locations where depths of water reach 50 ft. Marsh operations of Freeport Sulphur Co. are in the southeast section of Louisiana. In general, the country is low, flat, relatively uninhabited marshland broken by many shallow lakes and bayous which extend for irregular distances inland. Geologically, the coastal area is of sedimentary origin, having been built up gradually under the sea by deposition of material carried down by large streams to their deltas. Offshore bars were formed enclosing

Jan 1, 1953

By C. O. Lee, Z. W. Bartlett, R. H. Feierabend

DESPITE the fact that American brimstone production has increased 2 times since the prewar period 1935-1939, the demand for sulphur exceeds the supply. To alleviate this situation efforts are being made to increase the production of sulphur and bring the shortage to an end. The most important developments are being undertaken on the Gulf Coast. One new brimstone mine has been put into operation and three others are being developed. These projects are expected to account for a large part of the additional sulphur production now anticipated for the free world.'.' Except for a small amount of byproduct sulphur from sour natural gas and refinery gases, American brimstone is produced by the same process devised by Frasch 60 years ago, consisting essentially of the injection of superheated water at about 325°F into sulphur-bearing formations through wells which are drilled from the surface by standard oilfield methods. Sulphur deposits vary in depth from a few hundred feet to 2500 ft from the surface; in a typical deposit the sulphur occurs as crystalline aggregates in porous limestone and gypsum in concentrations varying from 5 to 40 pct, the thickness of the formation ranging from a few feet to several hundred.3 The deposits are usually surrounded by formations impermeable to the flow of hot water, the top and sides being enclosed by impermeable sediments and the bottom by dense impermeable anhydrite. As the hot water leaves the well bore, it percolates through the formation and transmits its heat to the rock and sulphur. When the sulphur reaches 240°F it melts, separates from the rock, and flows through the hot channels downward to the bottom of the well. Here it is freed from incoming water and from formation water, which saturates the porous rock, by gravity separation, liquid sulphur being 1.8 times as heavy as water. It then is pumped to the surface in a relatively pure state, 99.5 pct or better. Chief contaminants are organic impurities, such as petroleum residues, which are soluble in sulphur and tend to discolor it.' Sixteen deposits of commercial magnitude have been discovered in the Gulf Coast area. Five of these deposits have been depleted and abandoned with production totalling more than 26,886,000 tons. Eight properties are operating and have produced 65,875,-000 tons to Jan. 1, 1952, for a total Frasch-type production of 92,761,000 tons. Three new deposits are under development. Aforementioned deposits are listed in Table I. Each of these deposits has been found in the cap-rock overlying shallow intrusive salt plugs or domes and buried in several hundred to as much as 2500 ft of sediments. All salt domes do .not contain sulphur; only 16 sulphur deposits have been found in a total of 231 salt domes which are known to exist in the Gulf Coastal states of Texas, Louisiana, Mississippi, and Alabama. Ten of the salt domes lie in the Gulf of Mexico offshore from the Texas and Louisiana coasts. Additional offshore domes may be found, but their value as a sulphur potential is questionable owing to the great hazard and high cost that can be visualized at these exposed locations where depths of water reach 50 ft. Marsh operations of Freeport Sulphur Co. are in the southeast section of Louisiana. In general, the country is low, flat, relatively uninhabited marshland broken by many shallow lakes and bayous which extend for irregular distances inland. Geologically, the coastal area is of sedimentary origin, having been built up gradually under the sea by deposition of material carried down by large streams to their deltas. Offshore bars were formed enclosing

Jan 1, 1953

FRENCH steel makers are ready to support the Schuman plan. Pierre Ricard, vice-president of the French Steel Chamber syndicate, announced the industry's readiness to cooperate with the plan, which is aimed toward giving Europe an integrated steel industry. Steel men appear to have decided in favor of the plan because of its promise to unify the continent. Behind approval is the emphasis placed by French steel plant operators on continuation of the Franco Saar economic union. The French have an, abiding fear of German steel production potential. France is currently producing at an annual rate of 11 million tons, while Western Germany is producing 15.5 million tons of steel. The Saar output is placed at 3 million tons. French industrialists feel that as long as the marriage of French and Saar steel production continues, France can compete reasonably well with Germany. If Saar production should suddenly become part of the Western Germany total, it could result in an unequal competitive situation, giving Germany a production level of 18.5 million tons of steel annually, or 60 pct more than France.

Jan 1, 1952

By T. M. Geffen, J. L. Sanderlin, F. F. Craig, D. W. Moore

Scaled reservoir models have been used to study the effect of gravity on oil recovery performance in frontal-drive operations; namely, water, gas, or solvent flooding. The difference in density between the reservoir oil and the injected fluid causes their segregation, resulting in a non-uniform advance of the fluid front. In the laboratory flow tests, which simulated both five-spot and linear injection operations in flat reservoirs, the viscous, capillary, and gravity forces present in these operations were scaled. Dyed fluids were used so that the gross movement of the injected fluid could be observed. The studies covered a range of injection rates, formation thicknesses, and rock and fluid properties normally encountered in field operations. The results of the model tests indicate that the volume of the reservoir contacted by the injected fluid at its breakthrough into the producing well is less than that expected based on information which neglects gravity effects. This difference can often be as much as 80 per cent by gas or water injection in uniform sand bodies. Preliminary flow tests on a non-uniform sand body indicate that the uniformity of the flood fronts may in some situations be influenced to a much greater degree by permeability variations within the rock body than by gravity effects. The magnitude of fluid segregation due to gravity is controlled by the average injection rate, rather than day to day or week to week variations. INTRODUCTION One of the important factors controlling the oil recovery from a frontal-drive operation, such as water, gas, or solvent injection, is the volumetric sweep efficiency. This factor is a measure of the gross portion of the reservoir that is contacted by the displacing fluid. The volumetric sweep efficiency is influenced by gravity effects, well arrangements, and variations in rock permeability within the reservoir. The gravity effects are due to the displacing fluid being of different density than the reservoir oil. This causes the displacing fluid to move preferentially toward either the top or bottom of the formation. Non-uniform advance of the flood front can be caused by the relative positions of the injection and production wells. Variations in rock permeability also result in an uneven advance of the displacing fluid. Gas zones, representing paths of low resistance, may result in non-uniform movement of the injected fluid. The more uneven the advance of the displacing fluid, the lower is the volumetric sweep efficiency and thus the lower the oil recovery efficiency. The effects of well arrangement and permeability variations, upon the gross movement of the injected fluid have been the subjects of extensive investiga-ti0ns.1,2,3,4,5,6 Gravity effects have been recognized as being present in frontal-drive operations'.' but there has been little quantitative measure of their magnitude. Very likely the reason gravity effects have not been studied is that this problem does not lend itself to simple experimental or mathematical analysis. The development of reservoir modeling techniques has made possible a quantitative determination of the effect of gravity on fluid segregation and thus upon the oil recovery performance of frontal-drive operations. This paper presents a progress report on a laboratory investigation of gravity effects in fully liquid-saturated, horizontal, uniform as well as non-uniform systems. These results were obtained from scaled experiments on both linear and five-spot systems within the range of conditions normally encountered in secondary recovery operations. This study is concerned with the gross movement of the injected fluid to the time it first reaches the production wellbore. Therefore, it should be emphasized that the results of this paper can not be used to determine the effect of gravity segregation on oil recovery efficiency at abandonment conditions. MODEL SCALING The science of scaling models is relatively new as applied as petroleum production problems, Many of the scaling techniques have been adaptions of those used in basic studies of heat and fluid flow. There are

Jan 1, 1958

By V. A. Josendal, J. W. Wilson, B. B. Sandiford

Two radioactive tracers have been tested as a means of determining core saturation in multiphase flow studies. Cesium chloride was tried as a water-phase tracer, but complications in its use in low permeability cores resulted from sorption of cesium by the core or water-wet pads. IodoI3'ben-zene proved very satisfactory as an oil-phase tracer. The synthesis of iodobenzene from the sodium iodide as received from Oak Ridge is simple and direct. The tracer is insoluble in water and there was no evidence of sorption by any of the core materials used. use of the method to determine saturation profiles during capillary and dynamic desaturations and relative permeability measurements on oil-water and oil-gas systems is described. Comparisons of the dynamic and capillary methods of relative permeability determination were made using the tracer to check core saturation and saturation distribution. Other experiments are also described in which mobility of the oil phase at various saturations was measured by displacing labeled oil by flowing inactive oil. Similar experiments were made using water labeled with cesium 134. INTRODUCTION To be fundamentally sound. any laboratory method of determining relative permeability must meet, among others, the following requirements: (1) the core saturation between the pressure taps must be uniform, and (2) there must be uniform pressure difference between the phases in the region between the pressure taps. In practice it may eventually be shown that appreciable departure from either or both of these conditions may be permitted without introducing sensible error. but the magnitude of such error remains to be established. There is need then for methods of saturation determina- tion which will determine the saturation profile in a core as well as the overall average saturation given by the gravimetric or material balance methods usually employed. Methods which have received consideration include resistivity, X-ray absorption, gamma ray absorption, neutron diffraction, and radioactive tracers. The resistivity method has use in the determination of profile, but needs checking by independent means.' The X-ray method has been used successfully, but requires elaborate equipment and calibration.23 4 At present gamma ray absorption is practical only for very large cores. The neutron methodo does not appear adaptable to measurement of saturation variations in short cores since it is a scattering method. Russell, Morgan and Muskat' employed radiovanadium in a study of the mobility of interstitial water. Coomber and Tiratsook used radioiodine as an oil-phase tracer and measured profiles in unconsolidated sand packs. ADVANTAGES OF RADIOACTIVITY METHOD A thorough discussion of the theory of radioactive tracers and the technique of using them to study the movement of fluids in sands is given by Coomber and Tiratsoos and need not be detailed here. The method requires less equipment than the X-ray method; the counting problem is similar, but the generation and regulation of the radiation, which is a major problem in the X-ray method, is not required in the radioactivity method. In the X-ray method it is customary to add up to 20 per cent of absorber, usually an iodine compound, to the phase to be labeled. while in the radioactivity method a mere trace is sufficient. A possible disadvantage of the radioactivity method is that a disproportionate amount of the activity comes from the portion of the core nearest the counter, whereas the X-ray gives a true average saturation in the region traversed by the beam. 011 the other hand, this characteristic of the radioactivity method renders it peculiarly adaptable to study of certain types of radial variations in saturation. As with the X-ray method, a tracer may be added to either the oil or water-phase. An oil-phase tracer is more generally useful. however. since it permits work on oil and gas in the

Jan 1, 1952

By H. D. Outmans

The mechanics of filtration are described by a theoretical-empirical nonlinear diffusion equation which, under certain circumstances, may,be linearized and then solved explicitly. For filtration under static conditions linearization leads to a boundary value problem analogous to a heat flow problem with a known explicit solution. The corresponding solution for static filtration is compared with published experimental data. Under dynamic conditions filtration takes place in three successive stages. During each of these the rate of filtration and/or the thickness of the filter cake are different functions of the filtration time. The proposed mechanism explains the observed high resistance of dynamically deposited filter cakes against erosion and also the connection between filtration rate and viscosity of the drilling fluid. Several of the quantities governing dynamic filtration have no counterpart in the static filtration mechanism. The static filtration rate is, therefore, not a reliable measure for the dynamic rate and vice versa. INTRODUCTION Filtration under simulated borehole conditions, i.e.. either from a static suspension or from a suspension flowing parallel to the filter cake (dynamic filtration), has been the subject of several laboratory studies.1-7 This experimental and theoretical work showed that many aspects of the filtration mechanism cannot be explained by an elementary filtration theory based on the assumption that the filter cake is incompressible. For a more satisfactory theory compressibility should be taken into account. This has been done. at least to some extent, in the filtration theory developed for the chemical industry. Surveying the literature (see Ref. 8 for a bibliography) it becomes apparent that, although several properties of filter cakes deposited from many different suspensions have been measured, including compressibility, the filtration equations are essentially empirical in nature. No attempt has been made, for instance, to develop filtration theory along the lines of consolidation theory.12 This theory, upon which a highly successful development in soil mechanics rests, would appear to be an excellent starting point for a filtration theory since the compressibility concept is an essential part of it. As we will use this theory in the following development it is well to state the four assumptions on which it is based: 1. The fluid flow through a compressible porous medium is governed by Darcy's law. 2. The rate of change in fluid content of an element of the porous medium is proportional to the rate of change of solid pressure between the particles. 3. The solid particles are incompressible within the range of pressures considered. 4. The total pressure on a surface normal to the line of flow is equal to the sum of the fluid pressure and the pressure between the particles (solid pressure) at that surface. To calculate the rate of filtration and other quantities of interest it is necessary to know the filter cake compressibility and the permeability as a function of the solid pressure. It has not been possible to calculate these functions from theoretical considerations and they will therefore be introduced in this paper as empirical expressions. Both are determined in a compression cell where the cake is subjected to a mechanical load. Permeability and compressibility are measured after the solid pressure has stabilized, i.e., after the excess fluid pressure has been dissipated and the uniform pressure is transmitted entirely by the solids. The permeability and compressibility thus determined are not the same as during filtration in the borehole, under either static or dynamic conditions, because then, due to frictional drag, the solid pressure and hence also the permeability and compressibility vary along a line normal to the direction of the mean flow and can only be defined locally. DERIVATION OF THE FILTRATION EQUATION FOR COMPRESSIBLE FILTER CAKES As the filter cake in the borehole is thin compared to the radius of the hole the filtration may be considered as linear. Taking the x-axis normal to the wall, with its origin at the formation, we have, according to Darcy's law,

By T. L. Loucks, E. T. Guerrero

Pressure drop characteristics in a system composed of two adjacent concentric regions of different permeability were studied. The differential equations for continuity of mass flow in the two regions were solved using the Laplace transformation and the necessary boundary conditions to give the pressure distribution in the composite reservoir, the resulting equation for pressure drop at the inner boundary was evaluated for a variety of composite reservoirs and compared with the results for a uniform reservoir. From this study it was found that under certain conditions the permeability in both zones, as well as the size of the inner zone, can be determined from the pressure drop curve. INTRODUCTION The theory for the pressure distribution and pressure build-up behavior of a well producing a single, slightly compressible fluid from infinite and finite homogeneous reservoirs was presented by Hornerl and Miller, Dyes and Hutchinson.2 Extensions on this original work to provide improved and extended interpretations and better agreement between theory and observed results have been made by Matthews, et a1,3 van Everdingen,4 Gladfelter, et al5 Stegemeierand Matthews,6 Hurst and Guerrero,7 and Perrine.8 More recently Lefkovits, et al,9 studied pressure build-up behavior in bounded reservoirs composed of stratified layers. Houpeurtl0 has suggested various approaches to the general problem of variable permeability and porosity but presented no analytic solutions for particular permeability variations. Albert, Jaisson and Marionll studied the finite composite reservoir and presented numerical solutions to the unsteady-state case and an analytical solution valid only for large times. They also studied the so-called pseudo-steady state for several examples of radial permeability variations. Very similar examples have been treated in the unsteady state with application to pressure build-up by Loucks in an unpublished manuscript. More recently Hurst12 has presented the complete point-sink solution (valid for all times) for the infinite composite reservoir. He applied these solutions to interference between oil fields along with an even more elegant application of his explicit solution to the material-balance equation including water influx. Mortada 13 approaches the same application by avoiding the point-source limitation but gives the solution for the aquifer region which is valid only for large times. Hopkinson, Natanson and Temple14 have treated both the finite and infinite composite reservoir obtaining the pressure distribution for the inner zone valid for large times. This paper presents a theoretical study of the pressure distribution in an infinite composite reservoir composed of two adjacent concentric regions of different permeability. The object was to determine the manner in which pressure drop at the inner boundary of a composite reservoir depends upon time, the permeability of each zone and the size of the inner zone. Expressions for the pressure distribution in both zones are developed which take into account the radius of the sink and are valid for small times as well as large times. It was felt that an understanding of the pressure drop behavior in various composite reservoirs would be of assistance in the interpretation of some pressure build-up curves which do not behave according to the theory derived for uniform systems. Often the region surrounding the wellbore is either more permeable or less permeable than the reservoir because of the various drilling and completion practices. The effects of reduced permeability due to drilling-fluid invasion and of increased permeability due to fracturing or acidizing need to be more carefully defined. Therefore, an equation for the pressure drop in a composite reservoir was developed, and the effects of both the permeability in each zone and the size of the inner zone were studied. STATEMENT AND SOLUTION OF PROBLEM BOUNDARY CONDITIONS AND ASSUMPTIONS The physical system studied was a composite

By J. D. Doherty

That America's great coal deposits eventually will be our principal source of liquid as well as solid fuels is generally accepted. Moreover, the day when synthetic oil from coal will begin to supplement our petroleum supplies does not appear to be far off. The American petroleum industry has not spared effort or expenditure in its attempt to keep pace with the demand for oil, and recent production has exceeded expectations. However, the rapidly rising demand for liquid fuels plus the increasing difficulty of finding and developing the new oil needed even to maintain present production rates make it highly unlikely that oil from domestic wells can fully meet future oil requirements. Therefore, it appears that one or more of the following courses must be followed: 1. Curtail oil consumption. 2. Incr ase imports. 3. Develop new sources such as synthetic liquid fuels. All three courses may well be needed, as it is doubtful that any one of the three alternatives alone can satisfactorily solve the problem indicated by the prevailing trend in demand for oil. Curtailment of oil consumption is not a constructive policy, except where oil is being wasted or coal can be readily substituted as in stationary steam plants. Reduced oil supplies for most uses will curb our economic advancement and, in addition to inconveniencing consumers, will have a pronounced adverse effect on American industry. The oil-burner-manufacturing industry already has been dealt a hard blow. Shipments in the first 5 months of 1948 decreased 70 pct from those in the same period in 1947.1 The effect of a similar cut in the automobile industry can be imagined. A severe prolonged shortage of gasoline could seriously disturb our present economic well-being. It might be pointed out also that even the prospect of a shortage or lack of assurance for the future can discourage buyers of equipment, as occurred in the case of oil burners. An increase in our imports of oil seems to be a necessary expedient for the immediate future. Its advantages are that it will require a minimum of manpower and steel in a time of critical shortages and will conserve domestic reserves. Any major dependence upon foreign sources for our oil supplies should be avoided, however. Other nations are increasing their oil consumption more rapidly percentagewise than the United States and eventually will compete with us for the not unlimited world supplies. In peacetime, foreign countries might restrict ship- ments of oil to this country or impose exhorbitant prices. In the event of war, there is serious danger that such sources would be cut off, and American-developed oil fields overseas might even be used against us. Although synthetic fuels cannot relieve any oil shortage that might develop within the next year or two, an immediate start toward a substantial synthetics industry to supplement petroleum not only could help relieve shortages several years hence but also would help establish the much needed "know-how" for large-scale production. By assuring ample future supplies, such a start would permit sound planning by industries dependent upon oil and maintain or restore the confidence of prospective customers for oil-con-suming equipment. If it is agreed that domestic production of crude oil cannot be expected to meet future domestic demands, that oil rationing in general is undesirable. and that too great dependence on foreign oil should be avoided—and the weight of the evidence supports such conclusions—it is inescapable that commercial synthetic fuel production should be developed to supplement domestic petroleum supplies, which, of course, will furnish the bulk of our requirements for yean to come. Sources of Synthetic Oil The three principal sources of synthetic oil are natural gas, oil shale, and coal. A commercial plant using natural gas is under construction, and expansion of this industry is expected.

Jan 1, 1950

By D. J. Carney, E. Richard Randolph, E. Van Meter, J. J. Oravec, Stanley H. Ward, Gerald J. Anderson, Rolland L. 203-000-000-005 Blake

DURING the last 30 years the inductive electromagnetic method has been used chiefly in the search for massive sulphide mineralization. This application has met with varying degrees of success and in recent years has resulted in discovery of several large orebodies. Little has been written concerning its use in exploration for soft iron ores, but one of the present authors has reported on experiments with massive magnetic deposits.' To augment the exploration tools available to geologists in delineating iron orebodies, Cleveland-Cliffs Iron Co. and McPhar Geophysics Ltd. undertook in 1953 to apply the inductive electromagnetic method to Cleveland-Cliffs properties in the Lake Superior region. As a result of this project, equipment has been developed that enables simultaneous transmission of two audio frequency waves, and the field technique and interpretative procedure involved have furthered exploration in the district significantly. Thus far, inductive electromagnetic application in the Lake Superior region has been only a development tool, that is, it is used to locate obscured contacts and faults as a part of property expansion and development. However, its application to primary reconnaissance of unexplored areas may be feasible in the future. The method has assisted in placing drillholes efficiently, and the elimination of excess drilling foot-ages and/or actual elimination of unnecessary holes has amply justified the expense of the geophysical survey. Cost of the field work involved is comparable on a per station basis to the cost of a magnetometer or superdip survey. Since observations require no reduction, i.e., are directly interpretable, overall expenditure is low, and the scope and detail of the survey can be adjusted in the field as geological- geophysical correlation becomes evident. To a great extent, this eliminates the second-guessing so commonly arising after office calculations are completed on data obtained with other types of geophysical surveys. This unique feature of field interpretation and its associated intimate feel of the project area, is, perhaps, one of the most valuable aspects of the inductive electromagnetic method as applied to iron ore exploration. Basis of Method Fundamentally, the method involves transmission of an alternating electromagnetic wave, of a chosen audio frequency, which permeates the ground materials in the vicinity of a transmitting, or primary, coil, see Fig. 1. This wave, or field, induces an electric current in any conductor on which it is incident. The flow of an alternating current in a conductor sets up its own, or secondary, radiating electromagnetic field. These two fields form a resultant whose configuration depends on the following characteristics of the subsurface conductors: 1) size, 2) shape, 3) electrical conductivity, 4) magnetic permeability, and 5) frequency of the transmitted wave. To a lesser extent the resultant is also dependent on material adjacent to the conductor, topography, and surface conductivity. For illustrative purposes, the primary, secondary, and resultant fields may be represented by vectors. In operation, the direction of the resultant vector is measured by a small receiving coil tuned to the frequency of the transmitted wave. Generally speaking, the method can be compared to the transmission and reception of the familiar radio broadcast, with special variations permitting measurement of the effect on reception of intervening materials. Field Technique Mechanics of field operation are simple. The mast is set up in a vertical position and is then guyed in place. The transmitting loop then is raised by means of a sheave at the top of the mast and the coil connected to the motor-generator. A special plane table is clamped into position on the mast and the loop is plumbed. The plane table is oriented according to a grid system established over the project area. By means of this plane table it is possible

Jan 1, 1956

By J. J. Taber, W. K. Meyer

Experiments on consolidated sandstones have shown that a variety of conditions are responsible for the wide range of behavior observed when oil and water are displaced simultaneously by a solvent which is miscible with both. The type of displacement is influenced most strongly by the relation between the plait point of the ternary phase diagram and the composition path followed by the system as it achieves mis-cibility. Neglecting viscosity, the displacement becomes less efficient as the distance between the composition path and plait point is increased in either direction so that a very wide spectrum of displacements is possible with different alcohol, oil and brine systems. It is possible by choosing various composition paths as miscibility is achieved to exercise some control over the actual displacement mechanism. Control over the composition path is exercised by adding oil or water in specific amounts to the alcohol prior to its injection into the porous medium. This technique apparently makes it possible to obtain piston-like displacements with systems which are usually characterized by the efficient displacement of only one of the two phases i.e., either oil or water, while the other phase lags behind. However, the simultaneous displacement of oil and water is not as efficient as other miscible displacements at a similar mobility ratio. The evidence indicates that both oil and water "leak" into the alcohol "piston" in compensating amounts. With oils of low viscosities the displacement is inefficient because the low oil saturation in the stabilized bank causes oil to be trapped by water before miscibility is attained. INTRODUCTION The simultaneous displacement of oil and water by solvents such as alcohol has been investigated in the laboratory and in the field. The laboratorv workers investigating all-liquid miscible systems have recognized the great importance that the nature of the traingular phase diagram exerts on the efficiency of the miscible displacement. Gatlin and Slobod pointed out that displacement efficiency will be improved if miscibility can be retained for long periods and that this behavior tends to be followed if the applicable phase diagrams have very low binodal curves. In their unconsolidated sand tests the alcohol was considered an ideal miscible piston displacing both oil and water phases. Later workers have pointed out that an important feature of the phase diagram as far as oil recovery is concerned is the location of the plait point. This is particularly true in the case of consolidated Sandstone.3 Since the original discussion of this effect, the importance of plait-point location has been confirmed and discussed by other author The early workers394 recognized that the position of the plait point could be altered by changing the oil or the alcohol used in an experiment. In addition, recent work has demonstrated that the plait point can be shifted by altering the nature and concentration of dissolved salts in the aqueous phase. However, the entire scope of the relationship between displacement and plait point has not been discussed previously and a technique for changing the composition path as miscibility is achieved in a particular ternary system, i.e., oil, water and solvent, has not been demonstrated. * The importance of oil viscosity on the efficiency of oil displacement by alcohol has not previously been observed, probably because the range of viscosities used in earlier experiments was too restricted. It is the object of this paper to describe the relationships between the ternary phase diagram, fluid properties and the displacement achieved. A technique for controlling the nature of the displacement is also presented. THEORY AND DEFINITIONS PISTON-LIKE THEORY The theory of alcohol flooding has been discussed in some detail.2-4 The concept was advanced that

Jan 1, 1965

By P. A. Beck, Hsun Hu

It has been known for many years that in cold drawn polycrystalline aluminum the recrystallization texture is practically identical with the deformation texture.l,2,3 V. Goeler and Sachs4 stated that in cold rolled polycrystalline aluminum, too, the deformation texture is retained upon recrystallization. This behavior was interpreted by Dehlinger9 as an indication that each recrystallized grain inherits the orientation of the matrix in which it grew. However, Burgers and Basart showed6 that in deformed aluminum single crystals the orientation of the recrystallized grains strongly deviates from that of the matrix. Barrett demonstrated8 that even in deformed polycrystalline aggregates the local orientation within each deformed grain changes on recrystallization. No explanation has as yet been offered of how the aggregate texture can be retained, while the local texture is everywhere changing. According to Burgers and Louwerse6 the orientation change on recrystallization in compressed and rolled aluminum single crystals corresponds to a rotation around [112] axes lying in the active slip planes and perpendicular to active slip directions. This orientation change was rationalized by them on the assumption that the orientation of the recrystallized grains is determined by the orientation of the available nuclei, and that these nuclei are small fragments of the deformed crystal, rotated in the deformation process. Barrett pointed out,? however, that these assumptions were by no means proven, and that the total volume of material necessary for the nuclei is so small, that it must be available in any orien- tation whatever. It is, therefore, unlikely that an "oriented nucleation" theory could satisfactorily explain the orientation changes in recrystallization of a deformed crystal. Furthermore, in contradiction to Burgers and LOU-werse's conclusions, Barrett's results for the orientation change could be best expressed in terms of rotations around. [Ill] axes. Thus agreement is lacking not only in the interpretations but apparently even in the experimental results contributed by the various investigators. The orientation relationships on coarsening* in a highly oriented polycrystalline matrix were first investigated by Burgers and Basart.5 They produced a fine grained highly oriented matrix by the recrystallization of a compressed or rolled single crystal of aluminum, and studied the orientation relationships in three successive generations of crystals: the "deformation texture" in the single crystal, the recrystallization texture, and the coarsening texture. Burgers24 showed that the preferred orientation of each successive generation was almost always widely different from that of the preceding one, but that the coarse grains often approximately reverted to the orientation of their grandparent, the deformed single crystal. This observation, and the idea that the orientation of the coarse grains is determined by that of the available "nuclei," led to the concept that the coarse grains are nucleated by the remnants of the deformation texture.12,15 On the other hand, Bowles and Boas16 found, in a carefully conducted experiment, that in recrystallized fine grained copper of cube texture coarse grains grow in orientations which can be derived from the orientation of the recrystallized matrix by rotation around a [lll].] direction: the coarsening texture here does not appear to be related in any simple manner to the original rolling texture from which the cube texture had been obtained by recrystallization. It may be assumed that in a recrystallized material, even with a strong texture, there always are present some grains of practically any orientation. These may serve as "nuclei" for the coarse grains, provided that the conditions are favorable for their growth. The existence of a coarsening texture may be considered as an indication that grains with certain relative orientations with respect to the preferred orientation of their neighbors can grow much faster than others. This "oriented growth" theory was briefly suggested by van Arkel, as early as 1936,13 and it was mentioned by Burgers." Recently, C. G. Dunn produced direct

Jan 1, 1950

By Frank T. Weems

The basic operating properties of the DorrClone are discussed and certain metallurgical applications which exploit these properties are presented. An effective method of controlling the consistency of the DorrClone underflow is described. THIS paper presents in a general manner some of the applications of the DorrClone (Dutch States Mines cyclone) in the metallurgical and heavy chemical fields. Technical or mathematical analyses of the design factors and of the mechanism whereby the cyclone effects its separation have been capably treated in a series of previous papers.'-' Engineering and operational aspects of a few installations and laboratory tests have been chosen to emphasize the unique classification characteristics of the DorrClone and to illustrate its utility in certain difficult situations. Its use in coal washing and heavy-media operations are not considered. Some 25 or more industrial installations and applications of the DorrClone in the metallurgical fields are operating at present, ranging from single trial units to complete batteries composed of a multiplicity of units. The data were obtained in part from some of these, and in part from operations of units at the Westport Mill, the laboratories and testing plant of the Dorr Co. at Westport, Conn. The DorrClone was developed, in principle, by the research dept. of the State Mines, Limburg, Holland, during World War 11. Its first use was to dewater a —50 micron sand used as a dense medium in coal washing. The metallurgical wet cyclone was first publicized by Driessen and Yancey and Geer.6 ince then the cyclone has been studied as a means of de-watering, heavy media concentration, and fine size classification. The DorrClone is shown in Figs. 1 and 2. pulp to be treated is pumped through the feed nozzle, A, into the feed cylinder, B. The feed nozzle is of rectangular cross-section, the outermost edge being tangent to the feed cylinder walls. Feed shims, C, may be attached to the innermost walls to adjust the open area of the feed nozzle available to entering pulp. The tangential injection of feed under pressure supports the vortex action of the pulp that has been detained in the cyclone; the centrifugal forces of this vortex throw the coarse particles to the walls of the cone, D, where they collect and pass downward and out through the adjustable apex opening, E. The fine particles contained in most of the water that entered with the feed pulp move to the inner spiral of the vortex and flow out through the vortex finder, F, contained in the orifice plate, G, which forms the top of cyclone chamber. The overflow pulp may then spray freely into a spray chamber, H, surmounting the cyclone or pass directly into a 90' elbow, I, of somewhat larger diameter than the vortex finder. Installation Where more than one cyclone is to be installed, best overall efficiency and ease of control are obtained with equal distribution of both pulp volume and weight of solids among the cyclones, and with the same pressure being maintained at each cyclone feed nozzle. Fig. 3 is a suggested arrangement for feeding two or more cyclones in parallel. Feed pressure control: Under normal operating conditions it is not unusual for some surge to exist in the feed that is to be sent to the cyclone. As will be discussed later, surges in the solids content of the pulp are usually not of great operational consequence, but surges in feed volume are a problem. Several systems have been devised for absorbing surges in feed volume, each involving a surge tank. If the surges are small and fairly rhythmical, a tank of sufficient size might be installed to dampen out

Jan 1, 1952

By R. E. Collins, Paul B. Crawford

Potentiometric model studies have been made of ertically fractured reservoirs. All fractures originated at he well and extended into the reservoir for various distances. Studies were made to determine the areal sweep efficiencies for line-drive patterns. The areal sweep efficiency for the unfractured system studied war 70.6 per cent. It was found that if the vertical fracture war paralIel with the direction of flood, the areal sweep efficiency may be considerably reduced, approaching zero in some instances. If the fracture was at right angles to the direction of flood, the areal sweep efficiency may be greater than that for the unfractured system. The sweep efficiency depends on the length and orientation of the fracture and direction of the flood. It is concluded that considerable effort should be made to determine the nature and direction of fractures before initiating a flooding program. Such information is required if the maximum sweep efficiency is to be obtained and channeling is to be reduced to a minimum. INTRODUCTION The recent development and application of fracturing techniques to petroleum reservoirs has served to focus considerable attention on the effect such fractures may have on secondary oil recoveries. The opinion has been expressed that fracturing may not alter appreciably the water flooding possibilities. Others have thought that channeling may occur and that the creation of fractures may serve to substantially reduce the possibilities of conducting a successful water flood in the reservoir The purpose of this study was to obtain quantitative estimates of the effect of vertical fractures on the areal sweep efficiencies of line-drive flooding patterns. In presenting this work on vertical fractures, it is not to be inferred that the present fracturing techniques result in producing a vertical fracture. The types of fracture which are created are not known with certainty in every case. Some are believed to be horizontal, others inclined along bedding planes, and some data indicate vertical fracturing. Each fracture will probably exert a different influence on the sweep efficiency of the secondary recovery program; consequently each fractured well should perhaps be considered as a separate problem, requiring a careful analysis. Preliminary work on the effect of fractures on producing capacity of a well indicated that for practical purposes many fractures may be treated as having a nearly infinite permeability This assumption appears to be valid in some instances where the permeability of the fracture is only 10 or 100 times greater than the permeability of the matrix. It is known to depend on the type, orientation and length of the fracture. In realization that fractures of only 0.01 in. width have calculated permeabilities near 5,000 darcys, it is believed that many fractures may be considered as of near infinite permeability without incurring serious error. Primarily for this reason this study was made with fracture analogs of very great permeability compared to the matrix. FRACTURED SYSTEM ANALOG The pattern sweep efficiencies reported here were obtained with the aid of a potentiometric model. The application of this type model for solving reservoir problems has been described in the literature.1,2,3 The electrolyte reservoir was 20 in. wide by 30 in. long by approximately % in. deep. The liquid depth was constant, which corresponded to a constant permeability-feet product from the injection to the production well. The electrolyte reservoir was built to correspond to a unit in the line-drive pattern shown in Fig. 1. This figure shows part of an infinite array of wells having alternate rows of fractured and unfractured wells. The area within the dashed rectangle shows the area generally studied in the model. In using the model to represent a fractured system, a thin strip of copper was soldered to the well or wells and the length and orientation of the strip was made to conform to the vertical fracture under consideration.

Jan 1, 1955

By G. Sachs, E. J. Riping

All ferrous alloys can be made brittle by straining at sufficiently low temperatures. However, the changes in mechanical properties for different ferrous materials with decreasing testing temperature do not appear to follow any universal law. In particular, complex effects of testing temperature have been observed if cold worked steels were subjected to tensile tests at low temperatures. EFFECTS OF PRESTRAINING AT A TEMPERATURE ABOVE THE TESTING TEMPERATURE ON THE FRACTURE CHARACTERISTICS‡ A considerable amount of data has been presented by a number of investigators on the fracture characteristics of various cold worked steels.' These data usually relate to a two-step procedure first used by Davidenkov,² consisting of stretching by tension to a certain strain or " prestraining" at room temperature and then completing the tensile test, or "testing" at the temperature of liquid air. On the basis of data of this type made available to date, ferrous alloys can be classified into two groups with respect to their fracture characteristics observed on testing at a low temperature after prestraining at room temperature. Very complex phenomena have been observed for all annealed steels. On the other hand, some observations indicate that steels in certain other conditions represent a fundamentally simpler relation. In considering the effect of prestraining at one temperature on the properties obtained at some lower temperature, it should be expected that any cold work reduces the ductility retained in proportion to the magnitude of the cold work. However, the test data presented to date indicate that only heat treated (quenched and tempered) steels appear to conform to this expectation, according to the very limited test data in Fig 1, presented by McAdam, Geil and Mebs. This series of tests, Fig 1, shows that the retained ductility became smaller the larger the prestrain. However, this decrease is less than the amount of prestrain or, in other words, less than the decrease in ductility at the prestraining temperature. These effects of prestraining are fundamentally identical with those observed by Bridgman3 when a steel was prestrained (in tension) under hydrostatic pressure and then subjected to a regular tension test. It appears, therefore, that the basic effect of prestraining under conditions which yield a higher ductility than the (subsequent) testing procedure, consists of gradually increasing the total ductility of the metal from the initial low value of testing to the higher value of prestraining. On the other hand, all annealed steels, if cold worked by tension at room temperature and then tested at a lower temperature, provided that some ductility is retained, showed a far more complex behavior than that discussed above. This relationship is exemplified by Fig 2, for three pearlitic steels.4,5 These particular steels were selected because of the various shapes of their ductility-prestrain curves. All three steels, and any other investigated so far, suffered a rapid decrease in retained (and consequently also in total) ductility when subjected to small pre-strains. Then, after exceeding a certain prestrain it was generally observed that the ductility recovered.* This rather complex behavior of annealed steels may be tentatively correlated with the presence of stretcher strains at small restrains. Heat treated steels do not exhibit stretcher strains. This fact might possibly explain their simpler prestrain-retained ductility relationship. The destructive effect of these stretcher strains may possibly be associated with the presence of triaxiality, which may occur in any highly non-uniform stress and strain state (and which is retained as residual stress after unloading). Even a small degree of triaxiality may then cause a reduction in ductility, or even embrittlement at a sufficiently low testing temperature. The discussion presented above deals with the effects of cold working at a high temperature on the fracturing

Jan 1, 1950

By E. Martinez, M. L. Hollander

Sulfurization of copper oxides was investigated using differential thermal analysis (DTA) and thermal gravimetric analysis (TGA). When mixtures of cuprous oxide and sulfur were heated, the surface of the cuprous oxide was converted to cupric sulfide at the melting point of sulfur (119°C); additional sulfuriza-tion took place when the sulfur vaporized above 200°C. Cupric oxide also reacted with sulfur to form cupric sulfide but the starting temperature was approximtely 225°C. When the cupric oxide and sulfur were physically separated, sulfurization still occurred indicating a reaction with the vapor phase of sulfur. Sulfurization was obtained in runs with cuprite, chrysocolla and basic copper carbonate. Further decomposition of cupric to cuprous sulfide was noted at somewhat higher temperatures. The DTA-TGA data made it possible to set up postulated reactions in each system. These techniques were found to be well suited for studies of this type. Because of the difficulty encountered in flotation of many metallic oxide minerals, efforts have been made to find suitable reagent combinations to sulfi-dize these minerals in the flotation circuit. Recently Bautista and Sollenberger,1 using a different approach, showed that the surfaces of many oxide minerals can be converted to sulfides by heating them with sulfur to temperatures between 150° and 225°C. This technique was effective even with chrysocolla, a mineral which is very difficult to sulfidize. The primary objective of the present study was to obtain information on the reactions between the oxide minerals and suIfur. A better understanding of the mechanisms involved might prove useful in pointing the way to improvements in the process. A secondary objective was to demonstrate the value of thermo-analysis in investigations of this type. Bollin and Kerr2 have reported the use of a modification of differential thermal analysis to study the thermal reactions which occur on heating elemental constituents in a closed system to synthesize copper sulfides and iron sulfides. Differential thermal analysis (DTA) was used to detect enthalpic changes as mixtures of minerals and sulfur were heated. The DTA indicated the temperatures at which reactions started and whether they were exothermic or endothermic. Weight change data were obtained by thermal gravimetric analysis (TGA). These data could often be used to support postulated reactions and to eliminate consideration of other possible reactions. EQUlPMENT Differential thermal analysis (DTA) involves measuring the temperature difference between the sample being tested and a thermally inert reference, generally aluminum oxide, as both are heated at a uniform rate. Series connected thermocouples in the sample and reference are used to detect the temperature differences that occur as the sample undergoes enthalpic changes.3 Crystalline transitions, fusions, vaporizations, dehydrations, decompositions and many solid state reactions can be detected. A DTA unit manufactured by the Robert L. Stone Co., Austin, Tex., was used in this investigation with a temperature rate increase of 10°C per min. The samples and reference were placed in Inconel cups with wells in the bottom into which the differential thermocouples fit, and run in a nitrogen atmosphere. Thermal gravimetric analysis (TGA) measures the changes in weight that a sample undergoes as it is heated. A Chevenard thermobalance converted electronically for graphic recording was used with a heating rate of 5°C per minute. An X-Y recorder plotted temperature on the X axis and weight changes on the Y axis. A flow of 250 ml per min of nitrogen was streamed through the furnace. Samples were placed in a porcelain crucible open at the top, unless otherwise noted. EXPERIMENTAL RESULTS Sulfur: Two sulfur samples from different sources were tested. The DTA of a high purity sulfur and a reagent grade sublimed sulfur are shown in Fig. 1. Nearly all the tests were run with the sublimed sulfur due to the difficulty in grinding and high electrostatic charge encountered with the high purity sample. Sulfur undergoes three endothermal reactions below 200°C. The first is a solid-solid crystalline transi-

Jan 1, 1964

By D. R. Wieland, H. T. Kennedy

The object of the work reported here was to determine the content of elemental sulfur in gaseous methane, carbon dioxide, hydrogen sulfide, and in mixtures of these gases, at pressures and temperatwes encountered in natural gas reservoirs. Sulfur content at equilibrium is reported for pure methane, carbon dioxide, hydrogen sulfide, and on three binary mixtures of each of the three pairs of gases at pressures of 1,000, 2,000, 3,000, 4,000, 5,000 and 6,000 psia and at temperatures of 150°, 200° and 250°F. In addition, the sulfur content of three ternary mixtures at the same temperatures and pressures are reported. The results indicate that the sulfur content is higher in the gases at higher temperatures and pressures. The content is highest in hydrogen sulfide, intermediate in carbon dioxide and lowest in methane. INTRODUCTION At ordinary pressures and temperatures, the concentration of a nonvolatile material, such as sulfur in a gas at equilibrium, is a function of the vapor pressure of the material and is independent of the nature of the gas. As the pressure and temperature increase, the gas assumes some of the properties of liquids, including the power to dissolve other liquids and solids, to an extent dependent on the nature of both the gas and the material dissolved. At equilibrium, the content of sulfur in the several gases considered here may thus be considered as solubilities which are fixed for a given composition of gas, temperature and pressure. The study of the solubility of elemental sulfur in gases is of interest because sulfur is sometimes present in reservoirs producing natural gas and must be present in the vapor phase. Upon reduction of pressure and temperature, the sulfur precipitates from solution in the reservoir and in the tubing and fittings. Due to the fact that the greatest pressure drop in the reservoir is around the wellbore, the volume of sulfur precipitated will be greatest in this locality and can cause a substantial reduction in the permeability of the formation in this area. As the natural gas flows up the tubing string, the pressure and temperature are further decreased, causing further sulfur precipitation. If the volume of free sulfur is large and remedial measures are not taken, complete plugging of the tubing can occur. Knowledge of the content of sulfur as a function of composition, temperature and pressure will enable the operator to determine what changes in pressure and/or temperature are necessary to keep the sulfur in solution. If the sulfur solubility is large and can be controlled, the operator may desire to produce the well at a high wellhead pressure and temperature and reclaim the sulfur at the surface. The high solubility of sulfur in hydrogen sulfide (5.6 per cent by weight at 5,000 psi and 200°F) suggests the feasibility of recovering sulfur by injecting this gas into sulfur-bearing reservoirs and expanding the produced gas to precipitate out the sulfur. The present project was designed to measure the solubility of sulfur in carbon dioxide, methane, hydrogen sulfide and mixtures of these three gases at various temperatures and pressures. These gases were the major constituents of the gas well where plugging by sulfur was encountered. A study of the published literature shows no data on the solubility of sulfur in any gas, although Hannay and Hogarth,' in 1880 reported that it was soluble in carbon disdlide above the critical temperature of carbon disulfide. EQUIPMENT AND PROCEDURE Fig. 1 shows the layout of equipment employed to bring gases to equilibrium with sulfur and to isolate the quantity of sulfur contained in a known volume of gas. Pure gases were measured in the charging bomb at known temperatures and pressures and displaced into the reservoir bomb to make up the desired mixtures. When equilibrium was achieved

By J. Weertman

It is shown that conditions suitable for the conversion of straight dislocations into helices are common in crystals hardened either through long-range dislocation interaction or by jog formation on dislocation lines. For dislocations other than screw dislocations or dislocations nearly screw in orientation, helices can be formed with the aid of core difhsion at temperatures low relative to the melting point of the material. It is assumed that, once formed, helices will degenerate into dislocation tangles. THE dislocation tangle is one major dislocation arrangement observed by the transmission electron microscope which had not been predicted previously from dislocation theory. Since first being observed, the tangle itself has become important in applied dislocation theory. The Cambridge school (P. Hirsch) bases part of its theory of work hardening upon this phenomenon.' In spite of the fact that the tangle obviously is a structure of prime importance to a cold-worked crystal, until recently relatively little attention has been paid to the question of exactly why or how tangles arise. It was generally assumed at first that cross slip and perhaps jog formation will lead to tangles. However Wilsdorf and schmitz2 concluded that cross slip cannot markedly contribute to the tangles. The Wilsdorfs and Maddin3'* have proposed that tangles arise by means of prismatic dislocation loops and superjogs which are produced by a precipitation of point defects. Dislocations with superjogs or which have joined with prismatic loops are themselves dislocation sources and they can produce new dislocations, a process they call "mushrooming", which then tangle with each other. There is no question that the Wilsdorfs et al. mechanism as well as the cross slip one can pro- duce tangles. However these may not be the only paths leading to tangle formation. In this paper we wish to consider another way tangles can form. Our work will be based on the theory of dislocation screw We wish to show that whenever a crystal is cold-worked there always is present a "driving force" leading to helix formation and thus to tangle formation. We do not expect to observe well-developed, regular helices in cold-worked metals. Rather we would expect that after a helix is formed random interactions with nearby dislocations will cause a well-developed helical dislocation to go over into an irregular form. A dislocation tangle is, of course, a grouping of dislocations with irregular forms. Therefore we feel that, in accounting for the formation of dislocation tangles, it is sufficient to show that many dislocations in a cold-worked crystal will take on helical form. The crucial step is helix formation. In order to have a straight dislocation assume a helical form, diffusion of vacancies, or interstitials, must occur. Our discussion of tangle formation therefore will be limited to crystals which have been deformed at temperatures ranging from about one fifth to half their absolute melting point. In this tem per a ture range appreciable core diffusion is possible. (There is no problem in explaining tangle formation at temperatures greater than half the melting point. At such temperatures dislocation climb through a bulk diffusion of point defects gives an extra degree of freedom to dislocation motion. This extra freedom of motion makes tangle formation easy.) At temperatures much below one fifth the absolute melting temperature diffusion processes are sufficiently slow that helix formation does not occur. Of course helix or tangle formation could occur in material deformed at very low tempera-tures which was subsequently warmed in order to make the thin specimen necessary for electron-microscope examination. Since within the temperature range of approximately one fifth to half the melting temperature the diffusion of point defects in the core of the dislocation is rapid, we can reasonably assume that within

Jan 1, 1963

By R. A. Morse, C. R. Holmgren

The production of oil by water flooding can be substantially increased by the maintenance of free gas saturation in the reservoir during the flooding operation. This effect is accomplished by the alteration of oil relative permeability characteristics and the occupation by gas of pore space that would otherwise be filled with residual oil. The amount of reduction In residual oil can be calculated from appropriate water-oil relative permeability characteristics. This paper presents experimental data in support of the foregoing conclusions and an example of the calculations. The microscopic pore saturation concepts of the mechanism are discussed. A method of practical application to field floods is presented together with discussion of certain limitations. INTRODUCTION The presence of free gas has been reported by a number of investigators to significantly affect the oil recovery which can be obtained from sandstone flow systems by water flooding.1,2,3,4,5 The effect of gas, noted in every instance, has been to cause lower residual oil saturations than could be obtained by water flooding the same systems in the absence of free gas. The degree of improvement in recovery has been observed to vary widely, depending on the systems used and the conditions of the tests. The increased oil recovery obtained because of the presence of gas during a water flood has been variously attributed to changes in physical characteristics of the oil, selective plugging action of the gas, inclusion of oil mist in the free gas phase, and the additional sweeping or driving action of the free gas. All but the first of these suggestions imply changes in the displacement mechanism. The change in viscosity and inter-facial tension of the oil phase, within the pressure range used for all the experimental work, is certainly not sufficient to account for the differences in residual oil saturation noted dess there is a drastic change in the displacement process. One other effect which logically seems capable of causing differences in residual oil saturation of the magnitude noted in the experimental work is that of simple replacement. In a water-wet system containing oil, water, and gas, it is to be expected that the gas will exist inside the oil. This is the position of minimum free surface energy, since the gas-oil interfacial tension will be less than the gas-water interfacial tension. There is no apparent reason to expect that the existence of free gas within the oil phase should alter the saturation at which the non-wetting phase (now oil and gas) should become discontinuous and hence trapped so as to be unrecoverable by direct displacement by water. If this is the situation, then trapping of a certain percentage of gas saturation during water flood should result, at infinite water-oil ratio, in a like reduction of oil saturation below that attainable by flooding in the absence of free gas. It is visualized that the gas will exist as bubbles inside the discontinuous residual oil as illustrated in Fig. 1, with the size of the oil bubbles being substantially unchanged due to the presence of the gas. As a practical matter, it can be anticipated that the presence of a free gas saturation inside the oil phase will reduce the relative permeability to oil which will exist at any particular water saturation. This reduction will be caused by two factors — -the addition of the gas-oil interface, and the reduction of area available for oil flow in the pores containing gas. This reduction in oil permeability at any particular water saturation will result in water breakthrough at a lower water satu-

Jan 1, 1951