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By N. R. Morrow, C. C. Harris

The experimental points which describe capillary pressure curves are determined at apparent equilibria which are observed after bydrodynamic flow has ceased. For most systems, the time required to obtain equalization of pressure throughout the discontinuous part of a phase is prohibitive. To permit experimental points to be described as equilibria, a model of capillary behavior is proposed where mass transfer is restricted to bulk fluid flow. Model capillary pressure curves follow if the path described by such points is independent of the rate at which the saturation was changed to attain a capillary pressure point. Aemodified suction potential technique is used to study cyclic relationships between capillary pressure and moisture content for a porous mass. The time taken to complete an experiment was greatly reduced by using small samples. INTRODUCTION Capillary retention of liquid by porous materials has been investigated in the fields of hydrology,l soil science,2 oil reservoir engineering,3 chemical engineering," soil mechanics,5 textiles: paper making: and building materials In studies of the immiscible displacement of one fluid by another within a porous bed, drainage columnsl and suction potential techniques2 have been used to obtain relationships between pressure deficiency and saturation (Fig. 1). Except where there is no hysteresis of contact angle and the solid is of simple geometry, such as a tube of uniform cross section, there is hysteresis in the relationship between capillary pressure and saturation.2 The relationship which has received most attention is displacement of fluid from an initially saturated bed (Fig. 1, Curve R2), the final condition being an irreducible minimum fluid saturation Swr. Imbibition (Fig. 1, Curve A), further desaturation (Fig. 1, Curve R), and intermediate scanning curves have been studied to a lesser but increasing extent.2 ,3,9-12 This paper first considers the nature of the experimental points tracing the capillary pressure curves with respect to the modes and rates of mass transfer which are operative during the course of measurement. There are clear indications that the experimental points which describe these curves are obtained at apparent equilibria which are observed when viscous fluid flow has ceased; and any further changes in the fluid distribution are the result of much slower mass transfer processes, such as diffusion. Unless stated otherwise, this discussion applies to a stable packing of equal, smooth, hydrophilic spheres supported by a suction plate5 with water as the wetting phase and air as the nonwetting phase. The discussion can also be applied, in many

Jan 1, 1966

By J. H. Bain, D. C. Haigh, L. C. Parsons

Jan 1, 1964

By E. H. T. Whitten

Fundamental principles of trend surface analysis are briefly reviewed. Recent analyses of several granite masses illustrate the method of estimating the quantitative regional composition and also variation trends. Mineralogi-cal, bulk chemical, and other quantitative variates can be employed. Such results should improve gravimetric surveys (etc.) relying on correction terms based upon estimated rock composition. For the first time realistic estimates of the mean composition of rock bodies can be made with the aid of trend components. Deviation maps hold promise for delimitation of disseminated mineralized areas. Deviations comprise residual "anomalies" after removal of trend components. In petrogenetic work such deviations have been shown to reflect local influences (e.g., contamination of magma by assimilation of xenoliths or country rocks of the envelope). Similarly, mineralization should be reflected as deviations standing out from background trends. Actual examples are given. Present results largely involved projection of data onto a horizontal plane, but if sufficient data are available use of three spatial coordinates increases accuracy for prediction in "unexposed" areas. Regression analysis shows that statistical correlations between variates for regionally distributed specimens are often strong (particularly with percentage data). Hence, in preliminary surveys more easily determined variates may sometimes be employed to gain first estimates of the distribution of components more economically significant. The sampling plan is of paramount importance. Unless a suitable sampling plan is devised and adhered to rigorously during collection of the samples, all subsequent analysis is liable to strong bias and to yield spurious estimates of the truth. For a wide variety of purposes it is becoming necessary to assess the quantitative composition and variability of rock masses and mineralized zones of various types. In petrology and petrography this is something of a break with tradition, because virtually all descriptions heretofore have been qualitative. Although vast amounts of qualitative data have been compiled, little is known about the quantitative behavior of rock components. However, if variability of rocks could be understood and expressed with sufficient accuracy, there would be considerable advantage to both economic and petrogenetic problems. For example, if, on the basis of a limited series of observations, the three-dimensional geometry of a disseminated orebody (or ore-bearing formation) could be predicted accurately, it would be possible to extrapolate with confidence the structure into unexposed areas. The following example based upon the geometry of an igneous cone sheet illustrates the point. The significant rock-unit gives outcrops at a number of points on the exposed surface ABCD (Fig. 1A). Study of n exposures may enable a geologist to predict that the rock-unit is circular in form and thus indicate where the unit can be expected in unexposed terrain. Such observations are made at sites with u, v coordinates, but, if subsurface information is available at sites with uvw coordinates, it will eventually become possible to predict accurately the three-dimensional form of the rock mass. Geologic rock masses or mineral deposits are not generally as regular and symmetrical in geometric form as the body illustrated in Fig. 1A. However, even where the broad limits of a major rock mass are known, a more acute problem arises in attempting to obtain detailed quantitative estimates of its internal variability; it is difficult to predict the variability of a mass from a limited number of observa-

Jan 1, 1961

By A. Roberts

This paper reviews progress in equipment design and in the techniques applied to mine lighting in Great Britain. The incidence of the disease miner's nystagmus, which was a major source of concern only a few years ago, has now diminished, largely owing to improvements in standards of lighting in mines. The reorganisation of the coal mining industry, involving increasing mech-anisation, together with new safety legislation, has brought about the widespread use of mains electric lighting underground. An account is given of some of the results of research to determine the lighting conditions needed for compliance with the compulsory legal requirement of "sufficient and suitable" general lighting at specific localities in British mines. Some details are given of the techniques applied and the results of recent research in the problem of glare from miners' cap lamps. Of the various factors in the working environment of the miner, it is true to say that lighting is seldom given attention comparable with that devoted to other factors, such as dust, heat and humidity, or atmospheric gas content. No doubt one reason for this lies in the ability of the human eye to adapt itself to low brightness levels. Be that as it may, the fact is that at the turn of the 20th century the miner's working light improved little throughout the centuries during which mining technology has developed. Indeed, in coal mines which encounter a methane explosion hazard, flame safety lamps, with a luminous intensity less than one candle power, were virtually the sole means of lighting during almost the whole of the 19th century. The 20th century has witnessed a substantial improvement in lighting techniques underground in coal and metalliferous mining. In Great Britain the general pattern has been one of standards periodically raised by the implementation of Statutory Regulations imposed under successive hlines Acts, but it is fair to add that the more progressive mining companies usually anticipated the Statutory Regulations, which when they have been put into effect have served to turn into general practice what was already being done at the better mines. In earlier years, official requirements were limited to the specification of approved lamp designs, with stipulated minimum values of luminous intensity and light output, but more recently the necessity of satisfactory maintenance of standards during service has been recognized, and the current regulations not only require that a maintenance organisation should exist, but also specify a maximum permissible depreciation below initial approval standards.'

Jan 1, 1961

By Mehmet Guney

At the Armatcuk mine in Turkey, various modifications of sublevel methods have been tried during the last decade in an effort to eliminate gob fires, dangers from roof falls, and surface subsidence, and also to increase extraction efficiency. From the experience thus gained, it was decided that the most likely system to give maximum benefits, considering the existing geological conditions and coa1-seam characteristics, was hydraulic stowing. This paper examines trends in the working techniques of hydraulic stowing and discusses the favorable results and technical problems that the method produced at Armutcuk. The Armutcuk mine, a subsidiary of Eregli Coal Mines (EKI), produces 1300 tons of run-of-mine coal daily from thick (about 10-90 ft) and highly dipping (about 50-90°) coal seams. The coal is highly volatile with good coking properties that make it highly suitable for industrial use. Most of this coal is used in the iron and steel industry at Eregli on the Black Sea coast. Complete recovery of the coal is of vital importance to industrial development and progress. Initial coal extraction was carried out by means of a sublevel mining system modified to accommodate local geological conditions and coal seam characteristics. This method is similar to that employed in metalliferous mines. Several problems arose from the application of the method, one of them being the prevalence of gob fires which caused periodic shutdowns in some sections. To achieve maximum coal extraction with minimum dilution, to eliminate gob fires and surface subsidence, and to reduce fatal accident rates, a decision was taken to change from this method to a hydraulic stowing system. The pres- ence of large deposits of conglomerate and sandstone on the surface contributed to the decision to employ this new method. Although hydraulic stowing practices have been carried out in America and Germany, Upper Silesia may, so far as coal is concerned, be considered the birthplace of the method. Here the process was adapted to thick coal seams on a large scale to reduce dangers from gob fires and damage from surface subsidence. Today, the mining system is not only widely used in the coal mines of France, the Saar, India and Poland, but has also been successfully applied to the iron ore and potassium salt mines in Russia and Germany. LOCATION AND HISTORY The Kandilli-Armutcuk coal field, the most western outcrop of the North Anatolian coal basin, extends for five miles along the Black Sea coast (Fig. 1). The Armutcuk Mine is situated on the southern boundary of the coal field about 40 miles from Zonguldak and about 12 miles from Eregli. The history of coal mining in the North Anatolian coal basin goes back more than a century. Mining commenced on a small scale in the Kandilli-Armutcuk coal field in the late 1880's, and from this time until nationalization in 1940 the mines were operated by private Turkish and foreign interests. In 1940, Eregli Coal Mines was established to takeover the management of these enterprises. The Armutcuk Mine was developed for the first time in the mid-1940's. Since then it has been in continuous production and it now produces an annual 440,000-ton run-of-mine output from which 320.000 tons of salable coal is obtained. MINE GEOLOGY The carboniferous inlier of the Kandilli-Armutcuk coal field crops out over an area about three miles long and one mile wide. The major part of the inlier consists of the Namurian formation with only a relatively small area of Westfalian-A visible on the surface (Fig. 2). The Namurian formation, which has no exploitable coal seams in the Armutcuk Mine, consists mostly of arkose sandstones and black shales often having

Jan 1, 1969

By K. E. Brown, J. P. Brill, A. R. Hagedorn, T. C. Doerr

A recent correlation for multiphase vertical flow by Hagedorn and Brown1,7 has been used to examine the effect of numerous variables such as pipe size, gas-liquid ratio, liquid flow rate, liquid viscosity, liquid surface tension, oil API gravity, water cut, etc., on flowing pressure gradients. Most previous correlations were derived by using a form of the general energy equation which assumed negligible changes in kinetic energy. Under certain flow conditions this can lead to serious errors in predicting pressure traverses. Examples of traverses calculated both with and without the kinetic energy term are included here. The Chew and Connully correlation for calculating changes in viscosity with changing pressure and temperature has been extended so that the effect of a changing viscosity with depth on pressure gradients can also be predicted. Examples illustrating the effect of tubing size show the importance of this correlation in determining pipe sizes for initial well completions. Limitations on production rates in small pipe sizes from excessive friction losses can be predicted with greater accuracy. The combined use of a vertical-flow correlation with a horizontal-flow correlation provides a method for determining the maximum flow rate possible from both flowing and gas-lift wells. Examples are included to illustrate application of the combined use of vertical and horizontal-flow correlations in optimizing production rates and minimizing excessive costs from over injection of gas in gas-lift wells. INTRODUCTION The problems of multiphase vertical and horizontal flow are immediately encountered in any producing well. Fig. 1' shows three stages of production: flow in porous medium, vertical flow and horizontal flow. All three stages affect the production rate from a well. If we are confronted with a particular well and consider only the variables involved in the vertical and horizontal stages of Fig. 1, we should be capable of calculating the flowing bottom-hole pressure necessary to produce a particular flow rate. A change in any of the variables results in a new solution to the problem. Recent approaches in developing horizontal and vertical-flow correlations have improved to the extent that the solution can now be obtained with more confidence than previously. VERTICAL AND HORIZONTAL FLOW CORRELATIONS Since Poettmann and Carpenter's' original work in multiphase vertical flow, there have been many additional vertical-flow correlations developed which have greatly improved the accuracy of pressure-loss calculations. These

Jan 1, 1967

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

The Grand Isle sulfur mine is located in the Gulf of Mexico, approximately seven miles off the coast of Grand Isle, Jefferson Parish, La. The deposit is on acreage covered by oil, gas, and mineral leases originally issued in favor of Humble Oil & Refining Co. by the State of Louisiana which were continued, maintained, and redesignated by the U.S. Department of the Interior after passage of the Outer Continental Shelf Lands Act. The sulfur deposit was discovered in 1949 when Humble Oil & Refining Co. penetrated more than 200 ft of sulfur-bearing limestone in a zone between 1813 and 2075 ft below sea level. In 1954, Humble drilled ten more sulfur prospect holes, eight of which encountered sulfur ore. On September 19, 1956, Freeport Sulphur Co. acquired from Humble Oil & Refining Co, the sulfur rights underlying the tracts, and the actual design of the installation began the same month. The first structural contract was awarded in December 1957 and offshore erection began in June 1958. The initial phase of construction has been completed and production by the Frasch process commenced in April 1960. The estimated total cost of the project is $30 million, of which $8 million is the extra cost incurred by the necessity of offshore operations. More than $22 million was expended before production was started. GEOLOGY OF DEPOSIT Grand Isle is the third largest sulfur deposit in the U.S. The orebody embraces several hundred acres, but its outer limits are yet to be defined to the northeast, east, and south. Most Gulf Coast sulfur deposits occur in a caprock mantle of calcite (referred to as limestone), anhydrite, and occasionally gypsum, which covers the apex of an intrusive mass of salt. Commercial quantities of sulfur are usually confined to the calcite or limestone member. Most often such limestone is completely enclosed by dense anhydrite below and impervious sediments above, which effectively form a closed reservoir. The depth of the Grand Isle orebody ranges from 1800 ft to 2500 ft below sea level. Within the present boundary, the sulfur-bearing limestone varies in thickness from 220 ft to 425 ft, while the sulfur content varies an average of about 15 pct in the leanest hole to an average of about 30 pct in the richest. Rock containing less than 5 pct sulfur is not classed as ore, and holes assaying less than 20,-000 long tons per acre of sulfur in place are not considered commercial offshore. The sulfur enrich-

Jan 1, 1961

By P. D. White, J. T. Moss, J. S. McNiel

Results of experimental work on the in situ combustion process were first published in this country in 1953' when Kuhn and Koch described results of a three-well test in Jefferson County, Okla. Shortly there-after Grant and Szasz2 described field studies in Nowata County, Okla., in which several modifications of the basic combustion process were investigated by injection of various oxidizing gas mixtures other than air. In the past five years speculation concerning this method of oil recovery has continued, with a number of interesting papers on various aspects of in situ combustion appearing in the literature3,4,5,6,7. However, only one of these' provided actual engineering information on pattern-type field experiments. The primary objectives of the Oklahoma three-well test were to check operation of specially designed electrical ignition equipment and evaluate problems associated with initiation of combustion in a natural oil sand reservoir. Immediately following successful completion of this test in the Pontotoc sand, plans were activated for a second field experiment to be conducted in the same sand a short distance away. The objective of this second field test1 as to establish a relationship between field observations and information derived from laboratory experimentation and computations. Secondary objectives of the test were to develop operating tech- niques and define operating problems, and to obtain information that would assist in the economic and engineering appraisals of the process. Careful planning was required since this test was designed with the hope of providing basic information on the characteristics and operation of a combustion drive. It was necessary to include test facilities which would not only permit precise control and measurement of the process variables but would also provide sufficient flexibility of control to insure that variables in the combustion process could be studied during the course of the test under a wide range of conditions. In order to accomplish these objectives elaborate instrumentation and several control wells were included in the design of the test installation. This type installation was felt to be well suited for an experimental study, but was in no respect intended as a counterpart of a commercial-scale operation. PRELIMINARY LABORATORY WORK An important objective of the field experiment, as stated previously, has been to obtain reliable data on operating variables which might be compared with similar data obtained in laboratory combustion tests. The value of successful correlations between quantities that can be measured in the laboratory and those obtained in a full-scale commercial venture has been well established for other industrial processes. The difficulty of following a process underground should make such correlations even more essential here. Also. approaching the field test phase of development of in situ combustion, it was considered desirable to precede design of test equipment with laboratory combustion studies under a variety of conditions to establish likely ranges of variables. These included temperature, air injection rate, frontal advance rate and produced gas composition.

By E. H. Boswell, E. M. Cushing

The Mississippi embayment east of the Mississippi River is part of a vast geologic and hydrologic province. The abundance of water available is largely responsible for the agricultural history of the area and is perhaps the key factor in the rapidly accelerating trend toward industrialization. The multiple artesian aquifer systems that underlie the region and the alluvial aquifer along the Mississippi River are virtually undeveloped sources of fresh water in that they are yielding only a fraction of the water available. The potential yield of the 12 aquifer systems is estimated to be about 25,000 mgd (million gpd) of which only about 600 mgd is presently being withdrawn. The amount of water in storage in these systems is about 1600 trillion gal. Ground water having a dissolved-solids content of less than 500 ppm is generally available at depths of less than 1000 ft, and water having a dissolved-solids content of less than 1000 ppm is available in some places to depths of more than 3000 ft. Iron is the most common troublesome chemical constituent in the ground water. Water in varying amounts is also available from streams within the region. The amount of water which originates within the region and which leaves it as streamflow during a year averages about 50 million acre-ft (about 45,000 mgd). An additional 375 million acre-ft (about 340,000 mgd), which originated outside the region, leaves the region as streamflow during an average year. Some streams have considerable flow during periods of no precipitation and the water during these periods generally has a low dissolved-solids content. Large quantities of water from streams and waterbearing sands (aquifers) are available in the Mississippi embayment east of the Mississippi River. Most of the region is underlain by aquifer systems that will yield large quantities of water to wells, making ground water the most readily available source of fresh water. About 90% of the water used in the region is obtained from wells. Streams have been used primarily to dispose of, and dilute, wastes that have been dumped into them. The Mississippi, Ohio and Tennessee rivers, and the lower parts of the Tombigee and Yazoo rivers also serve as a means of transportation. This nominally water-rich region receives from 48 to 56 in. of precipitation in average years and is crossed by several large rivers. The largest, the Mississippi River, is the western boundary of the region discussed in this paper. The economy of the region is basically agricultural, but industry has become increasingly important since World War 11. The diversification and mechanization of agriculture have resulted in a surplus of manpower, most of which is being absorbed by the expansion of industry. Further industrial expansion probably will occur because of the available manpower, natural resources and economical transportation. Increasing demands on available water supplies will be made and the future economic growth of the region will be largely dependent upon wise utilization and management of the water resources.

Jan 1, 1969

By F. S. Young

Previous laboratory and field experimentation has demonstrated the effect of several variables on drilling rate.1-5 These results have been incorporated into optimization theories6-" for the purpose of reducing drilling cost. Minimum-cost drilling theories rely on a combination of historical data and empirical prediction techniques for selecting optimum bit weight and rotary speed. Past solutions have required extensive use of computing equipment because of both the complexity of the mathematical formulations and the large number of parameters involved. Field attempts to apply these computed results have frequently failed because of the uncertainty of input data requirements. Humble has developed an on-site computer system to control bit weight and rotary speed and thereby implement the concepts of minimum-cost drilling. This system can (1) perform short interval drilling rate tests for formation evaluation, (2) use the results of these tests as input information to solve minimum-cost drilling formulas, and (3) control bit weight and rotary speed in accordance with these computed solutions. The purpose of this paper is to describe the computer control system and present results of initial field testing. Theoretical Considerations Minimum-cost drilling (MCD) requires a quantitative evaluation of the variables involved. Several forms of a basic mathematical model have been sug-gested.'?,' "he relationships reported here form the basis for the solution programmed in this work. Four equations are used, expressing drilling rate, bit bearing wear, bit tooth wear, and cost. A solution for minimum-cost drilling assuming constant bit weight and rotary speed over the entire bit life has been programmed for use in computing MCD schedules. This solution is subject to certain limiting assumptions such as those discussed by Graham et a1.I2: 1. Drilling cost is the summation of bit cost, rotating cost, connection cost and hoisting cost. 2. Diamond bits are excluded. 3. Bit life is limited by either bearing failure or tooth wear, or by a combination of operational factors that make it cheaper to pull an incompletely consumed bit. 4. Circulating hydraulics are adequate and do not limit drilling rate. 5. Bit weight considerations exclude hole deviation. 6. Drilling rate is a function of only bit weight, rotary speed, and degree of tooth dullness; that is, the effects of pressure, lithology, fluid properties hydraulics and drill string dynamics are ignored. In equation form, the four MCD expressions are as follows:

Jan 1, 1970

By R. G. Bentsen, D. A. T. Donohue

The cyclic steam injection process has become the most widely applied and most successful thermal recovery technique in use today.1-4 Normally, steam stimulation is repeated several times during the life of a project. The problem is to select the optimum number and size of steam treatments so that the profits realized over the entire life of the project are maximum. Obviously, operating costs rise directly with the frequency and amount of steam injection. Operating efficiency, on the other hand, can be adversely affected if the amount and frequency of stimulation are insufficient. Thus arises a multistage decision problem; that is, a decision must be made at each sub-period (day, for example), as to whether steam should be injected, and, if so, how much. It is desirable that these decisions be made in such a way as to secure maximum net profit before taxes. This can be achieved by dynamic programming. To use dynamic programming, we must be able to predict not only the production rate-time curve resulting from a given stimulation, but also how changes in stimulation policy will affect this curve. In this study, the effect of steam injection on well performance is estimated on the basis of a simple model that takes into account both steady-state and transient flow. Oil production rate is calculated for both types of flow, and the larger of the two values is used. This allows the calculation to change to radial steady-state flow at such time as this mechanism becomes more effective than the transient mechanism. We propose to show how dynamic programming can be used to optimize the steam soak process with respect to net profit. For this, a mathematical representation of the steam soak technique is necessary. A further objective, therefore, is the formulation of a mathematical model capable of realistically simulating the physical process. Oil Production Response Model The advantage of using a mathematical model is its generality and ease of manipulation. However, the model must be an accurate representation of the physical process, for a solution derived from a model can be no better than the model itself. The question now arises as to how well the model should be expected to simulate reality. In general, the simplest model should be tried first, for additional accuracy is apt to require additional cost and time. Also, the search for a high degree of accuracy may yield only greater complexity and difficulty without yielding significantly better results. With this in mind, we kept our model as simple as possible, yet generally representative of the actual physical process. The number of state variables is limited to three, and stochastic variations in the parameters are ignored. As a consequence, use of this model should be restricted to cases in which the underlying assumptions are not severely violated. In

Jan 1, 1970

By Olav Mellgren

Part I. The interaction between potassium ethyl xanthate and lead salts has been studied thermo-chemically. It is shown that ethyl xanthate reacts with lead carbonate, basic carbonate, thiosulfate and sulfate according to principles of simple chemistry, whereas reactions with lead sulfite, metasulfite, basic thiosulfate and hydroxide at high pH are associated with secondary reactions. A new compound "xanthogen thiosulfate" is postulated. Part 11. Adsorption of ethyl xanthate on galena has been studied quantitatively and thennochemi-cally. It is shown that an ion-exchange mechanism governs the adsorption process and that the heat of adsorption of xanthate on galena is equivalent to the heat of reaction of ethyl xanthate with bulk lead salts. It is concluded that the entropy content of the surface "compound" on galena is different from that of a corresponding bulk lead salt. Alkali depression is in part shown to be due to the instability of the xanthate-galena system at high pH and to the formation of basic lead salts. Sulfate and carbonate ions are shown to have a stabilizing effect on the xanthate-galena system. PARTI. THERMOCHEMISTRY OF ETHYL XANTHATE AND OF ITS REACTION WITH LEAD SALTS In the past little attention has been paid to the chemistry of lead xanthate. It is known that xan-thates form slightly soluble compounds with lead and that suspensions of lead xanthates in alkaline solution decompose rather readily.' The solubility of lead ethyl xanthate is of the order of 2.6 x 10-6 moles per 1. At increasing pH the xanthate concentration of a saturated solution contains more xanthate. Thus at pH 11 this xanthate content is about 100-fold larger than at pH 7.1 Xanthates are known to be consumed when added to a suspension of slightly soluble lead salts such as lead sulfate and lead carbonate. It is unknown to what extent this xanthate consumption is due to a simple chemical reaction because, frequently, observations are made which reveal secondary reaction products in such reactions. Thermochemical study of the reaction between xanthate and lead salts offers a means to clarify the significance of these reactions as the enthalpy changes can be accurately predicted from heat of formation of lead salts in pure solution reactions. In the present work the heats of formation of lead ethyl xanthate from potassium ethyl xanthate and lead salts are determined and some thermochemical aspects of xanthate in solution are studied. The results of these investigations are presented in Part I. In Part II the heat of adsorption of ethyl xanthate on galena surfaces is presented. All enthalpy changes were measured directly in a microcalorimeter. Calorimeter: The calorimeter used for measuring enthalpy changes was similar to that used by Redinha and Kitchener2 which was based on a description by Derbyshire and Marshall.3 Other useful references4,5 are listed. A sketch of the calorimeter

Jan 1, 1967

By H. D. Outmans

A method has been developed for determining the relative water wet-tability (fraction of the surface wet by water) of porous media. This method involves the adsorption of methylene blue dye from an aqueous solution onto the solid surfaces of rock contacted by the injected dye solution. Experiments on Berea snndstone cores have shown that water-wet cores adsorb a large amount of dye from solution. In oil-wet cores, however, the injected aqueous dye solution is prevented from contacting the adsorptive surfuces by a film of oil and virtually no dye is adsorbed. This method was tested by experiments on mixtures of water-wet and oil-wet sand. Using the dye adsorption method, it was possible to determine quantitatively the fraction of water-wet and oil-wet sarzd in such mixtures. The dye adsorption test is readily applied to determinitrg the relative water wettability of fresh oilfield cores. The cores are not extracted before testing. Observed values of the wettability of field cores tested to date have varied from 100 to 6 per cent water wet. INTR OD UCTIO N Recent articles1 ' have emphasized the important role that wettability plays in almost all phases of reservoir rock behavior. It has been shown that wettability has a profound effect on the interstitial water saturation, residual oil saturation, capillary pressure, relative permeability, waterflood behavior, and resistivity index of oilfield cores. A quantitative investiga- tion of the effect of wettability on these core properties is severely handicapped by the lack of a simple technique for measuring the wettability of a porous medium. If such a technique were available, it would provide investigators with a means of gaining insight into the distribution of phases within a core. A number of qualitative methods of estimating wettability are known. These include contact angle measurements, flotation tests and studies of displacement pressure: imbibition7 and relative permeability data.' Using these tests, it is usually possible to classify a core as water-wet, oil-wet, or some intermediate degree of wettability. One recently proposed method involving measurement of nuclear magnetic relaxatione offers promise of determining quantitatively the fractional wettability of cores. The equipment is rather elaborate and necessary treatment of the cores before testing probably alters the natural wettability. This latter point also applies to most of the cited qualitative methods. This paper presents a new technique for determining water wettability of cores; it is based on measurements of the dye adsorption capacity of the core. This method has the advantage of requiring relatively simple equipment and involves minimum handling of the core before testing. It is important to distinguish between the various concepts of wettability referred to in the literature. The term "wetting" is defined by Bartell as that phenomenon which occurs when a solid and liquid phase come in contact in any manner so as to form a solid-liquid interface. A preferentially water-wet solid is defined by Jennings in terms of the advancing contact angle in the solid water-oil systems. Brown and Fatt regard fractional wettability as the fraction of the total surface area that is preferentially oil-wet or water-wet. However, none of these definitions adequately describes the type wettability measured by the dye test. This calls for the introduction of a new term, "relative water wettability", which we define as the fraction of the total surface area of a core contacted by injected water. DESCRIPTION OF METHOD The ability of a porous medium (especially the clays) to adsorb large quantities of surfactants, dyes, etc., is well known. It is reasonable to assume that a substance can be adsorbed from solution onto a solid surface only if the solution contacts the surface. In this connection Shapiro" has shown by experiments on silica gel that completely dry gel will adsorb methyl red dye from a benzene solution. On the other hand, if a film of water more than several molecules thick is present on the silica gel, the adsorption capacity of the gel for the dye is drastically reduced. Thus, a study of the dye adsorption capacity of cores should give some clue as to the fluid distribution on the surface of the core. TEST OF METHOD As a qualitative check on this theory, dye adsorption tests were run on similar Berea sandstone cores (Table 1, Cores 1-5). Cores saturated initially with water and flooded with 0.01 per cent aqueous methylene blue adsorbed 0.58 mg dye/gm of core. Similar cores saturated initially with water, driven to irreducible water with oil, and then flooded with the same dye solution also adsorbed 0.58 mg dye/gm of core. Another core, treated with a 5 per cent Dri-Film solution, dried and saturated with oil (Soltrol) adsorbed no dye when the dye solution was injected. These tests confirm

By T. R. A. Davey

The fundamental principles by which bismuth may be removed from lead by pyrometallurgical processes are enumerated. Qualitative discussion of the phase diagrams concerned is followed by presentation of quantitative diagrams. Brief mention is made of the practical aspects. Data presented show how chemical lead (<0.005 pct Bi) may be produced by the Jollivet, Dittmer, and Kroll-Betterton processes. BISMUTH is an element whose properties are very similar to those of lead, and its minerals are associated to a greater or lesser extent with nearly all the major lead ore deposits of the world. In consequence, the lead produced contains bismuth unless a special debismuthizing process is practiced. There does not appear to be any published comprehensive review of the effect of bismuth as an impurity on the properties of lead, and there is some uncertainty as to the beneficial or detrimental effects of small amounts of bismuth in lead used for particular applications. Standard specifications of most countries stipulate a maximum bismuth content of 0.005 pct for chemical lead. With one exception, this specification is met only by lead producers whose ores are relatively bismuth-free, or whose refineries are electrolytic. In lead for certain applications a higher bismuth content is preferred by some fabricators.&apos; In contrast to the refining for silver, copper, and antimony, the refining for bismuth does not usually result in a large overalil economic gain from the sale of byproduct. Thus, debismuthizing is customarily practiced only if market conditions demand a lead with a bismuth content lower than that produced by classical refining; i.e., softening, desilverizing, and zinc refining. Until this century, debismuthizing was carried out only a:; an incidental result of desilverizing, as later described. This century has seen the development of the Betts electrolytic process—the only successful one of many electrolytic processes proposed and patented —and a number of precipitation processes based on the pioneering work of Kroll,&apos; although only one of these, the Kroll-Better ton process,&apos; is in wide commercial use today. It is proposed in this paper to deal only with the pyrometallurgical processes, excluding those based on aqueous electrolysis. Historical Background Prior to 1833 silver (and incidentally bismuth) could not be removed from lead. To recover silver from rich bullion, the only course available to lead refineries was to cupel the bullion, forming a slag of litharge. The first slag tappings or skimmings, on reduction, yielded soft lead of very low silver and bismuth contents. Intermediate skimmings yielded a lead of somewhat higher silver and bismuth contents, which could if desired be recupelled. The last skimmings yielded a litharge very high in bismuth, which could by successive oxidation and reduction cycles be separated into high purity bismuth, and lead returns. This oxidation reduction process, with modern operating techniques, can still be used today to produce a portion of a lead refinery&apos;s output of very low bismuth content, as discussed later. In 1833 Pattinsone discovered that lead bullion could be purified of silver and bismuth by fractional crystallization, the primary lead crystals formed by partial freezing being purer than the melt. Repeated processing in pans produced a lead containing as little as 0.02 pct Bi. The simple explanation of this

Jan 1, 1957

By D. R. Parrish, F. F. Craig

In some respects, forward combustion (alias: fie-flooding, underground combustion, in-situ combustion, dry combustion) is an efficient oil recovery method. For example, its displacement efficiency (as much as 95 percent in reservoirs with high porosity and high oil saturation) is good. In its use of heat, however, forward combustion is grossly inefficient. Most of the heat generated during forward combustion is wasted. About one-fifth of the heat is picked up by the incoming air and re-used (regenerated); the remainder is left behind the combustion zone and ultimately is lost. Compressed air is expensive, and heat generated from compressed air via underground combustion is too valuable to be thrown away. Improvement is needed. Since the early 1950&apos;s, improvements in forward combustion by addition of water injection have been discussed, particularly in the patent literature, with increasing frequency.&apos;-&apos;&apos; These concepts are based on the fact that relatively inexpensive water can be used to pick up much of the heat that is ordinarily wasted during forward combustion, and transport it forward to a more useful place, thereby reducing the amount of air required to move a heat front through the reservoir. Several approaches have been proposed. Merriam and Squires1 taught that a combustible (fuel) gas should be injected along with the air and water. This, however, would give at least a tendency toward reverse combustion instead of forward combustion, and would reduce the velocity of the heat bank, defeating the primary purpose of the water injection. Pelzer2 described primarily a batchwise method of forward combustion and water flooding. He advocated burning part way through a reservoir with forward combustion, then switching from air to water injection alone to push the heat toward the producing wells. Though possible, this method has serious disadvantages, the major one being that, by the time water injection is started, much of the heat has been irretrievably lost to the overlying and underlying formations. We have described what is considered a practical Combination Of Forward Combustion And Water-flooding (COFCAW).3,4 Air and water are injected simultaneously (or alternately) after a small heat bank has been formed by forward combustion. Some of the injected fluid fills up the region behind the heat bank; the rest enters the heat bank. Upon encountering heated rock, the water is converted into steam, which then flows ahead of the combustion zone and displaces much of the oil in place. Only enough air is injected to provide heat for vaporization of the water and to compensate for reservoir heat losses. Since the size of the heat bank is minimized, heat losses also are minimized. Because of more efficient oil displacement ahead of the combustion zone, fuel consumption is reduced. Too, unlike a forward combustion zone that cannot move until all fuel at a point has been consumed, COFCAW leaves some

Jan 1, 1970

By John T. Norton

N order to attempt to arrive at a better under-Jl standing of the whole basic problem of sintering, these remarks will serve as an introduction for discussion that is included and will, perhaps, help to isolate specific questions which need to be answered or to suggest some definite avenues of investigation which should be followed. To bring some sort of logical order into the presentation, I will consider the various types of interaction between the metal to be sintered and the atmosphere which surrounds it, depending upon whether the phenomena are essentially chemical or physical in nature. For example, when the only necessary criterion for the satisfactory sintering of a certain powder is the removal of an oxide skin, then the problem of choosing a suitable atmosphere is primarily chemical; however, if a special surface condition as a consequence of the oxide skin removal is necessary for particularly effective sintering, then the problem becomes a physical one. Of course, the two aspects overlap considerably, but it may be possible to make a distinction in principle if not in practice. The chemical characteristics of the phenomena will be emphasized, since these are the better known. Metal-gas reactions involved in sintering are controlled primarily by the thermodynamics of the processes involved. In which direction will a reaction go and how far before it stops? The answer is to be found in the magnitude of the free energy change associated with the reaction. If a constituent is to be removed from the specimen as completely as possible or if a constituent is to be formed in the specimen as completely as possible, then one chooses conditions which are far from equilibrium so that the reaction is driven toward completion. On the other hand, if the composition is to be maintained at a desired value, then conditions are adjusted as closely as possible to the equilibrium point. This aspect of the problem is susceptible to quite precise analysis, provided, of course, that the significant reactions can be recognized and the required thermodynamic data are available. Conversely, if one asks how fast the reaction goes or how far it proceeds in a given time, the answer is frequently much more difficult to answer in quantitative terms. Yet the rate-con trolling factors of the reactions may be of primary importance in the success of a particular operation, especially where competing processes are at work. Both equilibrium and rate factors must be understood if a clear picture is to be obtained. For instance, in a process for carburizing titanium dioxide, is the difficulty of obtaining a stoichiometric Tic due to a true limitation of the equilibrium or simply to a very slow rate of reaction? An example of this appears in the work of Kalish and Mazza.&apos; They showed that the oxygen content of sintered iron compacts was lower when sintered in pure hydrogen than in the case where the hydrogen was diluted with either argon or nitrogen. The equilibrium oxygen content of the iron would be the same in the two cases, since it is determined by the ratio of the partial pressures of water vapor and hydrogen and this pressure ratio is unchanged by dilution. The rate of oxygen removal, however, under the conditions of a constantly replaced furnace atmosphere, depends upon diffusion and thus upon the concentration of hydrogen in the furnace atmosphere. Possibly the clearest way to illustrate the interplay of these two factors is to consider in more detail some of the typical metal-gas reactions. Adsorbed Gases It is common experience that fine metal powders with their very large surface areas often contain large quantities of gas. This gas, which results from exposure to air or perhaps from some step in the

Jan 1, 1957

By E. H. Herron, J. H. Perry

Mathematical simulation of reservoir behavior may be used to help understand reservoir processes and to predict reservoir behavior, thereby leading to the most economically desirable form of exploitation. In addition, simulation can be used as a tool for reservoir description to learn more about the physical nature of the reservoir and the mode of primary recovery. This use is essential in most reservoir studies and represents one of the more significant applications of simulation. Prediction of reservoir behavior provides information concerning displacement efficiency, optimum well locations, and the comparison of alternative producing processes. Since oil, water and gas all commonly occur in many reservoirs, a simulation that takes into account the simultaneous flow of three immiscible phases is a prerequisite for obtaining such information. Furthermore, a simulation that describes this flow in two dimensions provides the capability of evaluating combination gas- and water-drive reservoirs with either an areal or a cross-sectional description. Many reservoir problems require such a simulation. The objective of the research described here was to develop a mathematical model and associated computer program for accurate, efficient, and economical prediction of the reservoir flow of three phases in two-dimensional geometry. Several authors have discussed multidimensional reservoir simulation of two phases.l-3 Gottfried et al.&apos; presented an analy- sis of three-phase simulation in one dimension. Fagin and Stewart" and Garrett6 have discussed the simulation of three-phase flow in two dimensions, but their solution techniques were different from the method discussed in this paper. In particular, previous models and computer programs have usually involved either fewer capabilities or inefficient and less rigorous descriptions resulting in limited applicability. In the following sections, we present a description of the model, an evaluation of the method, and the application to reservoir problems. Additional and supporting material is presented in the Appendix. The Three-Phase Model General Description The three-phase model consists of the mathematical description of the flow of oil, water and gas in a reservoir. Conceptually this description considers flow in all three space dimensions, but in the subject simulator it is assumed that no flow occurs in the third dimension. The model includes the effects on reservoir behavior of fluid and rock compressibility, viscosity, gravity, capillary pressure, relative permeability and gas solubility. Within the two-dimensional restriction, the reservoir considered may be completely heterogeneous and anisotropic. The differential equations governing multiphase, multidimensional flow in a reservoir are too complex to be solved analytically, so they are approximated by a system of finite difference equations and solved

Jan 1, 1970

By L. B. Davidson

The petroleum literature contains many reports on the relative permeability properties of porous media. However, only recently have studies of relative permeability at elevated temperatures been made.1 -5 Each of these studies presents relative permeability data on water-oil systems in linear sandpacks or sandstone cores under isothermal conditions. The results of these investigations are dissimilar. Edmondsonl found that in Berea sandstone a temperature-dependent effect was present, while Shilobod,2 using the same material, found no temperature dependence after normalizing for initial water saturation. Workers at Texas A&M U.3-5 found that the ratio kw/ko was temperature dependent in an unconsolidated system. The differences in results of these studies are probably a consequence of differences in the material employed, in the experimental procedures followed, and in the properties of the porous systems used. This paper describes an experimental investigation of permeability ratio temperature dependence, conducted to clarify some of the results obtained by previous workers. Each experiment described in this paper involved the isothermal displacement of Chevron No. 15 white oil by either nitrogen, steam, or distilled water and displacement of water by nitrogen. All permeability ratios were calculated using the Welge procedure. Values of the water-oil permeability ratio were obtained over the temperature range 75OF to 540°F. Results indicate the ratio is temperature dependent at low water saturations, probably due to interfacial effects. However, as the saturation is increased, temperature dependence decreases until, above some minimum saturation, the ratio becomes insensitive to temperature. Previously published work indicates that the dependence reappears at very high water saturations, a region of the ratio curve not completely examined in the present study. It appears that water-oil permeability ratios are temperature dependent at the extremes of the ratio curve where changes in interfacial tension with temperature induce variations in residual saturations. Between the extremes, there is a region in which the permeability ratio is insensitive to temperature. The size and location of this region is probably a function of the characteristics of the porous system. Gas-oil permeability ratios calculated from nitrogen-white oil displacement experiments indicate a definite temperature dependence over the range 75OF to 500°F and over the entire gas saturation range studied. Evidence discussed in this report indicates that this dependence is a consequence of molecular slippage in the gas phase. This is an extension of the Klinkenberg effect6 to two-phase systems at high temperatures (the existence of slippage in two-phase systems at room temperature has been demonstrated7). Evidence for a similar source of temperature dependence in superheated steam-white oil experiments

Jan 1, 1970

By R. J. Watson, A. H. Juch

About half a million sucker-rod pumps are installed in oil wells in the U. S. alone. In Venezuela, too, the system is widely used; some 5,000, or 90 percent, of Cia. Shell de Venezuela&apos;s wells produce a total of 400,000 BOPD by this method. Most of the crude pumped is viscous, gassy and contains relatively small amounts of free water. API gravities vary from 90 to 16O; dead oil viscosities vary from 10 to 10,000 cp at the pump; and GOR&apos;s range from 100 to 2,000 cu ft/bbl. Pumps are set at depths ranging from a few hundred to 6,000 ft; the average setting depth is about 2,500 ft. From the literature, it appears that although recent years have seen significant progress toward understanding the rod pumping system as a whole, relatively little attention has been paid to those key items, the sucker-rod pump and the subsurface gas separator or gas anchor. Perhaps because of proration in the U. S., pump manufacturers have seemingly concerned themselves more with the durability of their product, achieved mainly through robust design and metallurgical know-how, than with its working efficiency. In 1963, CSV commenced a major rehabilitation and expansion of its heavy oil fields along the Bolivar Coast. The advent of the more efficient gravel-packed completion and of large-scale thermal recovery (mainly steam soak) operations resulted in well potentials *Now with B. I. P. M., The Hague, The Netherlands. greater than pump capacities. Hence, an urgent need arose to improve over-all pump efficiencies and to attack those special problems related to the production of both the extremely viscous and the hot, steam-laden crudes that formed an increasing proportion of the total stream. There followed a detailed investigation and testing program, carried out in close cooperation with a major pump manufacturer. This culminated in the introduction to the oil industry of a new line of sucker-rod pumps. Early Investigations and Experiments Field Tests Extensive field tests were carried out in three primary Bolivar Coast wells with an in-situ dead oil viscosity ranging from 400 to 6,000 cp. In these installations provision was made to (1) monitor bottom-hole pressures below, in and above the pump by means of pressure transducers, and record casing- and tubing-head pressures continuously; (2) measure accurately the annulus gas, as well as measure the tubing gas and liquid production from the well; (3) take special PVT samples of the well fluid; (4) measure power consumption of the prime mover; and (5) measure the rod loads at the polished rod. A typical test installation is illustrated in Fig. 1. It was established from the pressure transducers that with viscous oils, there is considerable flow resistance across the pump and gas anchor assembly. Pressure surges were observed over each pump cycle,

Jan 1, 1970

By L. F. Elkins

Water coming into wells with bottom water present in the Fosterton field, when their oil recovery was only 0.1 to 1.5 per cent of oil in place below the lowest perforation, confirms lack of shale barriers to vertical flow which also are not apparent in cores and electric logy. Low contrast of vertical and horizontal permeability, high mobility ratio betweerz oil and water zone and pos.rible rate effects due to gravity Combine to prevent easy analysis of water invasion pattern and efficiency by analogy or intuition. Theoretical analysis of performance including these factors using a new direct nurnerical .solution of potential distribution in a network led to unanticapted indications that water would under-run the entire oil reservoir with low volumetric coverage if supplied through natural influx or peripheral water injecfion below the oil-water contact. An unusual pattern of water injection is to he adopted in this recently unitized pool to provide more uniform water flooding in that two-thirds of the oil reservoir not underlain by bottom wafer. INTRODUCTION The Fosterton field, Southwestern Saskatchewan, Canada, was discovered in Jan., 1952. It produces at a depth of 3,100 ft from a pinch-out of the Roseray sand at the Lower Cretaceous-Jurassic unconformity. The field, covering 2,500 acres, contains 54 wells on 40-acre spacing. Development was essentially complete in June, 1954, but significant production did not start until May, 1955, when a pipeline outlet became available. Within one year rapid in- creases in gas-oil ratio and early encroachment of water created operating problems in the down-structure eastern half of the field and raised serious questions about reservoir performance and ultimate recovery. This paper describes the unusual behavior of water encroachment—on both well and reservoir bases—and the analyses made to interpret it. The field was unitized July 1, 1958, for water flooding. A somewhat unconventional