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By J. U. Messenger

A technique is described whereby the resistance of an emudian to breaking can be quantitatively determined. Produced ailfield emulsions are usually the water-in-oil type and, accordingly, do not conduct an electrical current. However, there is a threshold of A-C voltage pressure above which an emulsion will break and current will flow. The more stable an emulsion, the higher the required voltage. A Fann Emulsion Tester, modified so that low voltages (0 to 10 v) can be accurately measured, is suitable. This technique has application in evaluating the effect of a demuksifier on the stability of an emulsion. Emulsions can, in essence, be titrated with demulsifiers by adding a quuntity of demulsifier, stirring, and measuring the voltage required to cause current to flow. Any synergistic effect of two or more materials added simultaneously can be followed accurately. A demulsifier that significantly lowers the threshold voltage (from 100 to 400 v to 0 to 10 v for the emulsions in this study) is effective and can cause the enlulsion to break. A demulsifier that will bring about this drop in the threshold voltage at low concentration ir very desirable. The technique is also well adapted for rapidly screening demulsifiers. INTRODUCTION Stable emulsions in produced reservoir fluids resulting from certain well stimulation and completion procedures are common problems. The use of suitable demulsifiers can often mitigate these difficulties. At the present time, a rapid and efficient method for selecting satisfactory demulsifiers is not available. It is badly needed. Reliance is now placed primarily on trial-and-error procedures. A new test method has been developed which permits a more rapid and precise selection of demulsifiers. It involves measuring the electrical stability potential of an emulsion before and after a demulsifier has been added. This paper describes this method and shows where it should have application in field emulsion problems. NATURE OF OILFIELD EMULSIONS Two immiscible components must be present for an emuhion to form; we are concerned here with crude oil and water. An emulsifier must be present for tin emulsion to be stable. J Emulsifiers can be substances which are soluble in oil and /or mter and which lower interfacial tension. They can be colloidal solids such as bentonite, carbon, graphite, or asphalt which collect at the interface and are preferentially wet by one of these phases. Unrefined crude oils can contain both types of emulsifiers, A popular theory is that, of the two phases in an emulsion, the dispersed phase will be the one contributing most to the interfacial tension.' Usually this phase contains the least amount of emulsifier. The stability of a water-in-oil emulsion is affected by the fol1owing: l) viscosity; (2) particle or droplet size; (3) interfacial tension between the phases; (4) phase-volume ratios; and (5) the difference in density between the phases. A stable emulsion is usually characterized by high-viscosity, small droplets, low interfacial tensions, small differences in density between its phases, and slow separatian of the phases. It also has low conductivity (high electrical stability potential). Water-in-oil and oil-in-water emulsions"' are both common; however, oil field emulsions are predominantly water-in-oil emulsions. The emulsions which commonly occur during oompletion and stimulation operations contain a combination of several of the following: acids, fracturing fluids (oil, water, acid), and formation water and oil. Produced emulsions usually contain formation water and oil. Emulsions form in oil wells because oil and water are mixed together at a high rate of shear in the presence of a naturally occurring or unavoidably produced emulsifier. During the completion and stimulation of productive zones, and while formation fluids are being produced, oil and water are very often commingled. These mixtures are formed into emulsions by agitation which occurs when the fluids are pumped from the surface into the matrix of the formation or produced through the formation to the surface. Restrictions to flow (such as perforations, pumps, and chokes)".'" increase the level of agitation; tight emulsions are more likely to form under these conditions. Often an emulsified droplet is an emulsion itself.'" Therefore, emulsion-breaking problems can be quite complex. The complexity can be even greater if a third phase (gas) is included. Demulsifiers operate by tending to reverse the form of the emulsion. During this process, droplets of water become bigger, viscosity is lowered, color becomes darker, separation of the phases faster and electrical stability potential approaches zero. Any of these effects could be followed as a means of determining emulsion stability. However, electrical stability potential is the most reproducible and most easily measured parameter for following the stability of a water-in-oil emulsion.

Jan 1, 1966

By C. Chu

An investigation has been made of the radial heat-wave process using a mathematical model in two-dimensional cylindrical coordinates. This model considers combustion, convection and conduction inside the reservoir, but only conduction in the bounding formations. From a study of the general features of the process, an important phenomenon has been revealed, namely, the feedback of heat into the reservoir on the trailing edge of the heat wave. The effects of various process variables on the performance characteristics of the process have also been investigated. It was found that up to the time when the combustion front reaches a given point, the per cent heat loss, provided it is not higher than 40 per cent, is approximately directly proportional to the square root of thermal conductivity arid fuel content, but inversely proportional to the square root of gas-injection rate and oxygen concentration. The effecr of reservoir thickness is more pronounced, since halving the thickness doubles the per cent heat loss. The most decisive factor in determining the center-plane peak temperature is the fuel content of the reservoir. Within the temperature range investigated, doubling the fuel content doubles the peak temperature in the early stage, but the rate of decline of the peak temperature is high. Reservoir thickness is also a very influential factor. The peak temperature is lowered when the thickness is reduced; however, the effect of thickness becomes less pronounced when the thickness is high. Reduction of oxygen concentration increases the peak temperature in the early stage but lowers it afterwards because of the higher rate of decline of the peak temperature. Increase in gas injection rate or decredse in thermal conductivity geives a higher peak temperature which stays high for a longer period. The propagation range of the heat wave is chiefly governed by the fuel content of the reservoir. An increase of 0.2 1b/cu ft in the fuel content increases the propagation range by 100 per cent. The propagation range is more than doubled by doubling the gas injection rate, or reservoir thickness, or by reducing the thermal conductivity by 50 per cent. Comparatively, oxygen concentration has less effect on the propagation range. INTRODUCTION Several investigators have conducted theoretical studies of a radial heat wave. Vogel and Krueger1 studied a system with a moving cylindrical heat source of constant temper- ature, considering conduction in the radial direction only. Ramey2 included conduction in the vertical direction in his studies. Bailey and Larkin2 attacked a more general problem where initial well heating, vertical heat losses and arbitrary frontal velocities were included. In all these studies, however, conduction was considered to be the only means of heat transfer. Bailey and Larkin in a later paper included the effects of convection in a study involving both linear and radial geometries. Vertical heat losses were neglected in the radial case. Katz5 studied a similar problem in a one-dimensional radial model, using a heat-loss coefficient to account for vertical heat losses. Selig and Couch6 mployed a cylindrical model and investigated two limiting cases. In one case they considered no heat loss from the reservoir whereas in the other they assumed a constant temperature at the interface between the reservoir and its bounding formations. Thomas' studied a more general case but assumed a permeable bounding formation so that the convection effect is not confined to the reservoir. In the present work a more realistic and more generalized model is used. It involves a two-dimensional cylindrical system with combustion, convection and conduction inside the reservoir, but only conduction in the bounding formations. The purpose is to establish the temperature distribution both inside and outside the reservoir, to study the general features of the radial heat wave process, and to investigate the effects of various process variables on the performance characteristics of the process. THEORY We fist consider a circular porous reservoir of thickness H extending vertically from y = — H/2 to y = + H/2. The reservoir extends from a well bore radius r, to an external radius re. A stream of oxygen-containing gas is introduced into the reservoir through the wellbore. The oxygen-containing gas reacts with the fuel contained in the reservoir and forms a combustion front wherever the prevailing temperature can support the combustion. It is here assumed that this combustion front constitutes a cylindrical surface source of heat having an infinitesimal thickness in the radial direction and extending vertically throughout the whole thickness H. This is designated as Region I. We next consider a Region II corresponding to the upper and lower formations bounding the reservoir, extending from y = — - to y = — H/2 and from y = + H/2 to y = + m. Since r, is very small, we may assume that the two bounding formations have the same dimensions, symmetric with respect to the center plane of the reservoir. In this way, we may take the upper half of the system alone into consideration. In contrast with

By N. A. Warner

Dense cylindrical specimens of artificial hematite were reduced in hydrogen over a range 0-f total pressures between 0.1 and 1.0 atm and temperatures between 650" and 950°C. Hydrogen reduction at a total pressure of 1.0 atm in the presence of a chemically inert diluent and reduction in hydrogen/water mixtures were also studied Znter.face movement during reduction was followed using metallographic techniques. Substantiu1 partial-pressure gradients are shown to exist in both the gas film and the reduced iron layer. The results are consistent with a mixed-control mechanism involving an interaction of gaseous-difusion effects with a first-order reversible chemical reaction at the iron/wüstite interface. Over the hydrogen-pressure range of 0.1 to 1.0 atm, the rate is not directly proportional to the hydrogen pressure in the bulk gas stream. Nitrogen dilution of the reducing gas masks the true effect of hydrogen partial pressure by influencing the effective molecular dif-fusivity and gives an apparent first-order relationship. The transport of hydrogen and water vapor across the iron layer is consistent with molecular gaseous diffusion rather than a Knudsen diffusion mechanism. ALTHOUGH the literature on the reduction of iron oxides is very extensive, it is only comparatively recently that a definite quantitative model for the reduction of hematite has been proposed. This development has been largely due to the work of McKewan. An extensive literature review of previous work has recently been compiled by Themelis and Gauvin. Exclusive control by gaseous diffusion in the reduction of hematite has been recently advocated by Kawasaki and coworkers.' Although the results of the latter workers are of considerable practical significance, the extreme porosity (approximately 30 pct) of their specimens precludes their application to a kinetic evaluation of the reduction of dense polycrystalline hematite. The salient features of the kinetic model used by McKewan for the gaseous reduction of dense hematite at temperatures in excess of 560°C (when FeO is stable) are: 1) The reduction is a topochemical reaction taking place through 'the series FeO/FesO4/FeO/ Fe; 2) The gas-solid type of reaction takes place only at the FeO/Fe interface and the internal reduction: FeO proceeds by solid state diffusion; 3) The iron layer formed is quite porous and offers negligible impedance to gaseous diffusion; 4) The rate-controlling step in the reduction is a chemical process occurring at the Fe/FeO interface. In view of the relatively fast reaction rates involved when hematite is reduced in a stream of hydrogen, it seemed possible that the simplifying assumptions of negligible diffusional resistance in both the bulk gas phase and the reduced iron layer could introduce serious errors in the interpretation of experimental reduction data. The present work was initiated to elucidate the effect of gaseous diffusion on the reduction rate and to determine its possible influence in the formulation of the reaction mechanism at the metal/oxide interface. EXPERIMENTAL Procedure and Apparatus. Dense cylindrical compacts of artificial hematite were prepared by sintering pressed compacts of reagent-grade ferric oxide, containing 99.6 pct FezO, in air at 1200°C for 80 hr. The resulting compacts had a final porosity of less than 2 pct and a height and diameter of approximately 1 cm. Variations in sintering atmosphere from air to pure oxygen, in sintering time from 20 to 80 hr, and temperature from 1150" to 1250°C had no effect on the subsequent reduction behavior. The reduction of the samples took place in a vertical tube furnace in which was placed a 1-in. transparent silica tube. The 24-in. heated length

Jan 1, 1964

By R. E. Zinkham, R. J. Goodwin

A mathematical study has been made of the amount of support a cement sheath could provide to casing cemented into the earth. Several assumptions were required to make the analysis, but only two of them are limiting: (I) the pipe must be completely surrounded with cement, and (2) any mud filter cake between the cement and formation has the same physical properties as either the cement or formation. The calculations showed that little support would be provided to the pipe before an unsupported cement sheath failed in tension; however, when the cement is confined between the pipe and wellbore and is loaded in compression, the pipe could receive a considerable amount of support. In fact, the theoretical results indicate the lower grades and larger sizes of pipe could have their working pressures doubled when reasonable compressive loads were applied to a surrounding cement sheath. These data are shown in six charts. Other down-hole conditions such as setting the cement under pressure, increased temperature and cement confinement all tend to increase the potential usefulness of the sheath. Because of size limitations, a laboratory program to verify the most important results of this mathematical study would be very difficult. However, small-scale field tests would be practicable. This paper shows that, if a solid cement sheath can be obtained in the field by either primary cementing or by repair after detection of flaws by surveys such as the new cement-bond logs, the use of this approach to reducing pipe costs merits further consideration. INTRODUCTION A modification in casing design practices is proposed which may either reduce the amount and grade of steel required to contain a specified internal pressure or permit the working pressure to be increased for a specified weight and grade of pipe. One of the more important considerations in casing design is its resistance to collapse; however, Bowers' and, more recently, O'Brien and Goins' have shown many casing programs are unnecessarily conservative in this respect, and they have indicated how savings can be made by designing for more realistic down-hole conditions. Earlier, Saye and Richardson howed that pipe costs could be reduced by considering the cement sheath as a part of the casing string when collapse resistance was being calculated. More recently, Rogers4 has raised the question as to whether a cement sheath might be considered in the design for burst resistance of the cemented casing. Calculations have been made for the increased burst resistance a cement sheath would provide for casing in a wellbore, and the results show that a sizable amount of support could be obtained in some instances. These data are presented in addition to a discussion of several other factors that are considered to affect the burst strength of pipe supported by cement. Two types of support are treated: Case I for tensile loading of the unconfined cement sheath, and Case for compressive loading of the confined cement sheath. ANALYTICAL TREATMENT AND RESULTS CASE I—TENSILE STRESSES IN AN UNCONFINED CEMENT SHEATH Conditions like this would most likely occur in a greatly enlarged portion of the hole where the cement was not in immediate contact with either the formation or a thin and hard mud cake. The mathematical analysis for this condition, as shown in the Appendix, rests on the following concepts. Pressure inside a unit length of pipe causes: (1) a tensile or tangential stress to be exerted over the longitudinal cross-sectional areas of the pipe and cement; and (2) an equal amount of strain in both the pipe and cement that is uniformly distributed over the wall thickness of each. This analysis was then used to make several calculations for a cement sheath around 51/2-in. OD pipe. The results are illustrated in Fig. 1, which shows that a tensile stress of 500 psi is imposed on a 5-in. thick sheath when the casing contains a pressure of only 1,450 psi. It also shows that a 10-in. thick sheath would be stressed to 500 psi in tension when the pipe contained a pressure of only 2,350 psi. Alternatively, if the stress analysis is made by means of the Lame thick-wall cylinder theory, the inner fibers of the 10-in. thick sheath will be stressed to 500 psi in tension when the pressure in the pipe is only 990 psi. This, of course, reveals that an unconfined sheath is of little support to the pipe in burst; however, an entirely different result is obtained when the cement is confined between the pipe and formation.

By C. J. Bechtoldt, H. C. Vacher

Quenched alloys, prepared by powder metallurgical techniques, were examined by microscopic and X-ray diffraction methods. The compositions and heat treatments were chosen so that the chromium and nickel solvuses could be determined and a range of composition and temperature, in which a eutectoid had been reported, could be explored in small intervals. The results showed no evidence of eutectoid reactions having taken place. ALLOYS containing iron, chromium, molybdenum, and nickel are extensively used in high-temperature applications. In order to provide basic information on the solid-state reactions that occur in such alloys, the National Bureau of Standards is engaged in an extensive study of the equilibrium phases in the binary, ternary, and quaternary systems involving these four metals. Attention was directed to the chromium-nickel system because a review of the literature showed conflicting data. A recent compendium1 of the constitution of binary alloys gives two diagrams for the chromium-nickel system, one a simple eutectic and the second a diagram showing a eutectoid and a eutectic. The eutectoid was the result of an allotropic transformation in a high-temperature solid-solution form of a chromium-rich phase called 0. The approximate temperature and composition of the eutectoid was 1200°C and 30 at. pct Ni. In the preliminary study, at the Bureau, no transformation was indicated in the chromium-rich phase of ternary and quaternary alloys in which chromium and nickel were major components. Similar results have been reported from time to time in the literature,2-8 In consequence of this situation, a systematic study was made of the constitution of heat-treated chromium-nickel alloys using metallographic and X-ray diffraction methods. The compositions of the alloys were selected so as to determine the boundaries of the chromium-rich and the nickel-rich phases and to explore in small intervals the ranges in composition and temperature in which the eutectoid had been reported. The results of this study are reported and discussed in the present paper. EXPERIMENTAL PROCEDURES Materials, Alloys, and Heat Treatments—The alloys were prepared by a powder metallurgy technique similar to that used in earlier work.9 Analyses of the materials used are given in Table I. Powders were mixed using a vibrator in 30-g batches of predetermined composition; 2-g pellets were made from the mixture by compacting at room temperature in a 1/2-in. diam mold under 60,000 lb per sq in. pressure. The pellets were sintered in dry hydrogen for 10 days at 1300°C. At the end of the sintering treatment the specimens were quenched in water, which caused a pale green film to form on the chromium-rich alloys and thin black scale to form on the nickel-rich alloys. The pellets after sintering were approximately 1/2 in. diam by 3/32 in. thick. The purification train9 was modified by inserting a tube of titanium turnings, heated at 700°C to increase the efficiency of the removal of oxgen and nitrogen. It was found in the earlier work that the sintering treatment lowered the carbon, oxygen, and nitrogen contents of chromium-rich alloys to 0.01, 0.01, and 0.004 wt pct, respectively, and that there was a loss of chromium. In order to ascertain the extent of this loss, the chromium contents of certain alloys were determined chemically. They included those alloys used to determine the parameter-composition curves and those of critical composition, used to determine the chromium-solvus microscopically; these analyses were made on samples after the final heat treatments. The mixed powder values for the chromium content of those alloys that were not analyzed were adjusted to conform to a smooth curve based on the chemically analyzed values for

Jan 1, 1962

By Nicholas J. Grant, Ulf Kalling, John Chipman

THE operation of a blast furnace is dependent to an important extent upon the sulphur content of materials charged and the desired limit of sulphur in the product. It has long been known that the blast furnace is the most efficient tool for desulphurization in common use and that this efficiency is associated with the strongly reducing conditions of the hearth and is enhanced by increased basicity and fluidity of the slag. The chemical reactions of desulphurization may be studied from the viewpoint of the ratio of the process or of the final equilibrium conditions. Both kinds of studies contribute to an understanding of the process and both are included here. A simple measure of the desulphurization power of a slag is given by the ratio: Pct sulphur in slag (Pet S) Pct sulphur in metal [Pct S] This ratio was used by Holbrook and Joseph',' to measure relative desulphurizing powers under controlled laboratory conditions. It was also used by Hatch and Chipman3 as a measure of the equilibrium distribution. For the latter purpose it would be preferable to employ thermodynamic activities rather than percentages, but until very recently this has been impossible for lack of data. Now, thanks to the work of Morris and Williams and Morris and Buehl," the effects of carbon and silicon upon the activity of sulphur in the metal are known. The confirmation of this work and its extension to include the effects of other elements by Sherman and Chipman and by Rosenqvist and Cox' make it possible to calculate the activity of sulphur in pig iron of any composition. Hence it is now possible to use data on the equilibrium distribution of sulphur to find its activity in the liquid slag and to approach an ultimate solution of the thermodynamic aspects of the problem. The rate of transfer of sulphur from metal to slag is the problem of major industrial importance and indeed the principal need for equilibrium data has been as a necessary adjunct to the kinetic studies. The rate of approach to equilibrium under laboratory conditions seems slow compared to the requirements of industrial practice, and it is clear that further laboratory studies of rates are needed. In the research reported below, the items which were investigated were the following: I—The role of mechanical stirring on the approach to equilibrium. 2—The role of MgO in desulphurization as compared to CaO. 3—The role of MnO in desulphurization. 4— The limiting reactions which constitute the slow steps in desulphurization. Experimental Procedure The experimental set-up and procedure previously described by Hatch and Chipman" were essentially followed with several small modifications. The graphite crucible containing the slag and metal charge was altered to provide considerably more active stirring and mixing of the slag and metal in the carbon monoxide atmosphere. For this purpose the crucible was machined to provide two deep cylindrical wells which were interconnected at top and bottom as shown in Fig. 1. A graphite screw with a flat thread and of shallow pitch (4 threads per in.) spinning at 600 to 800 rpm was used to lift the slag and metal over the partition between the two wells and throw them over into the second well, where the metal settled through the slag into the reservoir at the bottom. It was possible to see actual particles of slag and metal being thrown over the partition. In this respect, the stirring was more vigorous than used in the work of Hatch and Chipman. A charge of 400 g of wash metal was first melted, and 20 g of FeS was then added to yield a bath containing 1.65 pct S. Immediately 400 g of slag (as pure mixed oxides) was added and fused. The slag was generally fused in 1 hr * 10 min. Within 30 to 45 min after melting, the temperature was adjusted to 1525"C, and the first slag and metal samples were taken. The slag was picked up on the end of a cold Armco iron rod, whereas the metal was sucked into a silica tube. The wash metal composition was (in percent): 4.29 C; 0.022 S; 0.021 P; 0.38 Si. The slags used were of four fixed starting compositions covering a wide range of acid-base ratios shown in Table I. Deliberate variations in MgO were made in these slags to check the role of MgO in blast-furnace desulphurization. Changes due to additions and reactions were followed by analysis of samples. Additions of Mn and MnO were made to most of the heats to note the role of Mn and MnO on desulphurization. Three heats (62 through 64) were made in an open pot induction crucible (graphite) using a

Jan 1, 1952

By Leah L. Naugle, H. G. Landau, H. H. Lowry

EVIDENCE has been accumulating in recent years, in part from the work of the Coal Research Laboratory, that coals belong to a family of natural polymers and that even in complex reactions the differences between coals are quantitative and not qualitative. This point of view leads to the expectation that if a series of coals were subjected to a closely controlled set of experimental conditions the results obtained should be related to the chemical analyses of the individual coals. The data accumulated over the past 10 years by the Bureau of Mines in its "Survey of Coke-, Gas-, and By-Product-Making Properties of American Coals," in what has come to be recognized as the Bureau of Mines-American Gas Association (BM-AGA) carbonization assay test,1-12 offer an unusual opportunity to check this conclusion. The present paper reports an analysis of the data on the first go coals and coal blends-including coals numbered I to 55b, inclusive -which have been carbonized according to a standard procedure at intervals of 100°C. from 500° to 1100° in either or both 13 or I8-in. cylindrical retorts." In Table I are given the name of the seam from which the sample was obtained, the analytical data used, and the reference to the original publication of the Bureau of Mines. The coals range in fixed carbon from 46.2 to 79.0 per cent, in volatile matter from 15.4 to 41.3 per cent, in ash; from 2.1 to 15.9 per cent, in moisture from o.8 to 19.7 per cent, and in total sulphur from 0.40 to 4.44 per cent; therefore the entire gamut of bituminous coals is represented. The petrographic nature of the individual coals is not considered in the following analysis, although both "normal" bright coals and splint coals are included in the samples studied. For information on the petrography of the coals and for further information characterizing the coals the original papers should be consulted. Although the coals that are included extend over the whole range of bituminous coals, they do not cover this range entirely adequately. In particular, only 13 of the go coals have moisture contents greater than 3 per cent. This concentration at low moisture values means that the effect of moisture, which is an important factor, cannot be determined with as much certainty as would be desirable. All the coals were not tested at every temperature and in both retort sizes. Only the first 30 coals were tested at 1100°, and only about 50 at the other temperatures, except at 900°, where nearly all of them were included. In the accompanying tables the actual number of observations entering into each correlation is given. In this study equations are given for calculating analyses, yields, and properties of coke and by-products from the coal analyses. To decide whether these equations are satisfactory it is necessary to know the accuracy with which these quantities were measured in the assay tests.

Jan 1, 1941

By Adrien Berton

FOR nearly a century, the Corocoro deposit has been renowned among geologists from the fact that it shares with the Lake Superior deposits of the United States the distinction of being the only important copper districts where native copper is worked commercially. The Corocoro district, named after the city of Corocoro, the capital of the Province of Pacajes (Department of La Paz, Bolivia) is situated towards the western edge of the Bolivian high plateau, at an altitude of a little over 13,000 ft. The most interesting part of the district is that immediately surrounding the city of Corocoro, at a distance, by railway, of 65 miles from La Paz and 210 miles to the Chilean port of Arica on the Pacific Coast. The climate of the region is that of the semi-desert, dry and relatively cold, with big differences of temperature between day and night. The rainy season begins in December and ends in March. The cupriferous lodes of Corocoro have not attracted as much interest as the silver mines of Potosi but they have been known for a long time. In the precolonial period the Indians were using the charquis, or natural native copper sheets, to make small brass objects, and the beautiful pale green brochantite of the outcrops as a source of green pigments. During the colonial period, the oxidized ores of the outcrops were worked for copper, which was used by the mint at Potosi for making currency. The native copper ores were neglected because the Spanish miners were at a loss how to concentrate and smelt them. About 1830, work by rudimentary processes, which were improved little by little, was begun on the native copper ores. The total production of native copper in the following hundred years amounted to 100,000 tons. This native copper, which was remarkably pure, was much appreciated on the European markets before the introduction of electrolytic copper. It was useful for making special ornamental brass or bronze and the granular concentrates of native copper, called barrilla, containing 80 to 85 per cent copper were suitable for making copper sulfate by direct oxidation and subsequent leaching with sulfuric acid.

Jan 1, 1936

By C. W. Allen, L. C. Moore

THE Mather mine, of the Negaunee Mine Co., is within the limits of the City of Ishpeming, on the Marquette iron- range in Michigan's Upper Peninsula. It is named for William G. Mather, who has served as President, and Chairman of the Board, of The Cleveland-Cliffs Iron Co. for well over 50 years. The property comprises nearly the square mile of section 2, T.47 N. R.27 W., which, except for 20 acres in the northeast corner, was leased by The Cleveland-Cliffs Iron Co. to the Negaunee company. The latter is a partnership of Cleveland-Cliffs and the Bethlehem Steel Co., organized to equip the property, retaining Cliffs in charge as operator. Shipments of ore from this area are mainly through Marquette, which is 16 miles to the northeast on Lake Superior, or through Escanaba, a Lake Michigan port, 65 miles to the south. Cleveland-Cliffs, in 1943, operated 12 mines in the Lake Superior district, with shipments of 6,635,576 tons for the year. GEOLOGY The north footwall of the Marquette Range synclinorium outcrops near the north line of sec. 2, the iron formation dipping to the south at an angle of about 40º. The south side of the trough reappears at a distance of 4 ½ miles on sec. 26 and the surface geology between shows iron formation or intrusive diorites. The latter are harder than most phases of the iron formation and, as a result of glacial action, appear as buttes or low-lying hills. The general elevation of sec. 2 is about 1450 ft. above sea level, or 850ft. above Lake Superior, and the higher diorite outcroppings about 1600 ft. above sea level. The geological structure has been complicated by a series of major and minor faults, one of which may be illustrated by the diorite sheet, which tilts south with the iron formation in the north half of the section and then reappears near the center to repeat this sequence. Sectionally the geological series includes a nearly eroded capping of Goodrich quartzite followed by the considerable thickness of Negaunee iron formation, which is cut by intrusive dikes or diorite sheets, and underlain by the Siamo slates grading into quartzites. The ore deposits occur mainly in troughs formed by the intersection of impervious dikes and the footwall slate, but include locally enriched lenses or bands in the iron formation and also interbedded with the Siamo slate. The ore is a soft red hematite with an indicated dried analysis from the surface drilling to date of 61.50 per cent Fe, 0.134 per cent P, 5.40 per cent Si, 2.87 per cent Al and 0.015 per cent S. EXPLORATION A diamond-drilling campaign started in 1937 actually had its inception in 1917, when a number of shallow test holes were put down for the purpose of locating ore that might be quickly developed and mined

Jan 1, 1945

By L. D. Hall, D. R. Mash

The paper presents the results of experiments on the anelastic. behavior of gold, as manifested by grain boundary relaxation. Two grain boundary internal friction peaks are found for 99.9998 pct Au. It is found that the peaks are associated with primary and secondary recrystallization. However, the existence of two discrete peaks cannot be explained on the basis of grain size and shape alone. It is suggested that grain boundary stability, as determined by orientation, plays a role in the observed effects. EVIDENCE for the viscous behavior of grain boundaries in metals has been presented in recent years by several investigators, based upon studies of various anelastic effects, especially internal friction. KG1 has contributed greatly to this field, having put forward a coherent body of evidence for stress relaxation by the viscous intercrystalline flow mechanism. In this connection, he has made extensive use of pure aluminum (99.991 pct) as the test material, although he has also studied other metals and alloys, including pure iron (Puron).² Rotherham, Smith, and Greenough³ have studied the internal friction of pure tin, interpreting their results in a manner similar to that of KG. In view of the importance of such studies in shedding light upon the fundamental structure and behavior of the grain boundaries in pure metals, it appears that the use of a very pure test material which is inert to its environment should provide useful information on anelastic properties and the source of such behavior in pure metals. The present work was carried out on spectrograph-ically pure, 99.9998 pct Au, free of all impurities except for a trace of silver, estimated to be present to the extent of about 0.0002 pct. The term "pure gold" will hereafter refer to this very pure material. Gold of commercial purity, 99.98 pct, was also studied to observe the effects of small amounts of impurities. A pure gold "single crystal" specimen was also tested for comparison. The variation of the internal friction and rigidity modulus as a function of temperature was determined by means of a torsion pendulum apparatus employing extremely low stress amplitudes and a frequency of vibration of the order of 1 cycle per sec. A 12 in. length of 0.031 in. (20 gage) gold wire formed the suspension element. The apparatus was similar to that described by Ke.l The test procedure and the basic requirements to be met for obtaining useful experimental data by this method have been given elsewhere.1,2 It should be made clear that in all of the experiments to be described, the internal friction and rigidity were independent of the amplitude of torsional vibration. The semilog plot of amplitude of vibration vs ordinal number of vibration was a straight line. This was carefully verified for each internal friction measurement. The linear variation shows that the internal friction was independent of stress; i.e., that the specimens were not being cold-worked during testing. The reproducibility of the internal friction curves, which were obtained by cyclic heating and cooling, indicates that the gold was unaffected by its environment during the tests. The measure of internal friction adopted in the present study is the conventional "logarithmic decrement," defined as follows: log. dec. = l/n In A0/An [I] where n is the number of cycles or vibrations; A,, the initial amplitude of vibration; and An, the amplitude after the nth cycle. When the logarithmic decrement is small, the shear modulus, G, of the wire is proportional to the square of the frequency of vibration provided the length and radius of the wire are kept constant. A plot of frequency squared vs temperature gives the following ratio:' This expresses the fraction of the stress which has not been relaxed at a given temperature. Gr and Gv are the relaxed and unrelaxed moduli, respectively. The frequency of vibration in the polycrys-talline specimen is fp, and the frequency of vibration of a single crystal is f8. This latter quantity is obtained simply by extrapolating the linear, low temperature portion of the curve of frequency squared vs temperature for the polycrystalline specimens. The theory of viscous grain boundary stress relaxation as demonstrated by the anelastic behavior of metals has been discussed in detail by Zener4 and need not be reproduced here. Experimental Results Initial measurements of the internal friction of pure gold were carried out on specimens which had been drawn with no intermediate annealing, resulting in a material which had undergone approximately 99 pct reduction of area in final processing. Annealing was then carried out at successively higher temperatures starting at 400°F for 1 hr and proceeding in this manner to as high as 1600°F in 100°F intervals. After each annealing treatment an internal friction and rigidity vs temperature curve was obtained over the range from room temperature to the particular annealing temperature. The resulting internal friction curves did not exhibit well defined maxima (peaks), but rather several fairly flat

Jan 1, 1954

By P. A. Witherspoon, R. W. Donovan, T. D. Mueller

The use of petroleum-barren aquifers for underground storage has become extremely important to the natural-gas industry. A critical problem in assessing the feasibility of a specific aquifer for such use is the permeability determination of the caprock over the proposed storage project. The approach used here is to conduct both static and dynamic field tests on the aquifer being analyzed. Valuable information on the possibility of communication between the storage aquifer and any other aquifers above can be obtained by measuring hydrostatic water levels and water analyses. Significant differences in such data give evidence of the lack of communication between the intended storage reservoir and other horizons. The dynamic approach requires that one well be pumped in the storage aquifer, and changes in fluid levels recorded in both the aquifer and its caprock. The interpretation of the data from such pumping tests involves the solution of nonsteady radial flow in an infinite aquifer and the influence on such flow of a leaky caprock. A finite-difference model has been used to investigate this problem, and the transient behavior has been solved numerically with a digital computer. It has been found that the pressure transients in the storage aquifer are not affected significantly by moderate caprock leakage. The pressure behavior of the caprock is a much better indicator of the degree of leakage, and generalized solutions for this behavior are included. Field data are presented to demonstrate both the static and dynamic approach. If is concluded that appropriate investigation of the groundwater hydrology in an aquifer-type gas-storage project can provide much valuable information for determining the effectiveness of the caprock to hold gas. INTRODUCTION Underground storage of natural gas in the United States has been developing at a rapid rate over the past few years. In 1955, the total gas-storage capacity was about 1.6 trillion cu ft; by 1961, this figure was almost 3.2 trillion cu ft, an increase of 100 per cent in six years.' This trend un- doubtedly will continue because the economics favor the development of gas storage, as opposed to the construction of new pipelines, to meet the inherent cyclic demand for fuel in the metropolitan areas of this country.' About 15 per cent of the current underground gas storage has been developed in petroleum-barren aquifers, i.e., geological domes or anticlines in which no commercial quantities of oil or gas had been produced prior to the storage operations. The necessity for using barren aquifers outside many metropolitan areas of this country has been due to the lack of depleted oil or gas fields that were near enough and large enough to meet the demands of such consuming areas. Pipeline companies have developed aquifer storage along their transmission lines to meet the fluctuating needs of their complex systems. Considerable thought has also been given to the problem of storing gas in a structureless aquifer, both in this country' and in the Soviet Union outside the city of Leningrad.'," Conditions such as these have led to the development of aquifer gas-storage projects in many parts of the U. S. Most of these developments have centered in the Mid-Continent area, and the greatest amount of activity has been concentrated in Illinois.6 Thus, the use of petroleum-barren aquifers for gas-storage purposes has become extremely important to the natural-gas industry. There are three basic problems in developing aquifer-type storage: (1) finding an adequate geologic structure, (2) finding a suitable storage reservoir within the structure and (3) determining the tightness of the caprock over the intended storage zone. The first two problems can be solved by applying conventional methods of exploration geology, but once these problems are solved, the question arises as to why no oil or gas is present in an otherwise favorable setting. Two situations are possible: (1) an adequate source bed was never present, or (2) a source bed was present but the petroleum seeped away because of a leaky caprock. Determining the tightness of the caprock is one of the most critical problems in assessing the feasibility of a specific aquifer for storage purposes. In attacking this problem, one usually takes cores of the caprock and subjects them to a rigorous investigation. Such core data are desirable, but they only detail the matrix properties and cannot be expected to reveal the gross characteristics of the caprock. Several gas-storage projects in the U. S. have had considerable leakage where

By Walter J. Johnson

The coals in northern Wyoming and Montana are free-burning and non-caking and range from lignite to bituminous C in rank. Strip and underground mining are employed to supply railroad, utility, industrial, and domestic fuel. The market area includes Iowa, Nebraska, Minnesota, North and South Dakotas, Wyoming, Montana, the Pacific Northwest, and western Canada. THE larger producing coal mines in northern Wyoming are located in the Powder River Basin lying between the Black Hills region of South Dakota, eastern Wyoming, and the Big Horn Mountains in north central Wyoming, see Fig. 1. The mines are located particularly in the area along the route of the Chicago, Burlington & Quincy Railroad from Gillette, Wyo., to a point approximately 15 miles northeast of Sheridan, Wyo. Fig. 2 is a graph of coal production in the state of Wyoming from 1918 to 1951. Across the Big Horn Mountains lies the Big Horn Basin, situated between the Big Horn Mountains and the Rocky Mountains proper. Mining in the Big Horn Basin is almost entirely confined to a small area known as the Gebo Field, near the town of Kirby, which is located on the Chicago, Burlington & Quincy Railroad. This paper will describe present operating areas, making only brief reference to the history of mining and marketing primarily because of the large area to be discussed. The coal beds presently mined in the Powder River Basin are all of Tertiary age and are of Fort Union and Wasatch formations of Paleocene and Eocene ages, see Fig. 3. The Fort Union formation, consisting of 2000 to 3200 ft of alternate sandstone, shale, and coal, is divided from oldest to youngest into the Tullock, Lebo Shale, and Tongue River members. Most of the mineable coal is in the Tongue River member, which is 500 to 800 ft thick. The Carney coal bed, varying from 7 to 20 ft in thickness, is considered the base of the Tongue River member. About 85 ft above the Carney is the Monarch bed, ranging from 18 to 42 ft in thickness. At approximately 210 ft above the Monarch is what is locally known in the Sheridan district as Dietz No. 3 bed, which varies from 12 to 30 ft in thickness. One hundred feet above the Dietz No. 3 is Dietz No. 2 bed, which is 7 to 12 ft thick. At about 100 ft above the Dietz No. 2 is Dietz No. 1 bed, 7 to 15 feet in thickness. Two hundred and fifteen feet above Dietz No. 1 is the Smith bed, approximately 5 ft thick. One hundred twenty-five feet above the Smith is the Roland bed, which is estimated to be approximately 13 ft thick. The Roland bed is considered the base of the Wasatch formation, which in the Powder River Basin is 1000 to 3500 ft thick and is composed largely of shale, sandstone, and coal. The foregoing measures are the only ones above the Tongue River member that have been mined in the Sheridan field. To the east of the Sheridan field, particularly in the area of Gillette, the Roland bed is considerably thicker and is considered the thickest and most extensive coal bed in Wyoming, reaching a maximum thickness of 106 ft. From 125 to 225 ft above the Roland lies the Arvada bed, average thickness 9 ft. Three hundred seventy-five to four hundred feet above the Arvada is the Felix bed, which reaches its maximum thickness of 30 ft near Echeta on the Chicago, Burlington & Quincy Railroad. East of the Powder River the bed averages more than 10 ft in thickness, but it thins in a northwesterly direction. The highest mineable coal in the Powder River field is the Healy bed, about 400 ft above the Felix bed and exposed only in the highest parts of the area where much of it has been burned along the outcrop. Where it has not been burned, the thickness at most of the outcrops is 10 to 15 ft.

Jan 1, 1954

By N. G. W. Cook

The conventional cyclic system of deep-level mining by drilling and blasting gives rise to an inadequate degree of stope sorting when mining thin reefs. This results in poor utilization of the capital facilities of a mine in the form of shafts, haulages, airways, and associated equipment. Continuous and controlled removal of the thin gold-bearing portion of the reefs would permit better stope sorting and hence greater utilization of capital facilities. Results of experiments to develop hard-rock cutting machines for mining are reported and the benefits which could be derived from their use are discussed. Mining, from exploration through refining, is essentially a process of sorting in which the payable mineral, or metal, is progressively separated from the other constituents of the earth's crust with which it was originally associated. This takes place more distinctly at each step of the operation. What is it that determines the degree to which sorting should be carried out at each of the several steps comprising a whole mining operation? The formal answer is that degree of sorting at each step which results in the lowest overall cost for the complete separation. In practice, individual steps are chosen from those available in current technology, each of which effects a degree of sorting such that the quantity of material which must be sorted in the succeeding step is economically acceptable. It follows that any new technological development has repercussions throughout the whole mining operation and, more important, that the solution to excessive costs in any one step of the operation may lie not in improving the costly operation itself so much as in increasing the degree of sorting preceeding that operation. This concept, particularly in relation to deep-level mining of thin, tabular gold-bearing reefs in South Africa, is discussed here, and the most recent results achieved in the development of hard-rock cutting machines for stoping more selectively than is possible with explosives are presented. Deep-Level Mining Deep-level mining involves operations which are either not encountered, or are of only trivial importance, in near-surface mining. Near-surface, the major operations are those of rock breaking, transport, and milling. In deep-level mining, hoisting, environmental control, and strata control assume major importance. Some idea of the relative magnitude of these operations may be gained by comparing the separate amounts of energy which are required, or which must be controlled, to effect the various operations when, say, mining a tabular deposit 40 in. thick at 8000 ft below surface, Table 1. It is true that the costs of handling a given quantity of energy are not the same for each operation. Nevertheless, Table 1 does emphasize the fact that the operations of hoisting, strata control, and environmental control are of unique and major significance in deep-level mining. In particular, hoisting and environmental control place a heavy load on the reticulation system of the mine—the shafts, haulages, and airways. Typically, a new, deep gold mine with an annual revenue of about $35 million requires a total capital expenditure of about $140 million of which some $100 million is invested in developing and equipping this reticulation system. The ratio between annual turnover and capital invested of about one-quarter is exceptionally low, and it typifies the poor utilization of capital by the current technology of mining hard rock at depth. The average thickness of the reefs in the new South African goldfields varies from 10 to 30 in.,l and even in the thicker reefs the gold is often confined within a small fraction of the nominal thickness. Nevertheless, it is universal practice to mine these reefs at a stope width of about 40 in. or more, so that the quantity of rock broken in the stopes and hoisted out of the mine is between two and ten times the quantity of rock actually carrying a significant amount of gold. The reason for the adoption of such excessive stope widths is to be found in the method of rock breaking by drilling and blasting. The only free surface to which a blast hole can break is the stope face. It follows2 that each hole cannot have a burden in excess of the height of the free face if it is to break satisfactorily. To

Jan 1, 1971

By J. A. Musselman, P. F. Gnirk

A study was made of indexed penetrations by a single dull bit tooth under statically applied loads into rock subjected to confining pressures from atmospheric to 5,000 p.si and atmospheric pore pressure. Experimental results obtained with a 45" wedge tooth over the above range of pressures are presented for two limestones and a sandstone, a variely of indexing distances and two degrees of tooth dullness. The optimum distance between successive bit-tooth penetrations required for maximum rock damage and chip formation decreases substantially with increa.sing confining pressure above the brittle-to-ductile transition pressure of a particular rock. However, the distance remains approximately constant for a variation in confining pressure below the transition pressure. At a given confining pressure, the bit-tooth force required lor chip formation is constant for indexing distances greater than optimum, but generally decreases linearly with decreasing indexing distance for distances less than optimum. The chip-formation force data obtained at confining pressures for which the chip-generation mechanism is macroscopic-ally of a pseudoplastic nature compare favorably with previous theoretical results for indexed dull hit-tooth penetrntion into an idealized, rigid, perfectly plastic rock. INTRODUCTION To study the cutting action of a roller-cone bit, the interaction of a penetrating bit tooth with craters formed in a rock surfacc by the passage of previous bit teeth must be considered. Current knowledge of the basic mechanics of bit tooth-rock intcract:on under simulated borehole environmental conditions has been extensively reviewed.',' Particularly of current interest are the effects of bit-tooth shape, distance between successive penetrations and differential pressure at the rock surface on the extent of the interaction. Pertinent to this paper are results of an experimental investigationb f the interaction between successive penetrations by sharp, wedge-shaped bit teeth. It was demonstrated that both bit-tooth angle and differential pressure influence the extent of rock damage between successive bit-tooth penetrations. Specifically, the optimum or minimum distance between successive penetrations required for maximum interact'on or chip generation tends to decrease with decreasing bit-tooth angle and increasing differential pressure. In addition, at differential pressures on the order of 2,000 psi for four va- rieties of limestones and sandstones, the macroscopic mechanism of chip formation exhibits a transition from brittle to ductile. In this paper, experimental consideration is given to successive or indexed penetrat ons by wedge-shaped bit teeth. Since pore pressure in a rock sample is maintained at atmospheric pressure, the differential pressure at the fluid-rock interface is equal to the confining pressure. The degrees of bit-tooth dullness include teeth with flat and round apexes (Fig. 1). Of primary concern in this paper are the bit-tooth forces required for chip formation, the macroscopic mechanism of chip formation and the minimum distance between successive penetrations, i.e., optimum indexing distance required for maximum rock damage, as functions of differential pressure. Of further interest is a comparison of actual bit-tooth chip formation forces at elevated differential pressures with calculated forces from previous theoretical results4 for indexed dull bit tooth penetration into a rigid-plastic rock. EXPERIMENTAL APPARATUS AND PROCEDURE The experimental apparatus consists of a pressure vessel equipped with a piston through the side of the vessel (Fig. 2). A single bit tooth inserted in the lower end of the piston is forced at a desired rate into the rock when the ram pressure chamber is pressurized. Electrical instrumentation incorporated into the apparatus yields a graphical plot of force on the piston as a function of bit-tooth penetration or displacement into the rock. Since the piston and ram assembly are in force equilibrium for a constant confining pressure in the main vessel, the fluid volume in the vessel remains constant during bit-tooth penetration. Hence, the force resisting penetration of the tooth is independent of the force exerted on either end of the as-

By K. E. Brown, A. R. Hagedorn

Continuous, two phase flow tests have been conducted during which four liquids of widely differing viscosities were produced by means of air-lift through 1%-in. tubing in a 1,500-ft. experimental well. The purpose of these tests was to determine the effect of liquid viscosity on two-phase flowing pressure gradients. The experimental test well was equipped with two gas-lift valves and four Maihak electronic pressure transmitters as well as instruments to accurately measure the liquid production, air injection rate, temperatures, and surface pressures. The tests were conducted for liquid flow rates ranging from 30 to 1,680 BID at gas-liquid ratios from 0 to 3,-270 scf/bbl. From these data, accurate pressure-depth traverses have been constructed for a wide range of test conditions. As a result of these tests, it is concluded that viscous effects are negligible for liquid viscosities less than 12 cp, but must be taken into account when the liquid viscosity is greater than this value. A correlation based on the method proposed by Poettmann and Carpenter and extended by Fan-cher and Brown has been developed for 1¼-in. tubing, which accounts for the effects of liquid viscosity where these effects are important. INTRODUCTION Numerous attempts have been made to determine the effect of viscosity in two-phase vertical flow. Previous attempts have all utilized laboratory experimeneal models of relatively short length. One of the initial investigators of viscous effects was Uren1 with later work being done by Moore et al.2,3 and more recently by Ros.4 However, the present investigation represents the fist attempt to study the influence of liquid viscosity on the pressure gradients occurring in two-phase vertical flow through a 1¼-in., 1,500 ft vertical tube. The approach of some authors has been to assume that all vertical two-phase flow occurs in a highly turbulent manner with the result that viscous effects are negligible. This has been a logical approach since most practical oil-well flow problems have liquid flow rates and gas-liquid ratios of such magnitudes that both phases will be in turbulent flow. It has also been noted, however, that in cases where this assumption has been made, serious discrepancies occur when the resulting correlation is applied to low production wells or wells producing very viscous crudes. Both conditions suggest that perhaps viscous effects may be the cause of these discrepancies. In the first case, the increased energy losses may be due to increased slippage between the gas and liquid phases as the liquid viscosity increases. This is contrary to what one might expect from Stokes law of friction,' but the same observations were made by ROS4 who attributed this behavior to the velocity distribution in the liquid as affected by the presence of the pipe wall. In the second case, the increased energy losses may be due to increased friction within the liquid itself as a result of the higher viscosities. The problem of determining the li- quid viscosity at which viscous effects becomes significant is a difficult one. Ros4 has indicated that liquid viscosity has no noticeable effect on the pressure gradient so long as it remains less than 6 cstk. Our tests have shown that viscous effects are practically negligible for liquid viscosities less than approximately 12 cp. Actually there is no single viscosity at which these effects become important. These effects are not only a function of the viscosities of the liquids and of the gas but are also a function of the velocities of the two phases. The velocities in turn are a function of the in situ gas-liquid ratio and liquid flow rate. Furthermore, the role of fluid viscosities in either slippage or friction losses will depend on the mechanism of flow of the gas and liquid, i.e., whether the flow is annular. as a mist, or as bubbles of gas through the liquid. These mechanisms are also a function of the in situ gas-liquid ratios and the flow rates. It would thus seem that the best one could hope for is to determine a transition region wherein the viscous effects may become significant for gas-liquid ratios and liquid production rates normally encountered in the field. The viscous effects might then be neglected for liquid viscosities less than those in the transition region but would have to be taken into account when higher viscosities are encountered. There are numerous instances where crude oils of high viscosity must be produced. The purpose of this study has been to evaluate the effects of liquid viscosities on twephase vertical flow by producing four liquids of widely differing viscosities through a 1 % -in. tube by means of air-lift. The approach used in this study was as follows:

Jan 1, 1965

By J. B. Campbell, V. V. Valleroy, B. T. Willman, L. W. Powers

A steam drive of heavy oil was field tested in a shallow, low oil-saturation formation near Deerfield, Mo. The pilot was conducted in the Warner formation, a sandstone containing an 18' API oil having 1,000-cp viscosity at the 60F origind reservoir temperature. The formation war at a depth of 160 ft. Steam was injected into nine input wells arranged in an array of inverted five-spot patterns. In the completely confined center pattern, 14 temperature observation wells were installed to obtain thermal data and observe test progress. Late in the test, slugs of ammonia were injected to trace the flow paths of injected fluids. From the test area about 7,000 bbl of oil were produced. Data were obtained on areal and vertical temperature distribution, steam front advance, reservoir fluid movement and terminal saturations. This field test of a steam drive (I) demonstrated the feasibility of the method, (2) confirmed that the low residual oil saturations observed in the laboratory are obtained in the steam-swept region in the field and (3) provided recovery and conformance data for one set of field conditions. INTRODUCTION The Deerfield steam drive pilot test was conducted in a shallow sandstone containing 1,000-cp oil. The venture was undertaken cooperatively by the research and production departments of Carter Oil Co., which organizations have since been consolidated into Esso Production Research Co. and Humble Oil & Refining Co.. respectively. The production department was interested in steam injection at Deerfield because it appeared to be the most promising method of commercially producing this heavy oil deposit. The research department was interested in applying the new recovery method and in evaluating its performance in the field. At the time the test was begun, the initial oil saturation was not well known. Subsequent air coring and early pilot results confirmed that there was too little oil in place for profitable commercial exploitation by steam. Pilot termination at that time, however, would have been premature for evaluating field performance of the process, and the tert was continued to obtain additional data on steam injection as a recovery method. The test was located in Vernon County, Mo., about 10 miles north of the town of Deerfield and only a few miles from the Kansas border. The pilot site was selected as typical of the area. The location represented neither the highest nor the lowest oil saturation region in the acreage under lease in 1954. The steam drive was conducted in the Warner sandstone of Lower Pennsylvanian age. At the test site the top of the Warner occurs at about 160 ft subsurface and the formation is a fine- to medium-grained micaceous sandstone that dips gently to the northwest at the rate of 12 to 15 ft/ mile. A cross-section and permeability profile of the test location are shown in Fig. 1. At the pilot location the average total thickness of the Warner formation is about 43 ft, but the effective thickness for steam drive is 26 ft. Two distinct types of hydrocarbon saturation are apparent. The lower portion of the total sand, averaging about 17 ft thick, contains a very heavy asphaltic material that will not flow under the influence of a steam drive. This bottom interval, referred to as a dead oil residue, was not considered as part of the net sand undergoing steam exploitation. The initial formation and fluid properties of the upper 26 ft in the test area are summarized in Table 1, and variation of oil viscosity with temperature is shown in Fig. 2. Imbibition tests on preserved core samples taken at the end of the pilot test showed that the Warner sandstone was then neutral or slightly water-wet. Initially, the reservoir may have been strongly water-wet as indicated by low relative permeability to water during both water injection testing and early steam injection. PRIOR HISTORY Initial production tests of wells at the pilot site produced water with only a faint show of oil. No gas was produced except at Well 7-W in the pilot area and at another well about 1/3 mile northeast of the pilot. Prior to the start of the steam drive, a two-well water injection test and a two-well air injection test were conducted. No oil was produced by either. Water was pumped into Well I-W in the northeast corner of the pilot area with simultaneous production from Well 1 (Fig. 3). The air-injection tat was run at input Well 9-W and its offset, Well 2, in the southwest corner. Air and water injectivities were about the same when corrected for viscosity and pressure differences.

By Robert D. Pike

In November 1939, on behalf of the Harbison-Walker Refractories Co., the author undertook the study of the problem of utilizing the dolomite of northwestern Ohio for the manufacture of calcined magnesia suitable for use in refractories. Grateful acknowledgment is made of the unfailing assistance and encouragement throughout this work from the executive and technical staff of Harbison-Walker Refractories Company. The dolomite of the Niagara formation that is exposed or near the surface of a wide area in northwestern Ohio1 constitutes a vast supply of almost pure dolomite. It offers a virtually unlimited supply of cheap raw material of uniform dependable analysis for the manufacture of magnesia. A typical analysis of dolomite from the vicinity of Luckey, Ohio, follows: Stone Completely Calcined CaO(Sro)a............. 30.35 57.806 Mgo................... 21.55 41.050 SiO2. ................... 0.30 0.572 R2O3................... 0.30 0.572 Ignition loss............. 47.50 a SrO about 0.06 pct. Brines containing magnesium chloride or sea water can be reacted with calcined dolomite to produce magnesia.2'3 In such reactions the MgCl2 of the brine supplies some of the magnesia and the amount of dolomite required is thereby reduced by an equivalent amount, but brines of commercial importance containing magnesium chloride are some distance away from the purest grades of the dolomite of northwestern Ohio. It was decided therefore to concentrate upon the development of a suitable process for separating the lime and magnesia of dolomite, depending upon the dolomite itself as the sole source of magnesia. This would make it possible to place a plant at the dolomite quarry, thus eliminating the cost of transporting the stone and also rendering the calcined magnesia available at a most convenient production point, considering the cost of delivery throughout the steel industry. The selection of a process depending solely upon the dolomite as a source of magnesia also necessarily entails production of the lime content of the dolomite as a by-product. It was recognized that if such a lime by-product could be produced in a suitable form, a plant location in northwestern Ohio would also be advantageous for marketing the lime. The problem, therefore, was the discovery and development of a low-cost process for separating the magnesia and lime of the dolomite of northwestern Ohio and producing each in a form relatively free from the other, and meeting the respective requirements of established markets. A satisfactory solution of this problem has been found, and it is the

Jan 1, 1948

By J. Chipman, J. C. Fulton

Reduction of Si from slag to carbon-saturated iron is a very slow reaction. The rate is nearly independent of stirring but is accelerated markedly by increased temperature. In a slag containing 45 pct SiO2, 38 pct CaO, 17 pct Al2O3, the energy of activation is approximately 130 kcal. AT temperatures of 1450" to 1600°C occurring in the hearth of the iron blast furnace, chemical reactions are normally expected to proceed with great rapidity. Many of the reactions of iron making are indeed quite rapid and attain a condition corresponding roughly to a state of equilibrium before metal and slag are tapped from the furnace. The one conspicuous exception is the reaction by which carbon in the coke or metal reacts with silica in the slag to deliver silicon to the metal. From the practical viewpoint the slowness of this reaction is indeed fortunate, for if it were fast enough to reach equilibrium during the time of contact, it would be difficult to produce pig iron of the desired low silicon content. The one other reaction which under certain circumstances can also be very slow is the transfer of sulfur from blast-furnace metal to slag. In their laboratory exeriments on this reaction, Hatch and Chipman found that at least 5 hr were required for the attainment of equilibrium in a small crucible and that the reaction was not accelerated by increasing the rate of stirring. Subsequently it was shown2 that the presence of a reducible oxide MnO greatly inhibited sulfur removal, and finally that SiO2 itself3 under some conditions has sufficient oxidizing Dower to interfere with sulfur transfer. The kinetics of sulfur removal are now rather well understood,4 and it has been shown3,5 that when the silicon content of the metal is high enough to prevent reduction of SiO,, the desulfurizing process is rapid. Thus the observations of slow removal of sulfur are associated with the coincident slow reduction of SiO2, a process which transfers both silicon and oxygen to the metal phase. It is, of course, the oxygen which interferes with sulfur removal. An explanation of the slowness of the silica reduction reaction has not been obtained. The sulfur transfer process has been shown by the authors5 to be at least partially transport-controlled in the absence of interference by silica. Under the experimental conditions. 99 pct of the total transfer at 1600" was accomplished within an hour. Under similar conditions the reduction of silica may not proceed half-way to equilibrium6 in 8 hr. It is scarcely imaginable that silica reduction could be transport-controlled when the slag contains 44 pct SiO2 and the metal about 1.4 pct C. The experiments reported here show definitely that it is controlled by a slow step or steps in the chemical reaction. One might expect to find such a slow step in the breaking of SiO bonds or in the slow removal of oxygen by carbon at the slag-metal or metal-crucible interface or by bubble formation. EXPERIMENTAL PROCEDURE The experimental procedure used in this investigation was similar to that used in the study of the kinetics of desulfurization.5 A sketch of the graphite crucible and stirrer used in the current work is shown in Fig. 1. The quantity of metal and slag used was adjusted so that the slag-metal interface was located between the top and bottom blades on the stirrer; the top of the slag layer was above the top blade. The stirrer shaft was hollow down to the metal level and served as thermocouple well or optical pyrometer target. Stirring speeds of 0 to 500 rpm were used. A carbon monoxide atmosphere was maintained in the furnace by flushing the gas over the slag surface, except in run No. 220 when it was bubbled

Jan 1, 1960

By Barbara A. Thompson

A previously reported high-resolution method for the location of boron-rich areas in metallurgical and biological specimens was been adapted for general use on a routine basis. The rnetlzod utilizes neutron activation and autoradiograpizy. Alpha-particles emitted by boron nuclei upon neutron capture are recorded on a photographic emulsion. The resulting a-particle tracks show the location of boron-rich areas. Experimental techniques, interferences, and limitations of the method are discussed in detail. The method is most useful where there is marked segregation of boron. In this type of sample, the segregation can be observed when the nominal boron concentration is as low as 0.0006 pct. THE positive identification and location of boron-rich areas in metals is frequently of great interest in metallurgical work. Unequivocal identification is often difficult to make by conventional metallo-graphic methods. Recently, a method has been described which accomplishes this objective by neutron activation and autoradiography.l-3 The method can be described briefly as follows. Upon neutron capture, a -particles are emitted by boron nuclei according to the following reaction: ,Blo + n - ,a4 + 3Li7 + 2.4 mev The energy is dissipated as kinetic energy of the products. By irradiating a boron-containing sample in contact with a photographic emulsion and subsequently developing this emulsion, a-particle tracks are obtained whose location corresponds to the location of boron-rich areas in the sample. Two factors combine to make the reaction extremely specific for boron. The first is the unusually high (755 barns) cross section of boron for thermal neutron capture. The second is the higher neutron energy required to produce (n, a ) reactions in essentially all other nuclei except lithium. These two factors make the method specific for boron by six to seven orders of magnitude when a predominantly thermal neutron source such as the Brookhaven reactor is used. The reported limit of detection of this method is of the order of 0.01 pct B., The present work was originally undertaken to determine whether this limit could be lowered by use of a thinner emulsion. However, initial experiments showed that in order to use the method at all, it was necessary to reestablish the optimum experimental conditions in terms of the available irradiation facilities. It is the purpose of this paper to describe these experimental conditions in detail, to discuss the factors influencing sensitivity, and to evaluate several techniques for increasing sensitivity. EXPERIMENTAL A) Preliminary Experiments—The first measure-ments were made using samples of crystal oriented silicon steel containing various concentrations of boron. In the later experiments, samples of various high-temperature alloys such as M-252, hcoloy 901, Nichrome V, and so forth, were used. Faraggi, et al.,2 reported that the lower limit of sensitivity in this type of sample was about 0.01 pct B using nuclear emulsions of 50- u thickness. but that it should be possible to extend this limit by the use of thinner emulsions. Accordingly, we first used Kodak Auto-radiographic Stripping Film (Permeable Base) which has an emulsion thickness of only 5 µ. This was mounted on the metallographic specimens according to the technique described by Boyd.4 The emulsion remained in contact with the metal surface throughout exposure and development. Since the emulsion is transparent after development, the autoradiograph and metal surface can be viewed simultaneously and any correlation between film blackening and structure of the metal can be made directly with no problems of realignment. Because the silicon steel is readily attacked by moisture alone, it was necessary to apply a protective coating to the metal surfaces before mounting the emulsion. The coating was made extremely thin in order to absorb as few a-particles as possible. Boyd4 and Gomberg5 have discussed various plastics used for this purpose; however, none was sufficiently impermeable to prevent chemical attack of the steel during the developing process. This attack resulted in the production of gross chemical artifacts in the emulsion. It was, therefore, necessary to use the method of Wolfsberg and John6 as follows. A very thin (approximately 1 µ) coating of Plexiglas II was applied by dipping the sample in a 2 pct solution of Plexiglas II in dichloroethylene. Then, because the emulsion will not adhere to Plexiglas 11, a thin coating of Parlodion was applied in a similar manner using 2 pct Parlodion in iso-amyl acetate. No protective coating was necessary with the high-tem-

Jan 1, 1961

By J. S. Aronofsky

The first step in a quantitative analysis ot the mechanism of oil displacement by water in a fractured reservoir is usually conceded to be the solution of the differential equation describing the saturation distribution of two immiscible fluids flowing in a porous medium, where the capillary pressure is taken into account. In such a system the production mechanism may consist of displacement of oil both by the flow of water due to natural or artificially imposed pressure gradients and by imbibition, which implies a flow of water not due to external pressure gradients. Owing to the presence of the two oil displacement mechanisms, the mathematical model given by the differential equation intended to describe the system may not properly represent the behavior of the physical system. In fact, in the reservoir the rate of water advance may be very slow, and in the case of a fractured reservoir with a great number of large fractures, the pressure difference determining the flow of water through the matrix may be much less than 1 lb/'psi over lengths of a few feet. In such a case, imbi-bition (the exchange between oil in the matrix and water in the fractures resulting from capillary forces) may become, with time. a significant element of the production mechanism. It occurred Lo the authors, however, that without going into a physical analysis of the process of production, it might be possible by means of simple abstract reasoning to throw some light on the variation of recovery with time under conditions occurring in a highly fractured oil reservoir with rising water table. The object of this paper is to present both the reasoning and its application to a reservoir of the highly fractured type. Specifically, the analysis given here was undertaken to try to explain the increase of recovery (as defined later) with time as observed in this reservoir, without having to assume unlikely variations in the reservoir parameters with depth. This attempt has been successful as will become clear upon comparison of the computed recoveries with the actual field data. ABSTRACT MODEL Let us consider a small volume. of porous matrix saturated with oil at time, t = 0. Let the process of oil displacement by water start at time, t = t,,. At some time, t, the process will have terminated. Then a volume of oil equal to or smaller than the original oil contained in the matrix will have been produced. The first basic assumption that describes the model and guides the forthcoming reasoning is that the oil production from the small volume. dv, is a continuous monotonic function of time and that it converges to a finite limit. Such an assumption is not inconsistent with the results of laboratory waterflood tests as well as with results of imbibition tests where this is, in fact, observed. The second basic assumption is that none of the properties which determine the rate of convergence change sufficiently during the process to affect this rate or the limit. Let it be assumed that the form of the function of time relative to production from the matrix volume. dv, is given by where V,(t) is the volume of oil produced up to that time t. R is the limit toward which the recovery converges, A is a constant giving the rate of convergence, and V,(t) is the volume of oil originally in place in the volume, dv. It should be noted that recovery at time I will be understood here to he It follows that r. tends to R as t tends to infinity. CONSTRUCTION OF RESERVOIR FROM ABSTRACT MODEL Let the reservoir consist of a series of identical blocks of porous matrix stacked vertically and separated by fractures. Let each of these blocks satisfy the conditions of our abstract model. These conditions are: (1) that recovery is a continuous mono-tonic function of time converging to finite limit, and (2) none of the properties that determine the rate of convergence change sufficiently to affect the rate or the limit. Let water be rising in fractures so that oil production from any part of the block starts when the water comes in conLact with it. TOTAL RECOVERY FROM THE RESERVOIR COMPARED TO RECOVERY FROM A SINGLE MODEL ELEMENT As stipulated in Eq. 1, in the case of the abstract model,