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By Thomas M. Garland

A field study was made by the Bureau of Mines in cooperation with oil companies to determine the feasibility of changing the injection profile of water-input wells after water breakthrough at producing oil wells. A secondary objective was to study the particle size and quantity of plugging material required to change the input profile and the methods of applying these materials. Fifty-three injection wells were treated with various amounts and types of plugging materials and the injection profile was definitely changed in most of the wells treated. Increased efficiency of water injection after treatment was indicated by tracer surveys and injection-well performance. There were some indications that the rate of water production was reduced and the rate of oil production was increased as a result of selective-plugging treatments, but ,s found that an immediate change in the rate of oil and water production did not normally occur. In many cases, beneficial results from a treatment may never be observed in the rate of oil or water production due to the many factors that affect the performance of producing and injection wells.

Jan 1, 1966

By C. M. Bartley

In world-wide mining circles countries become known by the principal minerals they produce. The production of iron, copper, phosphate and sulphur in the United-States-has-been particularly significant and has provided the base for aggressive developments in heavy industry, agriculture and chemicals. Mention diamonds and gold-and you will think--South Africa; silver-Mexico; nickel and asbestos--Canada. The main purpose of this paper is to point out that potash mast be added to the list of minerals by which Canada is known in the mining World. The potash deposits of western Canada must be classed as a major world source of chemical fertilizer raw material. We believe that they are both the largest and the richest of all known deposits in the world. The most knowledgeable people in the industry avoid making estimates of reserves because even where the arithmetic is correct the total is so large that it appears to be ridiculous. In 1957 Marion Goudie made a carefully qualified estimate of 6 billion tons of recoverable potash above 3,500 ft, and grading 25 per cent K20 or better. This figure can now be increased by the amounts available through solution mining. No one has bothered to estimate how much this is because it is so large that the actual amount is not significant.

Jan 1, 1966

By Robert L. Bates

United States production of the industrial minerals, ahead of that of the metals since 1946, has shown a steady and rapid growth. By 1963, their value was more than twice that of the metals. Yet papers on the metallic ores continue to dominate the meetings of the Society of Economic Geologists and constitute nearly nine-tenths of the lead papers in Economic Geology. Most of the geological communication that does take place concerning the industrial minerals deals with high-value special-purpose minerals, which are comparable to the metallic ores in geologic complexity. The large-bulk rock products, which are growing fastest in production value, are characterized by relatively simple geology and by thousands of small producing firms, many of which do little or no geological work. The need for geological advice by this very large segment of the industry is bound to increase. In the meantime, a plea is made for more geological communication among those concerned with the industrial minerals of all varieties.

Jan 1, 1966

By A. R. Hendrickson, C. F. Smith

Hydrofluoric-hydrochloric acid mixtures have been successfully used to stimulate sandstone reservoirs for a number of years. Hydrofluoric acid (HF) has a specific reactivity with silica which makes it more effective than HCl for use in sandstone. Kinetics of the reactions of HF have been studied to determine the related effects of reservoir composition, temperature, acid concentration and pressure on the spending rate of HF. Secondary effects from by-product formation are noted and described. Predictions are made concerning the improvement in productivity resulting from HF treatment of skin damage. The kinetic order of HF reaction in sandstone was experimentally determined to be first order, i.e., the reaction rate is proportional to concentration. HF reacts faster on calcite than on clay, which, in turn, is faster than the reaction rate of HF on sand. Static conditions retard the HF reaction rate. As HF is forced into cores, there is a temporary reduction as a function of flow rate and acid concentration. Extensive deposition of calcium fluoride in acidized cores was not observed. Although some CaF, was defected, it was not considered a major source of damage in cores containing moderate amounts of carbonate. Other fluosilicates could be potentially more dangerous than CaF, in reducing permeabiliry. INTRODUCTION Hydrofluoric acid has been widely used in stimulation treatments since 1935, when mud acid was introduced to the petroleum industry. Originally, this hydrochloric-hydrofluoric acid mixture was intended to remove mud filter cake, but it has since been successfully applied to many other oilfield problems. Mud acid treatments have been unusually successful in sandstone reservoirs where hydrochloric acid is unreactive due to a lack of enough calcite in the formation. The relatively small amount of hydrofluoric acid present (2.1 per cent) reacts with sand grains, clays and traces of calcite which are generally present in sandstone reservoirs. Since hydrofluoric acid (HF) is the key to mud acid success, this research effort has been dedicated to gaining a more thorough understanding of the basic chemical and physical principles involved as HF reacts. Hydrofluoric acid's reactivity with silica makes it unique in application. Other mineral acids such as hydrochloric, sulfuric or nitric are unreactive with most silicious materials which comprise sandstone formations. A typical sandstone reservoir may contain 50 to 85 per cent silicon dioxide, more commonly called sand or quartz. Hydrofluoric acid reacts as follows: 4HF + SiO2 + SiFO + 2H2O The silicon tetrafluoride (SiF,) is a soluble gas, in some ways similar to CO2, and is capable of undergoing further reaction when held in solution by pressure. These reactions will be considered in detail later. Kinetics of the reactions of HF have been studied to determine the effect of reservoir composition, temperature and pressure on the spending of the acid. Secondary effects from by-product formation have been noted and described. The individual reactions of HF on quartz, glass and clay are reported. Mathematical correlations have been drawn, then applied to studies of HF spending in cores obtained from actual producing sandstone formations. The research reported herein is only the beginning of a continuing approach to better understanding and use of HF in petroleum reservoirs. THEORY AND DEFINITIONS Through the years, a concentrated effort has been made to understand the effects of many variables on hydrochloric acid (HCI) spending in limestone. Hendrickson el al., have given mathematical relationships for HC1 reactions which made possible the engineered approach to acidizing. The same variables—temperature, acid concentration, formation composition, pressure and permeability-porosity relationships—which affect HC1 behavior in limestone also govern HF behavior in sandstone. Insoluble by-products of HF reaction have been isolated and identified. Their effect on fluid flow has been measured under varying conditions in an attempt to evaluate the extent of possible damage and means of eliminating it. In general, HF follows the same reaction paths as HCI. It will react with limestone and dolomite with speed and ease. Thin sections of acidized cores show the reaction of HF with limestone or calcite faster than its reaction with either clay or sand. When HF reacts with calcite (CaCO,), theoretically, calcium fluoride (CaF2) is precipitated, and has been blamed as a major cause of reduced permeability. On the other hand, pH and pressure such as that encountered in an underground formation under acid treatment definitely retard CaF2 formation,' so the whole question of CaF, deposition in wells is a subject for study.

Jan 1, 1966

Jan 1, 1966

By Earle S. Burnett

Rotating piston deadweight gages have been used for many years for measurement of pressure to several hundred atmospheres. They have been calibrated by comparison of fluid pressures produced by various loads bearing on the piston bases, as measured by corresponding heights of balancing columns of mercury. When expressed in appropriate units, these ratios of column heights to piston loads are called piston constants. Experimental arrangements and procedures for their determination are presented in this paper, followed by a discussion of their significance and of their subsequent applications.

Jan 1, 1966

By John P. Weir

The planning of an underground mine for successful extraction of a bedded deposit in sedimentary rocks requires the integrated evaluation of many interdependent problems. The development and coordination of feasible solutions are the responsibility of the mining engineer. One of these problems will be discussed herein; this is the design and .layout of mine workings to secure effective control of the strata above and below the deposit. The objective is the simplest possible repetitive system permitting safe maximum recovery at optimum cost. Mining conditions to be encountered must be predictable. The best mining equipment is ineffective unless strata are controlled. Conversely, a mining layout is only of academic interest, if equipment can not be adapted to work it with adequate provision for ventilation, compliance with mining laws, proper ingress and egress and other practical requirements. Strata control, then, is but one of the mining engineer's problems, and the solutions must be worked out concurrently with solutions to other problems. Dr. Karl F. Fetters in his introductory remarks before the Fourth International Conference on Strata Control and Rock Mechanics at Columbia University said that mining engineering ?has come from the stage of empiricism backed by intuitive reasoning, to where it is based on fundamental scientific and engineering principles?. The standard curriculum in mining engineering now reflects such a change. In common with other branches of engineering education, less and less emphasis is placed on practical skills and more and more on broad scientific education. Science, research and the quest for basic truth are stressed, while descriptive courses and the teaching of specific skills are limited.

Jan 1, 1966

By Willard L. Hunter

The Bureau of Mines studied the effect of temperature upon the reduction of chromite by carbon and the relative reducibility of chromites as a function of their composition. Ferric oxide was also studied to provide comparative data. Pellets weighing approximately 1 gram and containing 70 percent ferric oxide, chromic oxide, or chromite and 30 percent graphite were subjected to closely controlled temperatures under a flow of argon for 15 minutes. The amount of CO and CO2 evolved was measured, and the reduced sample was analyzed by X-ray diffraction techniques. The reduction of Fe2O3 was studied over a temperature range of 600° to 1,400° C, while the reduction of Cr2O5 and chromite was conducted from 9000 to 1,621° C. The temperature above which appreciable reduction of Cr203 by graphite took place was 1,125° C. The temperature at which significant reduction started for three of the four chromite samples was approximately the same, indicating that there was concurrent reduction of iron and chromium oxides in the chromite mineral rather than selective reduction of iron oxides followed by reduction of chromic oxide. Rhodesian chromite appeared to dissociate at a lower temperature with concurrent reduction of iron. Based on the temperature at Which chromite was 50 percent reduced in 15 minutes, Transvaal chromite reduced most easily, followed by Mouat, then by Kampersian, and finally by Rhodesian DFC material. Statistical analysis of test results indicated that the ferric iron content of chromites affects their reduction behavior more than any other constituent.

Jan 1, 1966

By G. W. Birge

The Bureau of Mines investigated the effect of temperature on the mechanical strength of cokes of the type normally used in blast furnace operations. Eight samples of industrially produced cokes were subjected to ASTM tumbler tests at temperatures as high as 1,100° C (2,012° F); these temperatures had no significant effect on tumbler results for cokes with stability indexes of 40.6 to 59.9. Two foundry cokes which were tested at only one elevated temperature (900° C) decreased slightly in tumbler stability. Iron are pellets made from a variety of ores and by various industrial methods were not significantly affected by temperature when tested in an oxidizing atmosphere at 1,000° C (1,832° F) by the tentative standard ASTM method.

Jan 1, 1966

By Byron N. Cooper

The Revenue Act of 1926 provided for five simple categories of natural resources to have the benefit of depletion allowances. In the 1947 Revenue Act, the number was increased to twenty-five, and in the 1951 Revenue Act to fifty-four. Of this number, fourteen were allowed 5 per cent; nine, 10 per cent; twenty-nine, 15 per cent; one, 23 per cent; and one (oil and gas), 27.5 per cent. The 1951 Revenue Act created a host of difficulties, including application of the "end- use criterion" and determination of the commonly accepted meaning of such terms as limestone, dolomite, chemical- and metallurgical-grade limestone, marble, calcium carbonates, and magnesium carbonates. Dolomite, for example, was listed at 10 per cent depletion allowance, but without definition. In the great amount of litigation growing out of the 1951 Revenue Act and its administration, it became essential to understand the derivation and subsequent usage of these common geologic terms. One thing that became clear was that our definitions changed significantly between the time that the 1951 Revenue Act became law and the time that later cases were tried. Some geologists neglected to learn about first usages of such terms as metallurgical limestone, and about meanings that were applicable when the 1951 Revenue Act was written and passed. Legal meanings in this paper are discussed in the light of certain famous cases that have been tried and settled.

Jan 1, 1966

By Willard L. Hunter

The smelting of tin slags was undertaken at the Bureau of Mines Albany Metallurgy Research Center (AMRC) to produce crude columbium-tantalum ferro-alloy as a unit operation in the production of pure columbium and tantalum oxides or chlorides. Columbium and tantalum-rich alloy was prepared during short unrelated campaigns over a total period of 12 years. Tin slags from Malaya and the Congo (Geomines) were smelted. These slags were reduced by carbon in a small, single-phase, steel-making furnace} a larger three-phase, steelmaking furnace, and a three-phase, submerged-arc furnace, In all cases depleted slags were fluid and easily tapped from the furnace. However, unless diluted by iron additions, the metal product was a viscous, high-melting, heterogeneous mixture that could be removed from the furnace only by hand rabbling.

Jan 1, 1966

By L. B. Pankratzt

The heat content above 298.15° K of ferroelectric lithium columbate (LiCbO3) was measured to 1,770° K. The Curie temperature was determined to be 1,450° K, the melting point 1,540° K, and the heat of fusion 16.94 kcal/mole. Heat content and entropy increments have been tabulated for the temperature range from i98.15° to 1,800° K. Heat contents are also given in equation form.

Jan 1, 1966

By M. E. Hawkins

This Bureau of Mines report provides information on all of the 329 proved salt domes in the Gulf Coastal States and offshore area of the United States. It includes specific data related to location, depth to the cap rock and to the salt, storage facilities for LPG, and production of salt, sulfur, petroleum, and rock related to or associated with the dome structure in the subject area. Also included is a brief history of the salt, sulfur, and petroleum industries as related to the salt domes. Gulf Coast salt domes were the scene of the first discovery of a large deposit of rock salt in North America, the birthplace of the Frasch sulfur industry, and the location of the first large oil gushers that ushered in the modern liquid fuel age.

Jan 1, 1966

By C. J. Walker

The Bureau of Mines undertook a theoretical and laboratory study to determine the feasibility of using ethylene as a tracer for natural gas in underground gas-storage reservoirs. The study indicated that ethylene was a useful gas tracer in underground gas storages. Tracer losses were not excessive. Laboratory tests were conducted at pressures as high as 500 psia in both wet and dry consolidated-sandstone cores, evaluating tracer loss with gas blends containing natural gas with different concentrations of ethylene tracer. Under certain conditions losses were less than 17 percent.

Jan 1, 1966

By M. S. Oudenhoven

This Bureau of Mines investigation was conducted to obtain an experimental solution of stress changes in the vicinity of a circular opening in an infinite plate. Plates were stressed biaxially in compression and subjected, by four different-length shoes, to a uniform pressure at opposing points on the opening periphery. The principal stresses along the vertical and horizontal axes, which result from peripheral pressure, were obtained from the photoelastic analysis of four frozen-stress epoxy models. These principal stresses were then super-imposed on the mathematically determined principal stresses (along the same axes) obtained from a theoretical biaxial stress field in which the magnitude of the lateral pressure was one-third that of the vertical pressure. The results indicate that an increase in shoe length increases the radial compressive stress and the tangential tensile stress (except tangential compression at r/a = 1, which exists for all shoe lengths). Also, a partial control of the stresses within one-half radius of the opening surface is accomplished by a change in the magnitude and placement of peripheral pressure.

Jan 1, 1966

By E. P. Ferrero

Analyses of 38 crude oil samples from 25 fields in Algeria, Libya, and Nigeria are presented in this report. The 38 crude oils are listed alphabetically by country and field. Also shown are the geographic and geologic sources of the samples analyzed, the companies that supplied the samples, the general characteristics and analytical and computed data, and the production for the fields from which the samples were obtained.

Jan 1, 1966

By H. A. Watson

Laboratory tests on three commercial methane detectors, two combustion-type detectors and one interferometer-type detector, were made by the Bureau of Mines to determine their response to certain single and multiple flammable gases mixed with normal and abnormal air atmospheres. Although both types of detectors responded accurately to methane-normal air mixtures, they did not show correct concentrations for other single flammable gases in air. Uniquely, the response of the interferometer-type detector to hydrogen was in a negative direction. The effects of individual gases in multiple flammable gas mixtures were approximately additive. In oxygen-deficient atmospheres the methane response of the interferometer-type detector erred on the high side, but only in very low oxygen concentrations were the combustion-type detectors affected-showing low, erratic methane readings.

Jan 1, 1966

By B. H. Caudle, L. H. Silberberg

Reservoir depletion by natural water drive is typified by the movement of water from an aquifer into the adjacent oil-bearing formation. Prior studies of this type 01 water movement have generally neglected the resistance to flow in the aquifer and its effect on the movement of water into the oil bearing zone. A method for designing and operating scaled models of such reservoir systems is presented. Experimental data on a model of an edge-water-drive reservoir are shown and discussed. INTRODUCTION Most petroleum reservoirs derive at least a part of their productive capacity from water influx. This water may be injected from the surface or it may come from an aquifer adjacent to the oil zone. In either case, the reservoir engineer must be able to estimate the advance of the water as a function of either the elapsed time or the fluid produced. This paper describes a type of fluid flow model which includes the effect of viscous and gravitational forces in the reservoir and the surrounding aquifer. Natural water influx can be divided into three general (but widely overlapping) categories according to the direction of flow in the aquifer. These are shown schematically in Fig. 1. Fig. l(a) illustrates an edge-water-drive mechanism. In this case, water advances updip along the stratum but the movement of water is essentially horizontal and very little of the oil is actually underlain by water. The bottom-water drive (Fig. l(b)) is characterized by a thick aquifer underlying the oil zone. The water movement is generally vertical in the aquifer. The third category is illustrated in l(c). Referred to as the "thin oil column", this type of oil accumulation consists of oil over water in a relatively thin stratum. Fluid movement is horizontal in both the oil and water zones, except close to the producing well. One characteristic which all three of these types have in common is that part of the water flow takes place in the water invaded region of the oil reservoir while the remainder of the water flow occurs in the aquifer. The resistance to the flow of water usually will not be the same in these two regions. This occurs because the porous rock normally contains only water in the aquifer, while the water-invaded region always contains microscopic globules of bypassed oil (residual oil) which interfere with the flow of water through the rock. The production history of any type of a water-drive system is a function of two phenomena — where the water goes, and how it displaces the oil in the area invaded by the water. It is usually impractical to study these two phenomena at the same time. In most cases one type of analysis is used to predict the gross movement of water in the reservoir, while a different type of analysis is employed to determine the amount of oil to be recovered from the gross volume contacted by the water. The portion of the oil reservoir which is invaded by water is mainly a function of the resistances to fluid flow in the several parts of the flow system. This gross water influx in the three types of natural water drive typically results in water cusping to the production wells either from the side or from below (water coning). In 1747, Muskat described a greatly simplified mathematical model for predicting the area invaded by water in a bottom-water-drive reservoir.1 This model used the Laplace equation and suitable boundary conditions to describe the isopotentials and streamlines in the flow system. The use of this model assumes that (1) the reservoir rock is homogeneous in nature, (2) the oil and water mobilities are equal, (3) there is no oil flowing in the water invaded region, and (4) external forces — such as gravity — do not affect the flow. This method has been used for both natural water drives and water injection projects. In this, as in most models, the method of images is used to reduce the size of the model necessary to describe the reservoir. The assumption of equal viscosities and permea-

Jan 1, 1966

By Raymond L. Lowrie

Coal deposits in the Boulder-Weld County coalfield in Colorado are analyzed in relation to economic factors governing the growth, stability, and competitive potential of the coal industry. Recoverable reserves, estimated to be 571 million tons, are discussed in detail, particularly those in the Erie and Frederick Quadrangles. Geology of the coal measures, quantity and quality of water resources, and chemical and physical properties of the coal are described. Coal production factors, including mining techniques and equipment, labor requirements, transportation facilities and rates, and markets, are considered for coal's position in competition with alternate fuels. Growth of the fuels market, through increasing thermal-electric power generation in the Denver Metropolitan Area, will stimulate coal production in Colorado. Reserves of the contiguous Boulder-Weld coalfield, if mined in a sustained, year-round, high-tonnage operation, could be used to supply much of that fuel demand.

Jan 1, 1966

By R. Barany

The heats of the glass-crystal transformation of nepheline (Na0.7794K0.2206AlSiO4) and wollastonite (CaSiO3) and the heat of formation of nepheline at 298.15° K were determined by solution calorimetry. For the glass-crystal transformations, the heat values were -9.0 ± 0.3 kcal/mole for nepheline and -8.1 ± 0.2 kcal/mole for wollastonite. The heat of formation of nepheline was -34.8 ± 0.6 kcal/mole from the oxides and -501.0 ± 0.5 kcal/mole from the elements.

Jan 1, 1966