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By Tripp R. M., C. A. Heiland, Dart Wantland

This paper serves to illustrate the application of geophysics to a virtually abandoned mine properly, an application that led to the discovery of an ore body and thus afforded an Opportunity to cOmpare subsequent geologic findings with geophysical data. The work herein described represents, however: more than mere ''case history." It demonstrates that it is possible to obtain satisfactory results by simple means and relatively inexpericnced personnel. The geophysical surveys were made by students as a part of their field assignments in the course of their regular training, and were supervised by Dart Wantland, J. E. Hawkins and R. Maurice 'Tripp. In the course of several seasons an appreciable amount of material was accumulated, which gave graduate students an opportunity for special studies. In this connection, the contributions by L. Massé, R. C. Hyslop, and J. E. Hawkins deserve special mention. The property owners cooperated wholeheartedly in the work, and special thanks are due messrs. J. F. Johnson and S. E. Zelenkov, of the American Smelting and Refining Co., for their interest and for permission to utilize the results of their development work for this publication. Location and Geology The Malachite mine is situated on the northcrn slope of Bear Creek Canyon, 4 miles northeast of Evergreen, I½ miles northwest of Idledale, and 4% miles west northwest of Morrison, in Jefferson County, Colorado. The location (Fig. I) is north of the center of set. 30, T. 45, R. 70 W., at an elevation of about 7500 ft, above sea level, Near the mine the terrain slopes rather uniformly southward at an angle of about 180 pigs. 3 and 7). The geology of the Malachite mine area has been described by J, underhill,' W, Lindgren,2 and J. Boyd.3,4 A map showing surface outcrops and mine workings appears in Fig, 2. the Malachite mine is in an amphibolite belt enclosed in gneisses and schists of the Idaho-Springs formation (probably early Algonkian age). The highly contorted beds are nearly vertical and strike slightly north of west. A series of granite-pegmatite dikes have been intruded almost at right angles into the gneisses and schists and doubtedless are postmineral. While most of the formations are exposed at the surface, a part of the 'lope is covered by slide rock and float, and in the eastern portion by alluvium and creek fill. A quartz-diorite dike cuts through the amphibolite schists at a small angle with nearly vertical dip. The copper sulphides, developed in this dike by magmatic segregation, occur in lenticular form. As far as the mine workings have revealed, the ore lenses are often discontinuous in depth and

Jan 1, 1946

By H. R. Joesting

Geophysical search for minerals is stepped up to meet requirements of expanded defense program - Seismic and electrical surveys become firmly established for ground-water and engineering investigations.

Jan 2, 1953

By P. E. Fitzgerald, Dana G. Hefley

An apparatus has been developed which permits selective acidizing of producing formations and determination of the relative permeability of a formation by fluid injection. This apparatus, known as the "Electric Pilot," is an electrical fluid-interface locator, the electrical circuit of which is completed when the elec-tcodes in the well are in contact with a conductive fluid, but is not completed when immersed in a nonconductive fluid. Results are given for a number of typical acidizing applications in which the interface locator was used to control the acid. Description of the method used in making a permeability survey and the data obtained are also included. Introduction Early in the development of the acidizing industry it was recognized that one of the most important problems to be solved in the chemical treatment of any well was the determination of what part of the exposed section in the well should be treated and the selection of the technique that would insure treatment of the desired section. One of the first techniques adopted for assisting in proper placement of the acid, which is still widely used, is the method of confining the acid to the producing section by means of a column of oil, which is known as the Carr1 method of treatment, named for its inventor. In the Carr method it is not possible to selectively acidize a specific horizon in a multiple pay zone, so many improvements and modifications of the basic Carr technique were devised to accomplish this result. In order to overcome the possibility of the acid entering an undesirable section at the bottom of the well, organic gel plugs2 were introduced into the bottom of the well, which served to halt the entrance of the treating solution into these zones.3 These chemical gels later liquefied because of bacterial action and were removed from the well with the produced fluid. In fields where a gas cap existed, as in the Goldsmith field of Ector County, Texas) it was imperative that a treating technique be evolved that would confine the acid to the oil-producing zone below the gas cap. By so doing the oil-productive capacity of the wells could be improved without greatly increasing the gas production and this would lower the gas-oil ratio of the well. ~h, technique employed4 to achieve this effect utilized two pumps, one for pumping the chemicals down the tubing, the other to simultaneously force oil down the annular space to confine the acid to the oil pay, thus preventing the chemicals from entering the upper gas-bearing zones. Experience has indicated that gas wells and certain types of oil wells respond better to ''stage treating.'' This technique utilizes the introduction of a certain volume of acid and then allows the well to ''clean up99 before introduction of the next and usually successively larger stages. Where such methods are employed steps must be taken to keep a disproportionate share of the acid from entering the most permeable and previously treated Zones. A special tool

Jan 1, 1944

By V. L. Minear

This paper presents some of the problems encountered and solved by the construction industry during recent years while pressure grouting the foundation rock of dams. Pressure grouting has become "Standard Operational Procedure" and consequently many hundreds of thousands of bags of cement have been used for that purpose. There is nothing weird, mystical, or even particularly difficult about the basic idea. Holes are drilled in the rock and grout is pumped into them. This procedure is used to shut off the flow of water under the dam and to reduce the uplift on the dam. Like most other engineering and construction problems, the fundamental principle is simplicity itself, but some of the "minor details" are rather complex. When faced with the problem of actually forcing the grout into the rock, or keeping it there once it has been injected, an engineer frequently has need for all of the ingenuity and initiative that he has at his disposal. It is proposed to discuss these minor details at length, even at the risk of boring the reader. The difference between success and failure in a grouting program can well hinge upon some such detail that may not be fully understood. Pressure grouting is a method used to make good foundations from bad ones by plugging actual or potential passages within the rock through which water might escape and thereby diminish or even destroy the usefulness of the dam. In some special cases, pressure grouting has been used for the purpose of consolidating broken rock to increase its bearing power. Lacking this useful method, many of the dams constructed during recent years could not have been built. Most of the really excellent dam sites in this country have been utilized long ago. Consequently it becomes necessary to find methods of utilizing the less desirable sites. Pressure grouting plays a vital role in the methods developed. Engineers have learned the hard way, that the term "solid rock" is a misnomer. Solid rock does not exist to any considerable extent in nature. Practically all rock contains imperfections such as shrinkage cracks, bedding planes, joints, solution channels, folds, shear zones, crush zones, and the like. All these imperfections are weaknesses through which ground water is likely to flow. The function of rock grouting is to rectify these imperfections and make the rock as nearly "solid" as practicable. The location, direction, depth and number of grout holes to be drilled are important. Clearly, a hole must pierce fractures in order to serve a useful purpose, for grout cannot be forced into the rock itself. Were it possible to determine the pattern and extent of the cracks within the rock, it might be feasible to drill two or three strategically placed holes so as to make practicable the grouting of the whole integrated network of cracks from them. Such is not the case. While a study of the geology, surface indications, and drill cores is helpful in gaining an idea of subsurface conditions, in the final analysis, the seams must be located by trial and error methods. There can be no doubt that the closer the

Jan 1, 1949

By P. E. Fitzgerald, Dana G. Hefley

An apparatus has been developed which permits selective acidizing of producing formations and determination of the relative permeability of a formation by fluid injection. This apparatus, known as the "Electric Pilot," is an electrical fluid-interface locator, the electrical circuit of which is completed when the elec-tcodes in the well are in contact with a conductive fluid, but is not completed when immersed in a nonconductive fluid. Results are given for a number of typical acidizing applications in which the interface locator was used to control the acid. Description of the method used in making a permeability survey and the data obtained are also included. Introduction Early in the development of the acidizing industry it was recognized that one of the most important problems to be solved in the chemical treatment of any well was the determination of what part of the exposed section in the well should be treated and the selection of the technique that would insure treatment of the desired section. One of the first techniques adopted for assisting in proper placement of the acid, which is still widely used, is the method of confining the acid to the producing section by means of a column of oil, which is known as the Carr1 method of treatment, named for its inventor. In the Carr method it is not possible to selectively acidize a specific horizon in a multiple pay zone, so many improvements and modifications of the basic Carr technique were devised to accomplish this result. In order to overcome the possibility of the acid entering an undesirable section at the bottom of the well, organic gel plugs2 were introduced into the bottom of the well, which served to halt the entrance of the treating solution into these zones.3 These chemical gels later liquefied because of bacterial action and were removed from the well with the produced fluid. In fields where a gas cap existed, as in the Goldsmith field of Ector County, Texas) it was imperative that a treating technique be evolved that would confine the acid to the oil-producing zone below the gas cap. By so doing the oil-productive capacity of the wells could be improved without greatly increasing the gas production and this would lower the gas-oil ratio of the well. ~h, technique employed4 to achieve this effect utilized two pumps, one for pumping the chemicals down the tubing, the other to simultaneously force oil down the annular space to confine the acid to the oil pay, thus preventing the chemicals from entering the upper gas-bearing zones. Experience has indicated that gas wells and certain types of oil wells respond better to ''stage treating.'' This technique utilizes the introduction of a certain volume of acid and then allows the well to ''clean up99 before introduction of the next and usually successively larger stages. Where such methods are employed steps must be taken to keep a disproportionate share of the acid from entering the most permeable and previously treated Zones. A special tool

Jan 1, 1944

By Robley D. Evans, Gerald L. Schroeder

Advanced techniques for control of radon (Rn) daughter product concenrrations (working levels, WL) in the uranium mines are discussed. Understanding the physical laws which govern the flux of radon into a mine, the growth and decay of the radon daughters, and the particulate nature of the daughters when suspended in air allows ventilation personnel to improve the quality of mine air with no increase in ventilation rate. The task of controlling, in a mine atmosphere, the short-lived nuclides produced in the decay chain of radon is a unique problem and as such should be approached with ventilation techniques specific to the problem. For most mines this has not been the case. Rather, procedures for removing these airborne radioactive nuclides have been borrowed directly from ventilation experience in mines where dilution ventilation was the traditionally accepted approach for air purification. With radon daughter products, this has often led to frustrating difficulties and expense. Primary origin of the airborne radioactivity is the a-ray-emitting noble gas, radon (222Rn, Rn), a nuclide formed by the decay of radium (226Ra, Ra). Radon, being a gas, may escape from its parent crystal and diffuse through the parent mineral into the interstices of the rock body. In a sandstone structure, about 20% of all the radon formed may find its way into the interstices of the rock. If a cavity such as a mine is nearby, the radon may diffuse through the rock interstices into the mine. While radium is usually highly concentrated in uranium ores, it is also found in varying concentrations in all minerals. Radon is therefore present in all minerals. In normal glacial till, the equilibrium interstitial radon concentration often equals 5000 pCi (picocurie, also uuCi) Rn per liter of pore volume.' In normal granitic rocks, the interstitial radon concentration often approaches 30,000 pCi per 1. Considering these typical, high-radon concentrations, radioactivity from airborne of daughter products is a potential problem unique not only to the uranium mining industry and should be considered as a potential hazard in all underground environments.

Jan 1, 1970

By R. E. Head, E. L. Tucker

In the metallurgy of precious metals, it has been standard practice for years to use cyanogen compounds, so it was but natural that early investigators in the field of flotation should consider these compounds as possible flotation reagents. In Australian Patent 9508, of 1913, alkali cyanides were described as suitable reagents for the separation of heavy sulfide minerals, the reagents being employed either in an alkaline or neutral circuit. In U. S. Patent 1236501, of 1917, to John M. Tibbet, the use of cyanide in conjunction with soda ash or lime is described. One of the claims of this patent reads, "An improvement in the cyanide process for the treatment of ores comprising, mixing the ore with cyanide solution and oil and alkali: emulsifying the oil in the presence of the ore, the alkali and the cyanide solution, floating a portion of the values in the pulp by producing gas bubbles in the mixture and removing the values floated." More recently, Sheridan and Griswold, in U. S. Patents 1421585 and 1427235, describe a somewhat similar process and have successfully introduced it in the mill of the Timber Butte Milling Co. U. S. Patent 1429544, of 1922, to Stevens, describes the use of double cyanides of copper, zinc, and lead. The success of cyanide as a reagent in the differential flotation of lead and zinc sulfides in highly complex ores is proof that these patents have a solid foundation. Although the technique of their application to particular ores has been worked out in many cases, no one, so far as is known, has attempted to describe the nature of the action of the cyanide or to determine the ideal conditions for its application. It was the purpose of the present investigation to gather information on these points. Naturally this would have been an exceedingly ambitious program had the attempt been made to study the effect of cyanide

Jan 1, 1926

By Fred H. Poettmann, A. L. Benham

correlation of waters and identification of mixtures of two and three waters is important in secondary recovery evaluation studies and studies involving underground movement of waters. The importance of such studies suggests the need for a method to correlate a great number of water analyses to accurately identify and improve the understanding of mixtures of waters. Geochemical analyses of waters furnish a quantitative measure of each of the ions present in a water. Table L shows a portion of the data on many oilfield water analysis report forms in use today. Under "parts per million" are listed the quantitative amounts of each ion in milligrams per liter. Following the work of Stabler' and Palmer", some laboratories have reported additional data to indicate the reaction capacity, or reacting value of each ion. Table I lists data under two subheads for the "reacting value". Under the first subhead, the reacting value is reported in gram equivalents per million, hereinafter called equivalents per million. This value is determined by multiplying milligrams per liter of the ion by a factor equal to the reciprocal of the equivalent weight of the ion. Under the second subhead (per cent) is listed the percentage of each ion based on the total equivalents per million. Sodium is not usually an analyzed value in routine analyses, but is determined by the difference between total negative equivalent per million values and the sum of all of positive ion values for which analyses were made. This difference is reported as sodium, hereafter labelled "sodium". On this basis, the subtotals of the equivalent per million and per cent reacting values of the positive and negative ions are equal. CORRELATION OF WATER ANALYSES DATA Previously reported methods for correlating oilfield waters have used part of the data in Table 1, and can be classified into two categories. Correlation by Chemical Character Correlation methods using the chemical character of waters, as represented by the per cent reacting values of the ionic constituents, have been used by Palmer2 and Tickell. These methods have the limitation of neglecting the ionic concentration of the waters. This limitation can be serious in areas where waters have the same chemical character, but differ in concentration. Correlation by Concentration of the Ionic Constituents The Reistle' and the Stiff methods use the ionic concentration in parts per million and equivalents per million. These methods are effective in differentiating waters of similar chemical character and varying concentration, as in the highly saline waters of the Mid-Continent area. These methods have the disadvantage that they correlate waters by comparing many graphs of individual water analyses to determine the similarity to, or the variance from "type" waters. PROPOSED METHOD OF CORRELATING WATER ANALYSES DATA Correlation graphs presented in Fig. 1 represent water analyses data as points to facilitate the correlation of waters. The graph on the left of Fig. 1 is a plot of per cent reacting value of magnesium vs calcium. The right

By M. Muskat, H. H. Evinger

ALTHOUGH the shooting of oil wells for the purpose of increasing production has been practiced since 1866, present-day shooting technique has been arrived at almost wholly by a process of trial and error. The difficulties attending either a theoretical analysis of the problem or an experimental attack become apparent when one actually embarks on a theoretical investigation or attempts to formulate an intelligent experimental program. The literature on the subject consists mainly of descriptions of current practice, scattered eye-witness accounts of events following the shooting of a well, and vague speculations on the mechanical processes involved. In contrast to quarry blasting, the results of oil-well shooting cannot be determined by means of visual inspection, and it is perhaps for this reason that only one attempt at what approaches a direct experimental attack has been reported in the literature.1 In these experiments, charges of liquid nitroglycerin were exploded in holes drilled in a sandstone outcrop. In order to observe the character and extent of the resulting fractures, the rock was blasted away so as to expose the original shot holes. After all this had been done it was found impossible to distinguish the fracturing due to the original shots from that due to the subsequent blasting. The enlargement of the holes due to the pulverizing action of the shots was. measured and an attempt was made to determine the effectiveness of 'sand tamping. Only five shots were made and few definite conclusions could be drawn. Some small-scale experiments to determine the effect of tamping were performed by Snelling and Hall,2 Small charges (20 grams) of dynamite were detonated at the bottom of a cylindrical hole in a lead block and the resulting enlargement of the hole was taken as a measure of the effectiveness of the explosion. It was found that when the shot was tamped with a sufficient amount of sand or clay, the volume enlargement was approximately double that found when no stemming had been used. The properties of the explosives have been the subject of much study by the manufacturers, the U. S. Bureau of Mines, and various other agencies. For example, velocities of detonation for many commercial explosives are to be found in the Blasters' Handbook, issued by the Du Pont company. Many other properties are given in a treatise on the subject by Naoum.3 The shock wave that accompanies the detonation of high explosives has been studied photographically by Payman4 and others. The hydrodynamical theory of the shock wave has received much attention, and an extended theoretical treatment is given by Bateman.5 Two aspects of the well-shooting problem will be considered in this paper; namely, the fracturing of subsurface strata, and possible damage to casing. With respect to the former of these, several calculations have been made giving the stresses in the rocks surrounding the shot. In order to arrive at numerical results at all, however, it is necessary to introduce a great many simplifying

Jan 1, 1941

By J. Szekely, R. G. Carr

A method is presented which allows the extension of the Ergun equation for the description of gas flow through packed beds in a nonisothermal regime. The pressure profile in the packed bed is calculated by the establishment of a differential energy balance and the iterative integration of the integral equation thus obtained. The predicted values of the pressure distribution were found to be in excellent agreement with those measured experimentally, under carefully controlled conditions. MANY metallurgical processes are carried out in systems in which a gas stream and particular solids are contacted in a packed bed arrangement under strongly nonisothermal conditions. Ore sintering, the firing of pellets, the operation of regenerators, blast furnace technology may be quoted as examples. Although many aspects of these systems have been extensively studied, an important variable, the pressure distribution and the relationship between pressure head and flow rate, received only little attention to date. The purpose of the paper is to present a brief survey of relevant previous work, followed by a more rigorously formulated model, together with experimental results that afford ready comparison of theoretical prediction with measurement. PREVIOUS WORK A great deal of information is available in the chemical engineering literature on flow phenomena in porous media.' The experimental results pertaining to gas flow were generally interpreted in terms of models based on the analogy with the flow through a pipe of an incompressible, isothermal fluid. Of the numerous, semiempirical correlations that have been proposed to relate pressure drop to the volumetric flow rate, the Ergun equation2 is generally regarded as the most satisfactory: The strong nonisothermality of the metallurgical systems previously mentioned would render the direct applicability of Eq. [I] rather doubtful as both density and viscosity are temperature-dependent. Ergun has used Eq. [I] for estimating the pressure drop in the stack region in the blast furnace by neglecting the viscous term and evaluating the gas density at the integral mean temperature.3 His calculations showed a rather variable agreement with measurements and it was uncertain whether the discrepancy found was attributable to the model or to the inaccuracies often inherent in measurements on an industrial scale. Other work on nonisothermal systems includes studies of the pressure distribution in sinter beds, notably by Voice et a1.4 and Mitchell.5 Mitchell developed a method involving the subdivision of the bed into several zones and assigning average property values (temperature, gas density, and so forth) to each zone. The pressure drop was then calculated for each zone by using an expression analogous to Eq. [I]. This method was an improvement over that described by Voice et al., but even here prediction and measurement differed by as much as 30 pct in certain cases. It would appear that no really satisfactory methods are available for the prediction of pressure drop in packed beds with a strongly nonisothermal regime. The method involving subdivision of the bed into small enough sections, that may be regarded as isothermal, would show promise; however its validity has to be tested by both a rigorous formulation and comparison with experimental data obtained under controlled conditions. In the following a formulation is presented together with experimental data allowing ready practical evaluation of the theory. FORMULATION The mechanical energy balance over an infinitesimal section of a packed bed may be written as follows:

Jan 1, 1969

By R. V. Higgins, A. J. Leighton

A fast method is needed for calculating thoroughly the performance of two-phase flobr~ in reservoir rock with complex geotrietry. The authors present such a method and .slzow its accuracy by romparison with laboratory performrrnce of a five-spot pattern. In making the performance c.alculations, the octant of the five-spot pattern was divided into four channels. The computer tinle required for the culculation was one rllinrcte. This is rorighly about minute per channel. INTRODUCTION By using an electronic computer it is now possible to make reservoir performance calculations in which fewer assumptions and more significant variables are included than was possible with a desk calculator. These performance calculations include such variables as the properties of the reservoir rock and its contained fluids, properties of the rock-fluid system and even different well-spacing patterns. Usually, the more variables that are included the higher the computer cost—and time on the computer is expensive. As a result, a short procedure is needed so the many variables will be included and accurate performance calculations will result. If a reservoir is composed of alternate layers of permeable and impervioi~s rock, and if each conducting layer has a different relative permeability, the combined computer cost for calculating each layer by the present long computer programs (which includes different well-spacing patterns and other variables) would be expensive. The performances of complex spacing patterns in a field often are studied by a potentiometric model, but in these model studies the analogy is to the flow of only a single phase. This paper presents a procedure to calculate the performance of a five-spot pattern with two phases flowing using a potentiometric model as a guide for the dimensions of channels and other related data. The time required to calculate the complete performance is about one minute on the IBM 7090 or four minutes on the IBM 704. The procedure can be extended to calculate the performance of more complex well spacings or an entire field with little modification. The procedure has been tested on the performance of the laboratory water floods of a five-spot pattern reported by Douglas, et alThe range of viscosity ratios in the laboratory experiments is from 0.083 to 754, which is extensive. The accuracy of the performance calculations is excellent as shown by the plotted points in Fig. I. The recovery as influenced by the geometry of the five-spot, taking into account the deviation from true radial character, has been predicted by Aronofsky and Ramey." The authors used a potentiometric model to determine the sweep efficiency to breakthrough of the flooding agent. Dyes, Caudle and Erickson,' by means of a laboratory model, show the influence of mobility ratio on recovery after breakthrough of the injected material. Dyes, et ai, used the X-ray shadowgraph technique and miscible phases in their studies. Craig, Geffen and Morse from the analysis of the performance of their laboratory model correlate many variables, including average saturation of a flooding agent determined by permeability relationship. Craig, et al, used X-ray shadowgraphs to determine the sweep efficiencies in sandstone models. In this report the sweep efficiency is not needed, and the important effect of continuously changing saturation gradients before and after breakthrough

By J. M. Markowitz

The movement of hydrogen in two-phase Zircaloy-2 under the influence of a thermal gradient was studied in specimens of cylindrical geometry. A gross displacement of hydrogen toward the cooler regions of the specimen was observed with consequent copious precipitation of 6-ztrconium (ZrH) there. The kinetics of the diffusion are analyzed and discussed. X HE temperature-gradient redistribution of hydrogen in a-Zircaloy-2 has been treated both theoretically and experimentally Hydrogen moves toward the cold side of the temperature gradient until a steady state has been established; tendency for further hydrogen movement because of temperature differences is nullified by the tendency to move in the reverse direction because of the concentration gradient. The steady state condition is described by the equation in which iV is the concentration of hydrogen at a point in the specimen corresponding to absolute temperature T, R is the gas constant,k is a constant of integration, and Q is a parameter called the heat of transport, characteristic Of the particular system. The value of Q has been determined for hydrogen in Zircaloy-2 by several investigators, using Eq. [11. There is considerable variation in the results, the cause of which has not been resolved; reported values lie in the range 3 to 6 kcal per mole. The physical situation for two-phase thermal migration is much more complex. The -phase boundary for the solubility of hydrogen in Zircaloy-2 ranges from a concentration of 25 ppm at 200°C to a maximum of about 600 ppm at 550°C.4a Thus, if the concentration of hydrogen in Zircaloy-2 is sufficiently great (>600 ppm), the specimen will be entirely two-phase, consisting of a matrix of a-Zircaloy-2 surrounding particles of zirconium hydride. At time zero, with a temperature gradient imposed, the relative amounts of hydride and a-phase in each infinite-simally thin isothermal section of the specimen can be determined from the phase diagram by the lever rule. Moreover, the concentration of hydrogen in the matrix phase varies from point to point, following the a solubility line. Over most of this temperature range (<450°C) 6 phase, Fig. 3, has a constant concentration.5 The diffusion rate toward the cold side should be governed by 1) the slope of the a solubility line and 2) the temperature gradient, The extra complication of two-phase thermal diffusion lies in the fact that migration of hydrogen would leave the a-phase concentration gradient unaffected, since it is fixed at any temperature only by the solubility; gross concentration changes would reflect only the relative amounts of matrix and hydride, which could vary continuously at every point. Migration of hydrogen out of a region would lead to dissolution of hydride, and

Jan 1, 1962

By E. P. Pfleider, C. A. Dufresne

The problem of mooing open-pit ores over large vertical distances is increasing in importance because of the immense deposits being mined. Gravity fall of ore through transfer raises to central haulage points underground has advantages for certain open-pit operations, and this method is being seriously considered for the Carol Project now underway in Canada.

Jan 6, 1961

By F. Kurata, A. F. Bertuzzi, P. C. Davis, T. L. Gore

The phase and volumetric properties of 10 very volatile mixtures are presented for temperatures from — 200°F to above the critical points. These mixtures consisted of natural gases and of mixtures of natural gases with methane and nitrogen. Existing correlations of compressibility factors have been extended to apply to these mixtures. Existing correlations of critical pressures and temperatures do not apply to these mixtures. Methods have been developed for estimating critical temperatures of these mixtures to ± 4°F and critical pressures to 2 5 per cent. These methods apply to other volatile and very volatile mixtures. The results of this work are particularly applicable to the separation of nitrogen from hydrocarbons by low-temperature distillation. INTRODUCTION Knowledge of the low-temperature phase and volumetric properties of natural gases and of other mixtures of the light hydrocarbons is becoming increasingly important as interest in low-temperature separation processes increases. Low-temperature distillation has been used to separate ethane and ethylene from natural gas and from refinery gases for petrochemical uses. Removal of nitrogen from natural gas by low-temperature distillation has been proposed 7,20 as a means of increasing the capacity of existing gas transmission lines and of improving the marketability of the gas. Further application of low-temperature separation processes has been retarded by lack of data on the phase and volumetric behavior of mixtures at low-temperatures and at high pressures. This paper presents the results of determination of the phase and volumetric properties of 10 very volatile mixtures at temperatures from - 200 °F to above the critical point. These mixtures consisted of natural gases with methane and nitrogen. Generalized methods are presented for estimating the critical temperatures, critical pressures, and the densities of such mixtures. EXPERIMENTAL APPARATUS AND PROCEDURES The apparatus and the experimental procedures have been described in an earlier paper13. The method consists of displacing the mixture from a reservoir which is maintained at constant temperature and pressure into an agitated glass equilibrium cell which is maintained at constant temperature. The liquid level within the glass equilibrium cell was visually observed, and the pressure was measured to within & 3 psi with a calibrated Bourdon gage. COMPOSITIONS OF MIXTURES STUDIED The compositions of the mixtures studied are summarized in Table 1. The measured properties included in Table 1 will be discussed later in this paper. The sources of these gases are described below: Gas "A-1&apos;&apos; was obtained from the Phillips Petroleum Co. Its composition was reported in connection with earlier work." The properties of this gas were reported in an earlier paper.13 Gases "A-2, A-3, A-4" were prepared by mixing nitrogen with gas "A-1." Gas "AB-1" was prepared by mixing methane with gas "A-1." The properties of this gas were reported in an earlier paper.&apos;" Gases "AB-2" and "AB-3" were prepared by mixing nitrogen with gas "AB-1." Gas "B" was obtained by W. W. Bodle of J, F. Pritchard & Co. from the primary separator of a well in western Kansas. Gas "C" was obtained from a Cities Service Co. pipeline at Lawrence, Kans. Gas "D" was prepared by mixing gas "AB" with gas "C."

Jan 1, 1955

By J. Wade Watkins, E. S. Mardock

The accurate evaluation of reservoir-performance characteristics in the secondary recovery of petroleum by water flooding requires use of a water tracer that may be injected into water-input wells and detected at oil-production wells to supplement data obtained from core analyses, wellhead tests, and subsurface measurements. Radioactive iodine has been used successfully as a water tracer in field tests to determine: (I) relative rates and patterns of flow of injected water between water-input and oil-production wells and (2) zones of excessive water entry into oil-production wells. Laboratory evaluations of potential water tracers, previous tracer studies, the value of using a radioactive tracer, general field procedures, and the use of surface and subsurface instruments for the detection of the emitted gamma radiation, are summarized. Data from the field tests are presented graphically and discussed in detail. It is concluded that the radioactive-tracer method, using radioactive iodine, may be used successfully to measure either the relative rates and patterns of flow or zones of excessive water entry into wells under conditions of comparatively rapid transit time between wells. INTRODUCTION Extensive use is made of data obtained from core analyses, wellhead tests, fluid characteristics, and subsurface measurements in evaluating the sweep efficiency of water injected into oil sands for the recovery of oil. Theoretical flow rates and patterns may be calculated from those data using radial-flow formulas, if it is assumed that the physical conditions in the productive formation are homogeneous. Unfortunately, homogeneous conditions rarely, if ever, exist in oil-productive formations. The use of a tracer that may be injected into an oil sand and detected quantitatively, or even qualitatively, at offsetting oil-production wells provides basic data that may be used in determining more accurately the subsurface rates and patterns of flow of injected water between wells than is possible by theoretical calculations based on assumed conditions. Consideration of the data obtained by using a water tracer assists in the application of remedial measures to water-input wells, such as plugging of channels, or selective plugging of highly permeable zones, thereby effecting a more uniform flood and a greater ultimate oil recovery. A water tracer should have the following characteristics: (1) low adsorption on solid reservoir material; (2) high solubility in water; (3) low or negligible solubility in crude petroleum; (4) a wide range of solubility of compounds that may be formed by chemical reactions with ions present in reservoir rocks or waters; (5) high detectability in low concentrations by portable apparatus; and (6) general availability at low cost. Additional desirable characteristics are that the tracer should be nonhazardous in nature under normal working conditions and quantitatively detectable in the well bore, as well as at the surface. Review of Previous Tracer Studies The need for a water tracer has been recognized for many years. As far back as 1906, Dole1 described the use of fluorescein in flow-rate studies made in France in 1901. In 1921, Ambrose" discussed in detail the use of organic and inorganic dyes, chlorides, nitrates, and other anions, lithium salts, and the Slichter electrical

Jan 1, 1955

By Augustus Locke

San Francisco Meeting, October, 1911.) Two Opposed Interpretations of the Tonopah Structure.-The important geological publications concerning the Tonopah mining-district are those of Spurr 1 and of Burgess.2 In these publications are presented fundamental differences of interpretation, which are the more interesting because both authorities have had ample opportunity for observation, and because both are geologists of proved ability. I was vastly puzzled to know which had the better of it, and in order that I might reach a conclusion in my own mind, I recently spent some time in the district going over the physical evidence. Surprising as it may seem, this evidence looks agreeably conclusive. A review of it will, I believe, be of interest to those who are familiar with the previous publications. The general geological features of Tonopah are shown in Fig. 1, and the differences of interpretation referred to are outlined in the accompanying notes. Briefly, Burgess regards the various rocks as flows, lying in the order of their deposition. Spurr regards them in part as flows, and in part as flat-lying intrusives. The disagreement, then, concerns the rocks regarded on the one hand as intrusives, and, on the other hand, as flows. These rocks are chiefly the so-called calcitic andesite, the upper rhyolite, and the lower rhyolite. Economic Importance of the Question of Interpretation.-The economic importance of the question of interpretation is, of course, limited to its bearing on the probable distribution of 1 Geology of the Tonopah Mining District, Nevada, Professional Paper No. 42, U. S. Geological Survey (1905). Report on the Geology of the Property of the Montana-Tonopah Mining Co. (1910). An abstract of this report is given in the Mining and Scientific Press, vol. cii., No. 16,p. 560 (Apr. 22, 1911). 2 The Geology of the Producing Part of the Tonopah Mining District, Economic Geology, vol. iv., No. 8, pp. 681 to 712 (Dec., 1909).

Feb 1, 1912

By Reynold Q. Shotts

Nitric acid oxidation rate analyses of three coals, previously studied microscopically by the Bureau of Mines, revealed three components. Relative quantities agree with those found for the four components given by the Bureau and results are consistent with current ideas of coal constitution. Possible multi-component composition for bright coal and a reactivity-rank relation are suggested.

Jan 5, 1953

By C. Richard Tinsley

Non-ferrous econometric metal models available from consultants are reviewed for structure and computer access, using copper as an example The evolution of a computerized metals price forecasting system for a consumer of non-ferrous metals is outlined including front ends, bridge equations, and supporting databases. An empirical sensitivity analysis technique is described. A postscript discusses the subscription costs of these models.

Jan 1, 1977

By Howard A. Meyerhoff

IN western Argentina, in the Province of Mendoza and the Territory of Neuquén, there is a series of solid bitumen deposits which are claimed to be the most extensive in the world. In a linear belt 500 km (311 miles) long, roughly paralleling the axis of the Andes but occupying a variety of positions with respect to the orogenic structures, more than 100 outcrops have been reported. Approximately 70 of these have been prospected, and some mining has been planned or attempted for about half this number. Limited tonnage, high sulphur content, inaccessibility, labor shortages, and disastrous fires have taken a heavy toll among these operations, and in 1947, only 4 deposits were being actively mined, but 8 more were being explored and developed with a view to placing them in production. Inasmuch as these deposits are currently yielding a substantial fraction of Argentina&apos;s limited domestic supply of solid fuels, a brief account of the deposits and of the small industry based upon them will provide a commentary on Argentina&apos;s fuel problem. CHARACTER OF SOLID BITUMENS The solid bitumens of Mendoza and Neuquén are petroleum derivatives, as is indicated by the following ultimate analysis: [CONSTITUENTS PER CENT Hydrogen6.8 Carbon82.4 Nit.rogenI.6 Oxygen2.7 Sulphur2.2 Ash4.3 100.0] In physical appearance they bear a close resemblance to coal and are commonly called carbón. Their specific gravity has an extreme range of 1.10 to 1.777 in 36 samples weighed, but the average is between 1.14 and 1.24. The material is black, lustrous to dull, with blocky to sub-conchoidal fracture. Though brittle, the purest material is softer than anthracite and exhibits slightly more cohesion. This bituminous material is generally known as asfaltita or asphaltite, but definitive chemical studies indicate that the term asphaltite or grahamite can be applied correctly only to the exceptionally pure material of the Auca Mahuida district in Neuquén. Some other name should be used for the chemically variable bitumens found in all other districts, and the designation "asphaltitic pyrobitumen" has been proposed by Carlos A. S. Piscione.1 At the present time these bitumens, are finding favor as solid fuel and as a gas-producing medium. They yield heat values of 8650 to 9750 cal,2 or 14,500 to 16,750 Btu per pound, and in consequence of their excellent heating qualities and the scarcity of imported coal, they are marketed as far away as Buenos Aires at a price of go to 95 pesos, or approximately $22 to 23, per metric ton. In burning, the material swells and decomposes into solid, fluid, and gaseous fractions which burn violently though nonexplosively. Its combustibility has been responsible for disasters and virtually complete destruction at Mina La Esperanza and Mina Santa Marta, and for minor mishaps elsewhere, as at Mina Escondida in August 1947.

Jan 1, 1947

By W. Philippoff, Donald E. Cadwell, S. R. B. Cooke

THE importance of contact angles in flotation has long been recognized, but little has been done to get quantitative relationships between the surface coverage of the mineral by the reagent, the length of the hydrocarbon chain, and the contact angle. It is well known that for a complete monolayer on the surface of a mineral the contact angle 8 is determined only by the reagent1 and principally by the chain length of the hydrocarbon radical. Although for flotation the monolayer usually is regarded as being complete, early experiments of Wark and Cox&apos; showed that at very small concentrations of potassium ethyl xanthate the contact angle on galena changed in a continuous way from 0&apos; to the equilibrium value of 60". Further, Gaudin and Vincenta showed a similar continuity using heptylic acid and sphalerite. This shows that with probably incomplete monolayers, 0 varies with the degree of surface coverage. At the time these experiments were made it was impossible to measure the actual amount of surface coverage, especially since the decrease of the collector concentration in the liquor could be influenced by chemical side reactions. Through the use of the radioactive tracer method for the measurement of the amount of collector adsorbed on the surface of the mineral, Gaudin and Bloecher&apos; were able to determine accurately the actual surface coverage of dodecylamine acetate on quartz, but they did not measure any contact angles. It is believed that the relationship between the surface coverage and the contact angle is extremely important in flotation, especially as Gaudin and Bloecher showed that a 95 pct recovery is possible with a coverage of only 5 pct. Theoretical Considerations The work of adhesion W is the energy bound (in ergs per sq cm) when an interface is formed. It is determined by the difference of the free surface energies (surface tensions) of the respective phases 7j and yZ before contact and the interfacial free surface energy y, after contact. The definition of the contact angle permits the elimination of the unknown surface energy of the solid and hence the calculation of W from the surface tension of the liquid y and the contact angle 8: W = y (1 + COS0) [1] Consider a surface consisting of two components, identified as 2 and 3, 1 being the liquid. The amount of 2 in the composite surface is x, where 0 < x < 1. The respective contact angles with 1 and air are 8, and 8.. The total work of adhesion of such a surface is the sum of the values of the components multiplied by their respective areas. A formal relation can be written: Wm = x-W2+ (l-x)-W, [2] in which W, is the work of adhesion of the composite surface. Eq 1 can be introduced into Wt and Wa, but in the case of W, some discussion is needed. If the two components are segregated, each component forming an integral part of the composite surface there is no physical meaning for a contact angle 8m calculated from W,, by using eq 1. If, on the other hand, the area of each patch of the components is small in comparison with, say, the diameter of the bubble used in measuring, it could be expected that 0m would have a physical significance, because of the action of the surface tension of the liquid-gas interface tending to smooth out sharp corners. How small these patches would have to be is difficult to predict, but by using composite surfaces with microscopically

Jan 1, 1953