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By Paul Giesecke

Since most modern metallurgical plants are operated continuously and on a large scale, successful operation at maximum efficiency demands that an accurate knowledge of the performance at each stage of the process be available at all times. Quantitative analyses provide the most practical process guides, and it is essential to have analytical procedures that combine accuracy and speed. In continuous plant operations, large losses may occur if the time interval between the development of trouble at any stage and its recognition and correction is great. Many metallurgical plants are using rapid colorimetric and spectrochemical methods of analyses for control purposes. So-called "color coppers" may be cited as an example of the colorimetric methods, in contrast with- the routine use of the ultraviolet spectrograph for the analysis of steels.42 By means of this more refined spectrochemical procedure, a complete quantitative analysis of the molten metal is obtained every few minutes. During the past two years the Physics Division and the Ore Dressing Laboratory of the American Cyanamid Company's Stamford Research Laboratories have collaborated in a study of the use of spectrochemical methods for the analysis of various metallurgical products. New methods have been developed, which have proved of practical value in plant operation. The following pages give a general review of the principles of spectrochemical methods and also the details of several specific analyses. Principles of Spectrochemical Analysis In general, it can be said that a visible light spectrochemical analysis can be performed for any ion or molecule that is naturally colored, or that can be made to react with another to produce a colored salt or complex. Whereas transmission measurements in the ultraviolet and infrared portions of the spectrum are most useful for the analysis of organic molecules, * visible light measurements are of particular value for metal salts. Such elements as copper, manganese, cobalt, nickel, iron, molybdenum, vanadium, chromium, phosphorus, mercury, zinc, lead, and a great many others, can now be determined with a high degree of sensitivity, accuracy and dispatch. From the simplest of qualitative determinations, color analyses have been improved to such an extent that, at the present time, through the use of recording spectrophotometers, hundreds of accurate quantitative analyses can be performed by a single analyst during an 8-hr. day after the standardization curves have been established for the ions to be determined.

Jan 1, 1947

By W. T. Bishop, G. A. Crowe

While the literature in the United States on general polarographic technique is extensive, very little appears to be directly applicable to the analysis of flotation tailings. For this reason, it seemed worth while to present a few polarographic methods of ore analysis that have been in constant use in the laboratories of the Hercules Experiment Station for the past few years. At the time of our initial investigation of the polarographic method, there was little or no mention of its specific application to flotation tailings. It was therefore necessary for us to establish suitable conditions for the analysis of our flotation tailings and to consider possible interfering constituents. The polarograph, or dropping mercury electrode, method was discovered in 1925 by J. Heyrovsky and M. Shikata,1 of the Charles University, Prague. This method has since received extensive development and the literature contains many articles on the use of the polarograph for the quantitative determination of metals as well as anions, oxygen in solution, and reducible organic compounds. Kolthoff and Lingane,² by the publication of their book, "Polarography," in 1941 did much to advance the knowledge and use of the polarograph. In chapter 25 of that book, methods for the polarographic analysis of brass, steel and iron products, alloys, and zinc ore are given. Aluminum,³ cadmium,³,4 cobalt,4 cop-per,³-9 gold,10 iron,3,11 lead,³,l2,l³ molybdenum,14 nickel,4,8,9 tin," and zinc³,4,5,7 in ores have been analyzed by the polarograph. However, most of the work on tailing samples has been published in Russian journals and translations are not yet readily available. In this paper we will describe the method that was developed and used in our laboratory for the determination of copper, zinc, and lead in flotation tailings. Principle OF the Method The polarograph is an instrument for applying a potential to a mercury pool and a dropping mercury electrode separated by a solution, and for measuring the resultant electrical current. The procedure is essentially a small-scale electrolysis, in which the voltage required to reduce or oxidize the material identifies it qualitatively and the current measures the concentration quantitatively. Different constituents in a sample may often be determined simultaneously provided they reduce at sufficiently different voltages. An example is the determination of copper and zinc in the same solution. The reduction potentials are quite far apart, as shown in Fig. I. The polarographic method is particularly useful in the range of concentration between those normally determined by spectographic and chemical methods. In

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By R. L. Boyer, F. Morgan, M. Muskat

In the last several years a type of application of the fundamental permeability-saturation relationships has been developed which offers great promise in the interpretation of general reservoir performance.l-' In these developments no attempt is made to solve the detailed flow dynamics in actual oil and gas-producing systems. That problem still remains unsolved. But the permeability-saturation phenomena are incorporated in the analysis of oil-producing reservoirs in a manner such as to reflect the true role they play in controlling the gross reservoir behavior. In particular, they are introduced in such a manner as to determine the gas-oil ratio of the production at any stage of depletion, and, when combined explicitly with the so-called material-balance principles in differential form, one can obtain a differential equation describing completely the average pressure and gas-oil-ratio history of oil-producing reservoirs. While thus far they have been applied directly only to gas-drive reservoirs, they are susceptible of extension to partial water-drive systems, and qualitatively the same principles are of value in the study Of complete water-drive reservoirs. Moreover, in addition to giving a means for computing the variation of the reservoir pressure and gas-oil ratios vs. the cumulative production, they automatically lead to predictions of the gross ultimate recovery under natural depletion—and when properly extended they provide means for predicting the ultimate recovery under gas or water injection. The data required for such applications are the initial fluid distribution in the producing section, the pressure-volume-temperature data on the gas and liquid phases, and the permeability-saturation relationship for the oil-satuiated zone. The former can be obtained with reasonable accuracy by methods that are well established and available throughout the industry. The permeability-saturation data, however, involve techniques that are not at all standardized. In fact, only

Jan 1, 1947

By John J. McKetta, Donald L. Katz

Recent experimental data on the methane-n-butane-water system have been combined with data in literature to present: (I) the water-vapor content of natural gases, (2) the solubility of water in hydrocarbon liquids, and (3) the solubility of natural gases in water. Since water is present in petroleum reservoirs, experimental data regarding the behavior of water in hydrocarbon-water systems is of increasing engineering importance. A survey of literature (Table I) shows that data of these types are fragmen-tary at temperatures above the hydrate region. Experimental data taken from the authors' recent investigation of the meth-ape-n-butane-water system are presented.17

Jan 1, 1947

By E. A. Nichols

The purpose of this paper is to present a contour map that shows the geographical variation in geothermal gradients in the Mid-Continent and Gulf Coast oil fields. Introduction Frequently there arises the need for an estimation of the temperature to be expected at a predetermined depth in working with a wildcat or in deepening old production into 'Ones that are relatively unknown. The study of geothermal gradients in oil fields has been made previously by many investigators. One of the pioneers in this work was C. E. Van Orstrand,' who, as well as most of the other investigators, was primarily interested in the relation between temperature and depth in a given locality. Between 192r and 1929, American Petroleum Institute Research Project NO. 25 fostered a thorough study of earth temperatures.2 K. IV. French did some work in California, the results of which were published in 1939.3 In most of these studies, an attempt was made to correlate temperatures in a rather localized area. This paper will show the results of an attempt to correlate temperature gradients over rather large Portions of the Mid-Continent and Gulf Coast area. Method of Obtaining Data It has been found that for complete thermal equilibrium to be established in a well, the well must stand undisturbed for a period of several hours to several weeks, depending upon the way the well was produced prior to the shut-in period. The data in this paper were obtained in conjunction with running pressures in wells or in taking samples of reservoir fluid. Glass maximum recording thermometers were used in all but a few instances. The wells had been shut in from one hour up to I. or 12 days. Since the wells were normal producing wells, some of the shut-in times undoubtedly were insufficient for complete thermal equilibrium to have been established and the temperatures measured do not necessarily represent the true earth temperatures. They do represent the temperature conditions that will be encountered in a well that is producing oil. The data, therefore, can be useful in working with or in estimating the temperatures to be expected in producing reservoirs. In obtaining a thermal gradient by dividing the difference in temperature of the formation and the mean annual surface temperature by the depth of the formation, one is assuming the depth-temperature line to be straight. Depth-temperature curves are almost straight lines (Fig. I). However, on close examination of accurate data, a slight curvature usually is observed. Most wells yield curves with slopes increasing with increasing depth. These curves are believed to be from wells that are in and are underlain by sedimentary material. Some few curves have slopes that decrease with increasing depth. These curves are believed to be from wells that are underlain rather closely by granite or some other igneous rock. Most investigators

Jan 1, 1947

By F. Morgan, M. Muskat, R. G. Russell

Core experiments with radioactive tracers are reported in which an artificial radioactive material, radiovanadium, was used in aqueous solution in a study of the mobility of connate water. Sandstone cores saturated with active water were first oil-flooded to simulate virgin sand conditions in which the pores are filled with oil and connate water. They were then subjected to flooding with inactive water. Measurements were made of the activity of various portions of the effluent as well as the activity of the core after the flooding process was completed. In additional experiments the distribution of activity along the core was measured during the flooding process. In still other experiments direct flooding tests were made on cores fully saturated with active water. In all cases it was found that after injecting into the core a volume of inactive water equal to a pore volume, the effluent contained more than 80 per cent of the active content originally in the core. It is felt that these results imply a high degree of mobility of the connate water when subjected to flooding, although at least a partial contribution of the effect of tracer transfer within the core cannot be definitely excluded. The implications of this result with respect to water-flooding, core analysis and electric logging are discussed. A better approach to determining the connate water saturation of oil-producing rocks, by measuring the fluid content of core samples at the surface, is by the use of crude oil or oil-base muds as the coring fluid. Although water flooding is of considerable importance in the recovery of ail, comparatively little is known with certainty about the role played by the connate water during the operations. Two possibilities exist. Either the connate water is retained in the formation while the flood water sweeps past, or it is pushed along to a greater or lesser degree by the flood. Thus far no explicit recognition in terms of quantitative studies appears to have been given to the displacement of connate waters by the intruding extraneous waters, although such a possibility might be important in determining the efficiency of the oil -displacement process in water-flooding operations, especially in argillaceous rocks. On the other hand, it is a common observation that the first water produced with the oil as a result of water-flooding is definitely saline.*.' Similar questions regarding the mobility of the interstitial water arise in the quantitative description of the advance of edge-water drives. In the interpretation of the water saturations determined from core analyses, when coring with water-base muds, it is generally assumed that the drilling fluid merely adds to the connate water without displacing the

Jan 1, 1947

By Henry Schaefer

Solution by electric analogy of performance problems of reservoirs containing oil and gas has heretofore depended upon a process of successive approximations based on material-balance calculations, because of variation in fluid compressibility. By the addition or subtraction of electric condenser capacity, the analogy network can be adjusted automatically for changing compressibility due to evolution of gas in the reservoir. The addition of a condenser is accomplished by an electronic circuit, which is described; subtracting a condenser is done by merely opening the electrical circuit by means of a relay. Introduction V. Paschkis and H. D. Baker1 first developed in this country a method of applying the analogy of flow of electric current in noninductive circuits to solution of heat-flow problems and suggested its application for certain other problems, such as flow of fluids or mass transfer and chemical diffusion. Necessary details for applying the analogy to flow of fluids in porous media were developed by IV. A. Bruce;= he classified3 the types of analysis and predictions that can be made by the analogy in class I, when the reservoir contains oil but no gas for the period under consideration; in Class 2, when both oil and gas exist in the free state in the reservoir sometime during the period under consideration. Duplication of bottom-hole pressure history and predictions for class I reservoirs can be obtained directly by electric analogy. Until now, the solution of problems pertaining to reservoirs in class 2 was obtained by successive approximations along with material-balance calculations. The object of this paper is to present a method for simplifying the application of electric analogy to class 2 reservoirs, resulting in a solution of these problems as direct as is possible for class I reservoirs. This is accomplished by an electronic control circuit, which adjusts the analogy network for changing compressibilities of fluids contained in the reservoirs. Analogy Network In electrical phenomena the analogy to two-dimensional fluid flow in a porous media is that of current flow through an ideal conducting sheet. This sheet, perfectly insulated on both sides, has resistance and capacitance uniformly distributed throughout its area but is of negligible inductance. The need for having the surface boundaries perfectly insulated is that good correspondence may be had with a permeable fluid-conducting stratum bounded above and below by impermeable media. 111 actual application the ideal conducting sheet, which has distributed parameters, is replaced by a network having lumped values of resistance and capacitance—the resistances are series elements and the capacitances are shunt elements. The larger the number of lumped

Jan 1, 1947

By O. F. Thornton, D. L. Marshall

Results of the determination of the inter stitial water content of several core samples from oil reservoirs are presented. Data obtained by the capillary pressure method, which has recently been developed, are compared with water saturations measured in cores cut with oil-base mud and with values calculated from the electrical resistivity of the formation. The agreement between the capillary pressure and other methods, combined with the fact that similar agreement has been obtained by others, indicates that the capillary method properly applied yields results sufficiently accurate for most engineering purposes. In some cases, it may be possible to extend the utility of data obtained with the capillary pressure method by correlation of interstitial water saturation with more easily measured physical properties of the media. Introduction Several methods are in use for determining or for estimating the interstitial water saturation at given points within oil and gas reservoirs. The direct measurement of the water content of cores obtained with nonaqueous fluid in the hole is believed to be an accurate method under most conditions. The water saturation may be calculated by use of the resistivity curves of the electric log,' although this method is not applicable under conditions that exist in some reservoirs. Recently, a method has been developed and described3.' wherein the interstitial water saturation of cores is measured at a capillary pressure such that conditions existing in the reservoir are simulated. The purpose of this paper is to present data obtained by use of this latter method, and to compare the results obtained with determinations made by other means. Method The theory underlying the capillary pressure method applied to petroleum reservoirs has been discussed adequately in the literature by Garrison,2 Leverett,5 and Others.3,6,7 Briefly, and simply, capillary pressure is defined as the difference in pressure between two contacting fluid phases, such as oil and water. For the simplified sand, water and oil system illustrated in Fig I, the pressure difference can be stated as follows:6 where Pc is the capillary pressure in pounds per square inch, ? is the interfacial tension between oil and water in pounds per inch, r1 and r2 are the radii of curvature of the interface between oil and water in inches. Capillary pressure varies in a given reservoir with depth because of the greater density of the water phase as compared with oil or gas. The following equation expresses the difference in pressure between two points: p1- p2 - h?p/144 [2] where p1 — p2 is the capillary pressure difference in pounds per square inch, h is

Jan 1, 1947

By M. Muskat

A theory has been developed describing the behavior of wells and reservoirs producing by the action of bottom water drives. It is assumed that the pressures are maintained above the bubble point, and that the permeability to viscosity ratio of the water in the flooded zone is the same as for the oil in the oil-saturated pay. Accordingly, the treatment is based on the homogeneous fluid potential theory. The effect of the difference in density between the oil and water is neglected. .4fter deriving the proper potential distrihutions, the nature of the rise of the water-oil interface below the producing wells is calculated. The primary clean-oil-production phase is expressed in terms of the displacement efficiency, defined as the fraction of the pay flooded out by the rising water table at tlle time of first water entry. The variation of this displacement efficiency is calculated as a function of the well spacing, pay thickness, the ratio of the horizontal to vertical permeability, and the well penetration. The important parameter, other than the well penetration, is found to be the ratio of the well separation to the thickness of the oil pay multiplied by the square root of the ratio of vertical to horizontal permeability. It was found that the displacement efficiency continually decreases as this parameter increases, and for values of the latter >3.5, the efficiency varies inversely as the square of the parameter. It also increases with decreasing well penetration. Perhaps the most striking result of this phase of the analysis is the conclusion that in order to explain the delay in entry of water in wells producing by bottom water drives for periods longer than a few days normal production, with drawdowns large compared with the differential density head between the oil and water, it is necessary to assume that the vertical permeability is a very low fraction of the horizontal permeability. An analysis is also given of the production history after the water has broken through, on the assumption that the production mechanism and details of the flow distribution continue to be the same as during the phase of clean-oil production. As is to be expected, it is found that the water cut will increase at an accelerated rate as production proceeds. However, the initial differences between systems of different well penetrations or well spacings with respect to the total clean-oil production gradually decrease in terms of the variation of the water-oil ratio with cumulative production. In particular, by the time the water-oil ratio has reached values of the order of 5 or greater the cumulative recoveries will generally differ much less among various producing systems than their corresponding clean-oil recoveries. Introduction On the basis of elementary geological principles, one may classify effective water-drive fields in two groups. In the first, the entry of water into the oil-producing formation may be characterized as an edge-water encroachment. This term is used to suggest that the motion of the water proceeds largely in a direction parallel to the planes of stratification. This type of water intrusion occurs usually in thin producing zones and in strata lying along structural flanks of appreciable dip. In the second group—"bottom water-drive" fields—the water-oil interface lies in a plane of zero or slight inclination to the

Jan 1, 1947

By E. C. Patton

Jan 1, 1947

By Helmut Thielsch

In recent years an ever increasing amount of interest has been directed toward research studying the principles and various applications of sonic and supersonic waves. Though still in their early stages of practical development, sonic vibrations are already used in the emulsifi-cation and degasification of liquids. Metals exposed to sonic or ultrasonic vibrations while solidifying show a considerable amount of grain refinement. Often sound waves are applied instead of radiography to test engineering materials for internal cracks and flaws.' In the field of pure research these waves are used in dispersion and also in coagulation of particles or liquids in gaseous or, under certain conditions, in other liquid systems. In the settling and thickening of slurries considerable time is necessary to compress the solid particles and to squeeze out the liquid to obtain as low a dilution (liquid to solid ratio) as possible. Various methods have been developed to increase the amount of coagulation of the very fine solids (colloidal or semicolloidal) and to shorten the over-all time. The addition of small amounts of electrolytes and the warming of the suspension represent merely the more important techniques. Some of the effects of supersonic vibrations have been reported previously. From preliminary studies, therefore, it was hoped that by application of sonic vibrations it would be possible to reduce the time required to thicken such materials to a specific dilution, as well as to thicken to lower ultimate dilutions than could be obtained by quiescent settling alone. By increasing the volume thickened per unit time—i.e., improving the plant efficiency— great savings in equipment and time would be obtained for industrial processes. Also, faster settling rates should result if coagulation of particles could be increased. Experiments have been conducted for a period of several months in the Allis-Chalmers laboratory to study the effect of sonic vibrations on settling of particles of different sizes and concentrations. Apparatus The sedimentation apparatus used in these experiments is illustrated in Figs. I and 2. The essential features are the stationary field coil and the movable voice coil. Both windings are placed around a solid iron core. A leather diaphragm connected to the steel frame holds the voice coil in place. A brass rod is fastened to the voice coil with a metal disk connected to the other end. This disk is sealed to the lucite cylinder with a flexible rubber diaphragm. The lucite tube is 17 in. long; its inner diameter is 2½ in. and the wall thickness is ¼ in. The tube is calibrated on the outside in 10 c.c. divisions for a total of 1000 cubic centimeters.

Jan 1, 1947

By Grover J. Holt

In order to provide a clear picture of the development of the sink-and-float process of concentration as applied to the iron ores of Minnesota, a few pertinent facts should be brought out concerning the ores and the products of concentration. Iron ore is primarily a cheap commodity handled in immense quantities. The price of iron ore at present, based on a natural iron content of 51.5 per cent, varies from $2.55 to $2.70 per gross ton f.0.b. cars at the mine or washing plant in Minnesota. Last year 92,000,000 gross tons were shipped from the Lake Superior district (Minnesota, Michigan, and Wisconsin) to the furnaces. Concentrated iron ores have no greater value per unit of iron content than ores that can be mined and shipped direct from the shafts or open pits. For years only the higher grades of concentrating ores could be treated and sold in competition with the immense reserves of direct shipping ore available. These higher-grade "straight wash" ores required only the simplest treatment; namely, the washing out of fine sand from coarse ore particles. As the exhaustion of the " straight wash " ore is reached, rock is found replacing part of this sand, and the ore no longer responds to the former sizing treatment. Substantial tonnages of this marginal (jig ore) remained to be treated. Because of the limitations placed on concentrates by the furnaces—namely, low price of product and minimum amount of fines—iron-ore concentration oil has been and must continue to be a one-pass process. Only an increase in price or a change in structure of concentrates allowed by the ore consumer will encourage departure from this practice. Faced with the necessity of handling large tonnages, with the limitations mentioned, iron-ore research men have found their search for new and more efficient methods of treatment seriously handicapped and removed from the field of fine crushing. Sink-and-float treatment appeared to offer the best field in coarse concentration and has been proved by several plants to be well adapted to our problem. The use of ferrosilicon as a medium solid was decided upon. In our present practice, the ferrosilicon metal, carrying about 83 per cent iron, 15 per cent silicon and 2 per cent carbon and nonmagnetics, is crushed to pass 65 mesh and used without further sizing. When mixed with water the specific gravity of the medium may be controlled to within 0.02 per cent above or below the required gravity. Table I shows examples of a change in solid content of the medium for varying gravities. the I is based on clean ferrosilicon, whereas some contamination is always present in the mill circuit, tending to

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