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By R. S. Pratt

IT is proposed to discuss the materials and furnaces, as well as the melting procedures used in preparing metal for casting billets, bars or cakes for mill fabrication. As far as possible, consideration will be given to the alloys that are commonly made in most brass mills producing strip, tube, rod and wire. RAW MATERIAL The basic raw material for such mills, of course, is copper, which may be obtained in the form of ingots, ingot bars or cathodes. Refinery-cast ingots and ingot bars, which are simply double ingots, are supplied in accordance with A.S.T.M. Specifications as regular electrolytic or fire-refined tough-pitch copper. In the wrought-metal industry, the electrolytic brands have been preferred, although during the war large quantities of fire-refined coppers sufficiently pure to be suitable for all existing requirements were imported from South America. With the exception of Lake copper, most primary fire refined coppers produced in this country have not been considered satisfactory for wrought metal alloys. Cathode copper, which is now widely used instead of ingot copper for alloying, is the electrolytically deposited metal that is normally remelted in the production of electrolytic tough-pitch ingots. It is in the form of rough, flat plates not suitable for processing but quite satisfactory for melting when sheared into suitable sizes. Raw zinc is perhaps the next most important raw material and this is obtained in various grades, depending on the analytical requirements of the alloy to be made. The grades of zinc as outlined in the A.S.T.M. Specifications vary in cost with the amount of impurities-lead, iron, cadmium-and are purchased in such a way as to produce the most economical mixture consistent with the purity required in the alloy. Other virgin metals (lead, tin, aluminum and nickel) are used in varying quantities for making copper alloys. These elements can also be purchased in accordance with the appropriate A.S.T.M. Specifications where available. Also available are a number of special alloys, which are used as deoxidizers or as means of adding relatively small quantities of elements not suitable for adding directly as virgin metal. In this category are such materials as phosphor copper or phosphor tin, silicon copper, manganese copper, cadmium copper, and copper-iron or zinc-iron alloys. Some of these alloys may be purchased on a definite alloy basis or may be produced in the plant itself for its own use. For largely economic reasons, however, a great proportion of the charge to the melting furnaces consists of alloy scrap. In the production of many finished products, as much as 70 or 75 per cent of the metal originally cast may be discarded at various points along the production line. This material eventually finds its way back to the casting shop as mill scrap, overhaul or scalping chips, skeleton scrap, rod turnings, or miscellaneous fabricating scrap. One of the most serious problems in the

Jan 1, 1946

By Edward H. Robie

In late November and early December a considerable portion of our time was devoted to obtaining a business manager for Institute headquarters. The advisability of creating such a position was suggested in 1949 in the report of the Johnson committee. In that year, however, the Institute had a deficit of $72,000 so every effort was made to minimize expense. At that time most of the duties that normally would be assumed by a business manager were given to Newell Appleton who became office manager, convention manager, purchasing agent, and assistant to the secretary. So many responsibilities were his that he could not devote the necessary time to all of the many things that needed attention. H. H. Vasoll, representing a firm that made a study of Institute head office procedures early last fall, made a recommendation that "a business manager and controller from outside the present organization" be obtained, who would supervise the work of accounting, addressograph, purchasing, book and journal orders, filing, and mailing depts. He further recommended that Mr. Appleton be made administrative secretary, in which position he would act as head of an "Institute Activities Dept." He would devote his time to convention planning, meeting arrangements, travel accommodations, membership control and promotion, and public relations, and would assist the Secretary on special problems. Thus, Mr. Appleton retains some of his former responsibilities and will take more of the load off our shoulders in the conduct of affairs at Institute headquarters. The rest of his former work will be in the province of the newly created "Business Office Dept." Peter J. Apol is the man finally selected for the post of business manager. He is a young man of 32, a native Michigander and a graduate of the University of Michigan where he received a B.S. degree in business administration in 1940. He then spent three years in the Navy and has the rank of Lieutenant in the U. S. Naval Reserve. Three more years were spent in the U. S. Maritime Service as chief purser, and another year as chief paymaster for the Pope & Talbot Steamship Co. The past four years have been spent as head of the Greenland Construction Co., Greenland, N. H., chiefly engaged in building construction. Mr. Apol will endeavor to increase the efficiency of Institute headquarters operations and remove all possible causes for complaints of individual members. He will coordinate as seems advisable the work of various departments and install such modern business office machinery as seems applicable to our needs.

Jan 1, 1952

By G. C. Wallick, J. S. Aronofsky

This paper presents an experimental verification of numerical solutions of the differential equation describing the transient flow of an ideal gas through a porous material including gas slip effects. Several experiments previously proposed by one of the authors are described together with the correlation of the experimental results with the numerical solutions. Excellent agreement is shown between experiment and theory, thus demonstrating the validity of both the basic assumption made in the derivation of the differential equation and of the numerical solutions of the differential equation. INTRODUCTION In a recent paper,' one of the authors has discussed a numerical solution of the differential equation describing the unsteady flow of an ideal gas through a porous material. This paper was primarily concerned with the effect of gas slip on the flow behavior. In steady state measurements, Klinkenberg2 and others have observed that the apparent gas permeability Kn of a porous material may be expressed as a linear function of the reciprocal average pressure 1/P of the form, ka = b + m/P........(1) where the intercept b is a constant for a given porous material and the slope m is a constant for a given porous material-gas combination. Aronofsky1 assumed that Equation (1) could be used to describe transient flow if P was replaced by the average pressure in an infinitesimal volume element. A number of numerical solutions of the resultant differential equation were presented and specific flow experiments were proposed as a means of testing the numerical solutions. The purpose of the present paper is to describe the results of several of these experiments and the correlation of the experimental data with the results of the numerical analysis. Reference should be made to the previous paper' for details of the mathematical and numerical analysis. EXPERIMENTAL PROCEDURE A simplified schematic drawing of the experimental apparatus is shown in Fig. 1. An 8.89 cm diameter limestone core of length L = 14.82 cm was mounted in a conventional rubber sleeve permeameter cell. The external sleeve pressure in this cell was maintained equal to 500 psig during all experimental tests, thus permitting only longitudinal flow through the core. One end of the core, X = L, was connected to an adjustable cavity of volume V as well as a pressure gauge or manometer. The other end of the core, X = 0, was connected to a Nullmatic pressure regulator which was in turn connected to a nitrogen cylinder or vacuum pump. In each experiment, the core and adjacent dead volume were charged with nitrogen to a uniform gas pressure P1. The pressure at X = 0 was then suddenly raised or lowered to a constant pressure P, and the resulting pressure buildup or pressure decline at X — L was recorded as a function of the time. The porosity + and the permeability constants m and b were determined using the transient method which was suggested by the results of the numerical analysis and which was described in the earlier paper.' The following average values for these constants were obtained as a result of 19 separate evaluations: 171 -0.259 2 0.005 md-atm; b = 0.374 5 0.008 md; and F = 0.098 ± 0.005*. It should be noted that in order that transient phenomena will be slow enough to be observed conveniently, it is desirable to use a porous material of very low permeability, e.g., less than I md. Moreover, it is in this low permeability range that the gas slip effects are most significant. Thus, such a low permeability sample is very suitable for use in an experimental verification of the numerical solutions previously described.

Jan 1, 1955

By E. H. Lancaster, M. E. Mitchell

A MUD-conditioning program found to be very effective for drilling and completion operations on routine field wells requiring relatively short drilling time involves a moderate alkaline-tannate-bentonite treatment resulting in an ultimate filtration rate of 10.0 cc or less (API test). Mud weight schedules are planned from pressure information on completed wells in producing reservoirs and drill-stem test data obtained on other zones not being produced at present. In general, terminal mud viscosities average 45 sec (Marsh). This value has been found to be sufficient to remove cuttings from the well bore on the average well, with the slush pumps in general use on the rigs. On field wells requiring drilling times in excess of approximately 30 days, an alkaline-tannate-lime-bentonite treatment has been effective in maintaining desirable viscosities and filtration rates with a substantial reduction in chemical costs. This system has shown particular advantage on heavily weighted muds and those with abnormal flow-line temperatures. For the most part, the chemical treatment utilized in wildcat drilling follows closely the program used on field wells, depending on depth and duration of drilling operations. Wildcat mud programs are planned from information available from various geologic and operational sources, taking into consideration the possibility of encountering mud problems of a special nature in the wildcat area. Careful planning of wildcat mud pro- grams has proved to have definite value in avoiding most serious mud problems. An analysis and recommended treatment are presented on several special. mud problems which have been encountered in the area in the past. Those problems discussed are lost circulation, blowouts, sloughing shale, excessive chloride contamination, sulphate contamination, and prevention and correction of cement contamination. Introduction Drilling-mud control in the Southwest Texas area, in general, does not involve the multiplicity of problems encountered in other coastal areas. For instance, it is rare that a mixture of problems such as lost circulation, abnormal pressure, severe sloughing shale, and others, occurs on one well within close enough limits in vertical depth not to be taken care of by a sensible casing program, together with a relatively clear-cut mud program. There are conditions such as the fairly widespread occurrence of abnormal pressure in the lower Frio and Vicksburg zones, and the tendency for sloughing shale in the Jackson section which make for rather expensive mud control. However, the availability of fairly accurate geologic and operational information makes possible a reasonable degree of standardization on mud treatment over a relatively large area. It may be said that, over most of this area where drilling is currently in progress, the natural mud made is very poor in quality, but responds readily to moderate chemical treatment to yield very good wall-building characteristics. AS far as field development drilling is concerned, the mud engineer's principal job, once the routine treatment best

Jan 1, 1949

By Philip R. Strand

Vermiculite is the name used for those micaceous minerals with a ferromagnesian aluminum silicate composition and the unique property of exfoliating to a low density material when heated. Commercially, the exfoliated products are also called vermiculite, or more exactly, expanded vermiculite. In its exfoliated state, vermiculite serves many markets, chief among them construction, agriculture, horticulture, and general industry. Composition and Properties Vermiculite, in a natural state, has the characteristic mica habit, splits readily into thin laminae, flexible but inelastic. In a mineralogical sense, vermiculite is a hydrated silicate with no exact chemical composition. The structural formula for a macroscopic, trioctahedral vermiculite may be written: [ ] The structure of vermiculite is basically that of a talc, and it could be regarded as a trioctahedral member of the smectite group. Macroscopically, vermiculite displays the prominent monoclinic crystal faces that are commonly marked by lines at 60° and 120°. Hardness varies from 1.5 to 2.8 or more; specific gravities are between 2.1 and 2.8; color is amber, bronze, brown, dark green, or black. When heated quickly to an elevated tempera¬ture, vermiculite expands by exfoliating at right angles to the cleavage, into wormlike pieces (the name vermiculite is derived from the Latin `vermiculare,' to breed worms). This characteristic of expansion, the basis for commercial use of the mineral, is the result of the mechanical separation of the layers by the rapid conversion of contained water to steam. The increase in bulk volume of commercial grades is 8 to 12 times, but individual flakes may expand as much as 30 times. All expansion occurs at right angles to the basal cleavage. Vermiculite may also be expanded by a number of chemical processes such as soaking in hydrogen peroxide, weak acids, and other electrolytes. There is a color change during expansion that is dependent upon the composition of the vermiculite and furnace atmospheres. Heating in an oxidizing atmosphere produces dull gray colors. The iron is generally not oxidized during chemical expansion. The exfoliation of the vermiculite crystal results in large pores being formed between groups of platelets. Thus exfoliation can make available a large increase in void volume without significantly changing the surface area of the platelets. This characteristic is important in the chemical carrier applications of vermiculite. Although there has been much research on the chemical and structural composition of vermiculite, an exact formula and composition cannot be described. This is to be expected since vermiculite derives from a number of different mineral sources. As has been proposed, vermiculite is not a single mineral species, but families of related minerals. Additionally, commercial interest in the end product has resulted in the name vermiculite being applied to the very voluminous, bloated products from calcination of baueritized (bleached) phlogopite. This has also resulted in many names for the specific vermiculite found in a particular deposit. All of this difficulty arises from the nature of its crystal chemistry. Consequently, vermiculite is now thought of as several related variable mineral series rather than a group of related species. The vermiculites have a common silica tetrahedral sheet structure with separating ions. It is now generally agreed that vermiculites must also be regarded as true clay minerals. The properties of the mineral, such as cation exchange capacity, organic complexing ability, and vari-

Jan 1, 1975

By J. A. Hafford, J. K. Kerver, J. G. Richardson, P. M. Blair, J. S. Osoba

This paper presents the results of laboratory measurements of relative permeabilities to oil and gas on small core samples of reservoir rock by five methods, and describes the influences of such factors as boundary effect, hysteresis, and rate upon these measurements. The five methods used were the "Penn State," the "single core dynamic," the "gas drive," the "stationary liquid," and the "Hassler" techniques. In those methods in which the results are subject to error hecause of the boundary effect, the error may be minimized hy the use of high rates of flow. In order to avoid complexities introduced by hysteresis, it is necessary to approach each saturation unidirectionally. Observed deviations of relative permeabilities with rate can be explained as a manifestation of the boundary effect, and disappear as the boundary effect vanishes. The results indicate that all five methods yield essentially the same relative permeabilities to gas. Of the four methods applicable to the determination of relative permeability to oil, three, the Penn State, single core dynamic, and gas drive, gave relative permeabilities to oil which were in close agreement. The Hassler method gave relative permeabilities to oil which were consistently lower than the results obtained by the other methods. INTRODUCTION The relationship between the effective permeability of a reservoir rock to each of the fluids flowing through it and the corresponding fluid saturation is an important characteristic of the reservoir rock. Knowledge of this characteristic is and gas reservoirs and of the ultimate recovery to be expected extremely important in the prediction of the behavior of oil under various operating conditions. These effective permeabilities are usually expressed as the "relative permeability" to a fluid phase, defined as the ratio of the effective permeability to the permeability of the rock to a single phase at 100 per cent saturation. Relative permeability-saturation relations are not the same for all kinds of reservoir rock, but may vary from formation to formation, and within the different portions of a heterogeneous formation. In studying the performance of a specific reservoir, it is necessary, then, that the relative permeability characteristics of the individual portions of the reservoir be measured. These measurements may be made in the laboratory on small core samples from the reservoir. Various techniques have been proposed for the measurement in the laboratory of relative permeability-saturation relations. In varying degree, difficulties attend the use of all of the methods which have been proposed. It is the purpose of this paper to discuss the factors which influence the measurement of relative permeability, the difficulties encountered in several methods, and to present comparative results obtained by the use of various techniques. FACTORS WHICH INFLUENCE THE MEASUREMENT OF RELATIVE PERMEABILITY It is necessary that the relative permeability data measured in the laboratory yield the same relative permeability-saturation relationships that would govern the flow of fluids through the sample if it were to occupy its original position in the reservoir. Since the core sample upon which the laboratory measurements are made is not surrounded by similar core material as it was in the reservoir, an error in measuring the relative permeabilities may arise from the "boundary effect" which results from a discontinuity in capillary properties of the system at the effluent end of the core. Again, the rates of

Jan 1, 1951

By John D. Sullivan, Chester R. Austin, Edwin J. Rogers

The problem of making a building unit combining the necessary physical and mechanical properties and good thermal insulation has been foremost in the minds of architects and ceramic and construction engineers for many years. This paper presents the results of studies on thermally expanding shales or clays to produce lightweight cellular products suitable for making building units. An expanded clay block suitable for building purposes should be large enough qo that substantial savings may be effected in labor costs in laying the wall. The permeability should be low and it should have sufficiently good "dry-wall" characteristics to permit exposing the exterior surface to the elements, and to permit plastering directly the inside wall surface. The thermal conductivity should be low and the mechanical properties should be adequate. Obviously, a unit possessing satisfactory qualities for constructing an - outside wall would be satisfactory for interior walls and for back-up purposes. The results of studies on bloating various shales or clays† and the properties of the expanded products are reported. In another paper1 basic factors involved in bloating of clays are discussed. Manufacturers of ceramic products, partitularly structural clay, may encounter bloating of the ware during burning, and precautions must be followed to avoid this phenomenon. About 1927 the C. F. Burgess Laboratories, Madison, Wis., while carrying on an investigation for the American Face Brick Research Corporation, conceived the idea of intentionally bloating clay while holding it in a restrained condition, with the hope of producing a unitary cellular mass. Work was carried on until about 1931, when studies were terminated because of business conditions. These studies were continued later by The Western Brick Co., Danville, Ill., which developed a process of "inwardly expansive bloating."² The major purpose of the latter investigation was to produce back-up tile to compete with concrete blocks made from Haydite or cinder aggregate. Haydite is a light-weight aggregate formed by heating certain clays or shales rapidly in a rotary kiln. While the investigations at the C. F. Burgess Laboratories or at Western Brick Co. were not carried far enough to lead to the commercial production of material for the construction of walls, particularly outside walls, they showed that certain clays could be thermally expanded and that it was possible to produce a material of low permeability with a large percentage of the total voids or cells closed. commencing in 1939, the Ozark Chemical Co. sponsored a research program at Battelle Memorial Institute for the Purpose Of determining whether it is technically feasible to make thermally expanded building units, and specifically to get answers to the following questions:

Jan 1, 1942

By A. F. Henderson, C. F. Cornell, A. F. Dunyon, D. A. Dahlstrom

IN processing magnetic taconites several steps of crushing, grinding, classification, and magnetic separation are required to produce a 60' pct Fe concentrate. Usually the final concentrate is in a slurry form of 55 to 70 pct solids by weight and is further characterized by a particle size of 60+ pct —325 mesh. In taconite plants already completed or under construction the conventional method used to obtain pellets suitable for blast furnaces is to filter the concentrate slurry, ball the filter cake, and then harden the green pellets in a traveling grate or in a vertical shaft furnace. Large tonnages must be handled in minimum floor space, with reduced maintenance and lowest possible operating cost. Filtration must therefore achieve two objectives: I) high filtration rate—in terms of pounds of dry solids per hour per square foot of filtration area—at a low filtrate solids concentration, and 2) a filter cake moisture that will always permit efficient balling within the normal fluctuations of ' plant operating conditions. If moisture contents are too high, balling may be impossible or result in a mushy ball .without enough green strength for the firing operation. Development work has met these objectives. At low investment and operating costs, filtration rates of 250 to 600 dry lb per hr per ft2 have been attained for concentrates of 60' pct —325 mesh. By combining the disk-type continuous filter with proper agitation, the Agidisc filter produces a homogeneous filter cake, easily discharged from the disk sectors. This application provides the lowest initial cost per square foot of filtration area, minimizes floor space, reduces down time for changing filter media to a negligible factor, and simplifies process control and maintenance for the operator. It is now possible to predict very closely the taconite concentrate filtration rates for a wide variety of conditions—either by experience or with a few simple leaf tests. When balling and pelletizing operations began on a continuous basis, it became apparent that moisture content of the filter cake was a critical factor and must always be controlled by the filter operator below some maximum allowable value. Accordingly the Reserve Mining Co. and the Eimco Corp. joined in a study of the many variables affecting filter cake moisture content. The study was conducted at the Reserve Mining Co. taconite plant at Babbitt, Minn. To process plant tonnage the Babbitt plant utilizes a 6-ft diam Agidisc filter with six disks and an 8-ft diam drum filter with 10-ft face. However, most of the plant filter investigations were made on the Agidisc because of its superior performance. A considerable amount of small-scale test work was first carried out to study more closely the individual variables and ascertain their effect on filter cake moisture content. A general correlation method was then developed which allowed reasonable prediction of moisture content at any operating conditions. This step was made necessary by the fact that in full-scale filtering, operating variables usually interact to produce a combined rather than a singular effect. Studies were then made on the full-scale filters to prove the validity of the correlations developed, and past operating records were examined to ascertain whether or not significant variations could be traced to any single factor or to a combination of factors.

Jan 1, 1958

By E. E. Thurlow

The Geology Div. of Northern Pacific Railway Co. has adapted to its exploration efforts field procedures for geochemical sampling and semi-quantitative analysis which have been developed through research by the U. S. Geological Survey. The sampling is done in conjunction with reconnaissance geologic mapping on aerial photographs or during field checking of maps which have been prepared largely by photo-geologic interpretation. Stream sediment or soil samples are taken and readily soluble combined heavy metals are extracted with ammonium citrate followed by colorimetric titration with dithizone at the sample site. The effectiveness of this approach has been demonstrated both in positive and negative results, thereby assisting in the elimination of large areas of land from further immediate attention and in providing targets for followup exploration. An occa sional sample is submitted for spectrographic analysis as a check on the possible presence of other elements of economic significance. Field laboratory procedures are also being implemented for determining molybdenum, mercury, and other metals which may be valuable in themselves or useful as pathfinder elements in outlining mineralized areas. A lead-zinc occurrence in Oregon and a copper deposit in Montana were readily detected and outlined by stream sediment and soil sampling and a heavy metal anomaly that lacks obvious interpretation has been found in northwestern Montana. Detailed mapping and additional sampling are followed by other exploration techniques if warranted. Northern Pacific's program of reconnaissance mineral evaluation of company-owned lands and adjoining areas was outlined in a paper presented at the American Mining Congress meeting in Las Vegas four years ago. That report included policies and procedures with respect to mineral development on Railway Co. lands and may be referred to for information on these matters.1 In a sense this paper is a progress report on the use of geochemical prospecting in Northern Pacific's continuing mineral evaluation program. At this time there are positive results but as yet there is no real success story in the form of a minable ore body. GEOCHEMICAL PROSPECTING PROCEDURES The decision to use geochemistry as a reconnaissance exploration tool must be followed by research into sampling and analytical methods and into the interpretation of results. Various analytical methods were tried and evaluated by the Geology Div., including hot and cold acid extraction with and without fusion of the sample, panning and magnetic separation followed by dithizone testing of the magnetite, and cold aqueous extraction of metallic ions followed by indicator tests. Samples were first sent to the laboratory for analysis; later field laboratories were established and now virtually all testing is done at the sample site. It was concluded that, where applicable, the quickest dependable methods for reconnaissance use are the dithizone field tests for readily extractable heavy metals. This involves the simultaneous treatment of a sample, usually of soil or stream sediment, with two immiscible liquids; one a cold aqueous extractant (ammonium citrate) and the other a solution of dithizone in toluene or xylene.2 Dithizone is a colorimetric indicator that reacts quantitatively with copper, lead, zinc, and several other metals to form colored complexes in organic solvents. Results may be expressed in ml of 0.001 pct dithizone that are required to reach the blue end point, or calibration of the test results can be carried out with standard solutions of zinc; conversion factors would then be expressed in ppm, zinc equivalent. Calibration of dithizone solution with zinc standards indicates that 1 ml of 0.001 pct dithizone is equivalent to approximately 0.25 ppm of zinc. An authoritative report on dithizone field tests authored by H. E. Hawkes in the June-July 1963 issue of Economic Geology* states "The appeal of these techniques has been the simplicity and speed of the determinations as compared with more tedious laboratory determinations of trace metals in weathered rocks, soils, or plant materials. This obvious appeal, however, has often been more than matched by misuse of the method in such a manner that the results are

Jan 1, 1964

By Edward B. Walker, Michel Grosmangin

The geological and economic conditions peculiar to the Greater Oficina area are presented to demonstrate the necessity of a low-cost, well-site method of distinguishing gas-bearing formations. The method of gas detection with the neutron log is briefly discussed and its limitations are explained. A new method is described which consists in running a second neutron log with a larger source-to-detector spacing. Field data indicate that under favorable conditions the larger spacing response is proportionately more influenced by the virgin gas zone than is the shorter spacing response. One important condition is that the gas sands be invaded, with a diameter of invasion equal to about two to three times the hole diameter. The calibration of the longer spacing log is made so that the two logs read the same deflection in shale and in a known water or oil sand. Under such conditions, gas is indicated by a positive separation, i.e., the curve for the longer device is displaced to the right of the curve for the shorter device. Because of the non-linearity of the long spacing response, low porosity formations also show positive separations. In sands with large porosity variations, the gas sands can no longer he located visually. They can be detected on a plot of shorter spacing vs longer spac-ing deflections. INTRODUCTION In the Greater Oficina area of Eastern Venezuela, the rapid and accurate detection of gas from well logs is of primary importance because of a combination of economic, geologic, and operational conditions. Briefly, these conditions are: economic—there is no market for gas at the present time; geologic—a single well may contain as many as 30 or more oil or gas sands for which intervals -to be tested must be selected; opera-tional—first, once opened to the casing through perforations, gas sands are extremely difficult and expensive to squeeze off, and second, gas detection must be rapid because the geologist must decide immediately, at the well, which sand to perforate. During the early period of exploitation in Greater Ofi-cina, when clay base muds were used, sidewall samples, together with electric logs, gave fairly good distinction between oil and gas sands. When exploitation became concentrated on deep fields of poorer sidewall sample recovery, and after the advent of oil emulsion muds, now the standard drilling fluid in Greater Oficina, the regular neutron log became the most reliable indicator of gas. In 1953, R. Norelius devised the dual-spacing neutron technique for gas detection. The dual-spacing neutron log has proved to be highly successful in detecting gas and has been adopted as a regular survey by all of the oil companies of the area. Several hundred dual-spacing neutron logs have been run in Eastern Venezuela and several tests per well are available for positive evaluation of the logs. The findings outlined below are based upon this extensive field experience. GEOLOGICAL CONDITIONS OF THE GREATER OFICINA AREA The Greater Oficina area lies on the south flank of the Eastern Venezuela Basin (Fig. 1). Nearly all accumulations of oil and gas in the area are trapped, in whole or in part, against normal faults. All known oil and gas reservoirs in Greater Oficina occur in the Ofi-cina formation (Miocene-Oligocene) or in the "U" sands. The U sands are the lithologic equivalent of the Merecure group (Otigocene-Eocene), which contains oil in many fields north of Greater Oficina. Most of the petroleum produced in Eastern Venezuela is from the Oficina formation.

Jan 1, 1958

By James H. Courtright, Kenyon Richard

L. H. Hart (Chief Geologist, American Smelting & Refining Co.)— Because of a widely recognized association between breccia pipes of one form or another and many important copper deposits, conditions under which breccia pipes develop have been of great scientific interest for many years. Since these phenomena first attracted attention, many theories have been advanced to explain their origin. This is not unexpected, since it is likely that they have been formed by and under a wide range of conditions. Moreover, the entire subject is confused by the fact that the term brec-cia pipe is applied to a wide variety of occurrences. To discuss any part of the subject intelligently, therefore, it is necessary to start with definitions of the terms used. In their discussion of the Toquepala deposit, Richard and Courtright have carefully defined the terms they have used in their presentation of a very logical geological history of Toquepala breccias. This is a real contribution, as there is no reference in the literature known to the writer where the history of a series of breccia pipe epochs, confined essentially within one channelway, may be read with the degree of certainty that appears to be possible at Toquepala. Although the following comments are intended primarily to emphasize points brought out in the article by Richard and Courtright, certan subsequent detailed mapping by Hollister and Houston7 within the main central mineralized area of the Toquepala deposits not only supports most of Richard's and Courtright's con- clusions but also contributes additional facts that strengthen and broaden the whole concept of the origin of the Toquepala breccia pipes. In detailed mapping by Hollister and Houston,' the most significant feature disclosed is a well developed system of concentric fracturing in rocks peripheral to the main breccia pipe throughout an arc of 300°, interrupted only by the late dacite agglomerate in the north quadrant. Although Richard and Courtright noted that such fractures were developed in the southern and southeastern areas, continuity in the east and west quadrants is established by consistent orientation of the stronger set of fractures and joints. The existence of these structural weakness trends is emphasized by the emplacement of dike-like phenomena in and along members of this fracture system. Richard and Courtright described one of these dikes in the southeast quadrant. They referred to it as a ring-dike, composed of dacite porphyry. This suggests an apparent structural control of at least a part of the dacite porphyry intrusion by features related to the Toquepala breccia pipe center. This raises a perplexing question, since the dacite porphyry intrusion had been presumed to antedate breccia pipe activity. However, if this ring-dike is related to the breccia pipe center, it may indicate that some part of the dacite porphyry intrusion advanced in a manner resulting in an intensely localized stress center, which produced the concentrically arranged fracture system. The ring-dike would then appear to be evidence strongly sug-

Jan 1, 1959

By J. K. Kerver, J. S. Osoba, J. G. Richardson, P. M. Blair, J. A. Hafford

This paper presents the results of laboratory measurements of relative permeabilities to oil and gas on small core samples of reservoir rock by five methods, and describes the influences of such factors as boundary effect, hysteresis, and rate upon these measurements. The five methods used were the "Penn State," the "single core dynamic," the "gas drive," the "stationary liquid," and the "Hassler" techniques. In those methods in which the results are subject to error hecause of the boundary effect, the error may be minimized hy the use of high rates of flow. In order to avoid complexities introduced by hysteresis, it is necessary to approach each saturation unidirectionally. Observed deviations of relative permeabilities with rate can be explained as a manifestation of the boundary effect, and disappear as the boundary effect vanishes. The results indicate that all five methods yield essentially the same relative permeabilities to gas. Of the four methods applicable to the determination of relative permeability to oil, three, the Penn State, single core dynamic, and gas drive, gave relative permeabilities to oil which were in close agreement. The Hassler method gave relative permeabilities to oil which were consistently lower than the results obtained by the other methods. INTRODUCTION The relationship between the effective permeability of a reservoir rock to each of the fluids flowing through it and the corresponding fluid saturation is an important characteristic of the reservoir rock. Knowledge of this characteristic is and gas reservoirs and of the ultimate recovery to be expected extremely important in the prediction of the behavior of oil under various operating conditions. These effective permeabilities are usually expressed as the "relative permeability" to a fluid phase, defined as the ratio of the effective permeability to the permeability of the rock to a single phase at 100 per cent saturation. Relative permeability-saturation relations are not the same for all kinds of reservoir rock, but may vary from formation to formation, and within the different portions of a heterogeneous formation. In studying the performance of a specific reservoir, it is necessary, then, that the relative permeability characteristics of the individual portions of the reservoir be measured. These measurements may be made in the laboratory on small core samples from the reservoir. Various techniques have been proposed for the measurement in the laboratory of relative permeability-saturation relations. In varying degree, difficulties attend the use of all of the methods which have been proposed. It is the purpose of this paper to discuss the factors which influence the measurement of relative permeability, the difficulties encountered in several methods, and to present comparative results obtained by the use of various techniques. FACTORS WHICH INFLUENCE THE MEASUREMENT OF RELATIVE PERMEABILITY It is necessary that the relative permeability data measured in the laboratory yield the same relative permeability-saturation relationships that would govern the flow of fluids through the sample if it were to occupy its original position in the reservoir. Since the core sample upon which the laboratory measurements are made is not surrounded by similar core material as it was in the reservoir, an error in measuring the relative permeabilities may arise from the "boundary effect" which results from a discontinuity in capillary properties of the system at the effluent end of the core. Again, the rates of

Jan 1, 1951

By Ihor A. Kunasz

Lithium minerals occur predominantly in pegmatites which contain mineral assemblages derived from the crystallization of postmagmatic fluids or from the metasomatic action by residual pegmatitic fluids. They have been the traditional sources of raw materials for ceramic and chemical industries. However, with the discovery of Searles Lake, brines became new sources of lithium. Indeed, the 1960s may well be referred to as the "brine decade" because several brine bodies of significant economic importance were discovered. In the United States, the brines of Clayton Valley, Nevada, presently exploited by Foote Mineral Co., and the Great Salt Lake of Utah, to be exploited by the Great Salt Lake Chemicals Corp., have been defined as major sources of lithium. Also a lithium-bearing brine has been discovered in Chile. Following the termination of the AEC purchase program in 1959, several companies such as Maywood Chemical Co., American Lithium Chemicals, and Quebec Lithium Corp. were forced to close down their operations. Nevertheless, with the development of new applications in glass ceramics, air conditioning systems, synthetic rubber, and metallurgy (aluminum potlines), the lithium industry grew steadily, and with the potential application of lithium metal in batteries and nuclear reactors, a healthy growth can be foreseen. New products and new applications are likely to stimulate exploration for expanded reserves as well as the search for new sources from which lithium could be extracted economically. Geochemistry of Lithium Lithium is the third element in the periodic table. It is the lightest of all the metals, having an atomic weight of 6.938. Its ionic radius is 0.60A and its charge is + 1. The geochemistry of lithium has been extensively studied and has been summarized by Rankama and Sahama (1950), Goldschmidt (1937), and Hortsman (1957). The distribution of lithium in igneous rocks is controlled by its size and its charge, and by the (MgO+FeO)/Li2O ratio. In the early stages of crystallization of a magma, that ratio is very large. Consequently, both magnesium and iron are removed by ferromagnesian minerals in preference to lithium which is then concentrated in the residual magma. This results in an enrichment of lithium in silicic rocks and pegmatites (Strock, 1936). Pegmatites are coarse-grained igneous rocks formed by the crystallization of postmagmatic fluids. Minerals within pegmatites may also form by metasomatism (Jahns. 1955). Genetically, the pegmatites are associated kith neigh- boring intrusives. Mineralogically, granitic pegmatites contain feldspar, quartz, and mica as the main constituents and a variety of exotic elements such as lithium, beryllium, tantalum, tin, and cesium, which may or may not occur in economically significant concentrations. Detailed studies by numerous investigators (Cameron et al., 1949, 1954; Hanley et al., 1950; Jahns, 1953, 1955; Page et al., 1953) indicate that pegmatites often exhibit an internal zonal arrangement, with each zone containing a specific suite of minerals. The lithium minerals are usually found in the intermediate zones, and although as many as 13 zones have been recognized by Cameron, a complete zonal arrangement is rarely found. Zoning of pegmatite bodies has also been observed on a regional basis. The regionally zoned pegmatite sequences exhibit mineral assemblages and complexity according to their respective distance from the granitic bodies to which they are genetically related (Mulligan, 1965). Lithium is also found in small proportions in a variety of rocks. The average lithium

Jan 1, 1975

By A. D. K. Laird, C. A. Johnson

Drag coefficients for a cylinder being towed through water at constant velocity and also at constant linear acceleration were measured. Drag coefficients for constant velocity towing showed reasonable agreement with previous results. The drag coefficients found for constant acceleration showed little correlation with either the magnitude of the acceleration or the value of the modulus AD/V2 and tended to be slightly lower than those for constant velocity. INTRODUCTION For the design of offshore structures, wave forces acting on immersed cylinders are of importance. Several investigations have been made of these forces and of how they can be predicted from wave theories. A paper by Crooke' summarizes much of the work already done. More recent research by the Wave Research Laboratory at the University of California, Berkeley, has added much to the body of data collected under ocean wave conditions, but has not found a reliable method of force prediction from basic theories of wave motion. The present investigation is part of a long-range program to collect data with which to test current and future theories and correlations. The immediate objective was to measure drag forces on a circular cylinder subjected to linear accelerations over the range of Reynolds numbers between l04 and 105 where the drag coefficient was a constant for constant velocities. In particular, the effect of constant acceleration from rest and from uniform motion was to be investigated. The effect of acceleration may be evaluated in terms of drag coefficients. A useful resistance coefficient, C, is defined by the equation for total drag force, D, exerted by the fluid on the cylinder. DT =CSp V2/2.........(1) The coefficient C may be plotted as a function of the parameter AD/V2. Here D is the diameter and S is the projected area of the cylinder. The acceleration and velocity are A and V. The mass density of the fluid is p. An alternate drag coefficient, C, corresponds to the total force of the fluid opposing the motion minus the virtual mass force. This drag coefficient, arising from the velocity of the fluid, may be compared with that for the same cylinder in uniform motion. The similarities and differences between this coefficient as calculated for accelerated and for steady motion are of interest in the inverse process of predicting drag forces on cylinders under arbitrary conditions. One serious difficulty in this method is the specification of the virtual mass which depends also on the flow picture about the cylinder.1 EXPERIMENTAL EQUIPMENT The experiment was performed in the combination wave and towing tank at the Engineering Field Station of the University of California. The tank is 200 ft long, 8 ft wide, and 6 ft deep. The tow carriage is externally propelled by a cable, and the velocity of the carriage is maintained essentially constant by means of an am-plidyne. For the purpose of the present investigation, the speed control of the amplidyne was modified by inserting a linear speed control rheostat, which was rotated at a constant speed by a small d-c motor equipped with a slip-clutch. Accelerations which were constant over a reasonable length of time were thus produced. The magnitude of the acceleration depended upon the speed of the d-c motor and the limiting speed of the carriage. Data were obtained for a range of accelerations of 2 to 10 ft/sec,2 and a range of velocities of 2 to 15 ft/sec. An accelerometer (Statham Type C-2-350) with a range of ±2g was attached to the carriage and connected to a Brush analyzer and penmotor. A continuous coil of wire with 10 turns/ft wound around a fixed wooden form extending for a distance of 40 ft along the length of the tank was connected by an electrical contact mounted on the carriage to a Brush analyzer and penmotor, to give the time-position history for each run. The test cylinder was machined from solid aluminum alloy, 17-ST. to a diameter of 1.250 in., and could be

Jan 1, 1957

By F. H. Buttner, E. R. Funk, H. Udin

Gold wires, 5 mil in diam, are found to creep viscously up to approximately 5.5x106 dynes per sq cm around 1300°K. Beyond this point, an additional slip mechanism appears. The average coefficient in the viscous range at these temperatures is 18.9 ± 7x10 12 poises. This observation and other visual observations made during the experiments agree with Herring's predictions. EARLY creep studies by Chalmers on single crystals of tin produced some of the first experimental evidence to suggest that metals deform viscously under very light stresses. That is to say, over a small initial stress range up to 150 g per sq mm, the single crystals of tin elongated at a rate proportional to the stress. The proportionality constant between strain rate and stress is by definition the coefficient of viscosity. Chalmers named this range of proportionality the microcreep range. One of the first theoretical attempts to explain the microcreep phenomenon was given by Kauzman,' who applied Eyring'sQ eneral statistical mechanical theory of shear rates to creep data then available. From the rate theory, he deduced the general hyperbolic sine law for shear rate on the assumption that the distortion of the reaction path due to stress is negligible and that the system is an infinite continuum. In order to fit the available data to the equation, it was necessary to assume that creep occurs by shear of rather large blocks of material, rather than by an atomistic shear process as in diffusion. The size of the shear units was shown to increase with increasing temperatures and lower stress, or lower strain rates. In applying the hyperbolic sine law equation to the microcreep data of tin, it was shown by Kauzman that the unit shear blocks became quite small, which suggested to him that microcreep might be a self-diffusion process. Making this an assumption, Kauz- man reworked the rate theory and arrived at an equation where the shear rate is proportional to the stress. In the form of viscosity coefficient, the equation is: o- _ \LkT V = 2qAlA where u is the stress; S, the shear rate; X, the distance in shear direction moved by flow units relative to one another in the unit process; L, the distance between layers of units of flow; T, the absolute temperature; k, Boltzmann's constant; qAL, a constant proportional to the size of flow units; and kT A, the diffusion coefficient = ------kTe-Q/RT = K X2 h Kauzman applied the expression to molten lead with a fair degree of success, the calculated viscosity being low by a factor of four. For solid lead the result is 5000 times too high. Taking q = 1, and X = dA = L = 21 = nearest neighbor distance, Udin, Shaler and Wulff8 found the equation low by a factor of lo7 for solid copper. On the basis of the discrepancy in lead, Kauzman indicated that microcreep is probably not a simple diffusion process of molecular shear units, but one involving preferential diffusion paths, or even that diffusion in solids does not involve shear at all. Cottrell and Jaswon4 treat the microcreep phenomenon on the basis of slow moving dislocations and apply it to Chalmers' data on tin with fair success. Nabarro Suggested a microcreep model in which mass movement in the direction of pull is effected by the diffusion of holes. The tension on the crystal effectively creates a greater hole concentration at regions near the crystal surfaces perpendicular to

Jan 1, 1953

By G. Osuch, G. Derge, G. M. Pound

Using a new dternating-current potentiometer circuit and a specially designed four-terminal cell, the specific conductance of molten Cu2S-FeS mattes was measured as a function of temperature, from the liquidus to 1500°C, over the complete range of composition. The high conductivities, about 1500 ohm-I cm-l for FeS and 100 ohm-l cm-l for Cu,S, indicate that the conduction is electronic rather than ionic. Molten FeS has a negative temperature coefficient of specific conductance, resembling metallic conduction. Molten Cu,S has a positive temperature coefficient, resembling semiconduction. The binary roughly follows an additive rule of mixtures with respect to both magnitude and temperature coefficient of specific conductance. Metallic bonding in the liquid is postulated to explain these phenomena. MUCH has been learned in the past about the nature of liquids and the ionic or molecular species in solution by means of electrical measurements. Thus, dielectric constants','2 have given information about molecular liquids such as water and benzene. Measurements of dielectric constant usually are impossible in electrically conducting liquids, such as aqueous solutions of ionic salts and molten ionic salts. However, measurements of electrical conductance and ionic transference have provided much knowledge about the latter systems.a-" In recent years, the ionic nature of certain molten metallurgical slags has been established by Derge and Martin7 through electrical conductance and electrolysis measurements. Chipman, Inouye, and Tom-linsonq ave studied the electrical conductance of molten FeO and report a high specific conductance of about 200 ohm-' cm-' (compared with 4 ohm" cm-' for an ordinary ionic liquid such as molten NaCl) and a positive temperature coefficient of conductance. They interpret these results in terms of p-type semiconduction by analogy to the situation in solid FeO.Y imnad and Derge" have studied cell efficiency in the electrolysis of molten FeO-SiO, systems and conclude that ordinary ionic conductance increases with SiO, content. Very recently, interest has been revived in the electrical conductance of liquid metals and liquid metallic solutions. Scala and Robertson1' report a close resemblance between the liquid and solid states with respect to thermal, structural, and compositional relationships. Molten sulphides have not received a great deal of attention. Bornemann and von Rauschenplat" measured the specific conductance of molten Cu2S as a function of temperature with a four-terminal cell using direct current. A high specific conductance and a positive temperature coefficient were found in that investigation." Using a two-electrode apparatus, Savelsberg" electrolyzed various molten sulphide mixtures. He concluded that pure molten Cu,S and FeS were electronic conductors but that the mixtures exhibited some ionic conduction. In the present investigation, the specific conductance of the industrially important Cu-Fe sulphide mattes was measured as a function of temperature and composition in order to investigate the mode of electrical conduction and the structure of these molten mattes. An alternating-current circuit was used to eliminate the effect of any possible electrode reactions. Apparatus The Conductance Cell: Due to the high specific conductance of the systems studied (10' to 10" ohm-' cm-'), the classical two-terminal cell and Wheat-stone bridge apparatus could not be used. A four-terminal cell was developed in order to eliminate lead resistance, and an ac potentiometer circuit was designed to give rapid and sufficiently accurate measurements of the cell resistance. A diagram of the conductivity cell is given in Fig. 1. The molten matte is contained in a dense alundum crucible, and spectrographic graphite rods that dip into the molten matte serve as the four conductance terminals. Two of the graphite rods on opposite sides of the cell serve as current-carrying leads, and the other two graphite rods are null-current probes that detect the potential drop across the cell. These graphite rods are contained in silica tubes, and the lower constricted portions of the two silica tubes define the column of liquid whose electrical resistance is being measured. The electrical resistance of the broad ex-

Jan 1, 1956

By John D. Sullivan, Edwin J. Rogers, Chester R. Austin

The problem of making a building unit combining the necessary physical and mechanical properties and good thermal insulation has been foremost in the minds of architects and ceramic and construction engineers for many years. This paper presents the results of studies on thermally expanding shales or clays to produce lightweight cellular products suitable for making building units. An expanded clay block suitable for building purposes should be large enough qo that substantial savings may be effected in labor costs in laying the wall. The permeability should be low and it should have sufficiently good "dry-wall" characteristics to permit exposing the exterior surface to the elements, and to permit plastering directly the inside wall surface. The thermal conductivity should be low and the mechanical properties should be adequate. Obviously, a unit possessing satisfactory qualities for constructing an - outside wall would be satisfactory for interior walls and for back-up purposes. The results of studies on bloating various shales or clays† and the properties of the expanded products are reported. In another paper1 basic factors involved in bloating of clays are discussed. Manufacturers of ceramic products, partitularly structural clay, may encounter bloating of the ware during burning, and precautions must be followed to avoid this phenomenon. About 1927 the C. F. Burgess Laboratories, Madison, Wis., while carrying on an investigation for the American Face Brick Research Corporation, conceived the idea of intentionally bloating clay while holding it in a restrained condition, with the hope of producing a unitary cellular mass. Work was carried on until about 1931, when studies were terminated because of business conditions. These studies were continued later by The Western Brick Co., Danville, Ill., which developed a process of "inwardly expansive bloating."² The major purpose of the latter investigation was to produce back-up tile to compete with concrete blocks made from Haydite or cinder aggregate. Haydite is a light-weight aggregate formed by heating certain clays or shales rapidly in a rotary kiln. While the investigations at the C. F. Burgess Laboratories or at Western Brick Co. were not carried far enough to lead to the commercial production of material for the construction of walls, particularly outside walls, they showed that certain clays could be thermally expanded and that it was possible to produce a material of low permeability with a large percentage of the total voids or cells closed. commencing in 1939, the Ozark Chemical Co. sponsored a research program at Battelle Memorial Institute for the Purpose Of determining whether it is technically feasible to make thermally expanded building units, and specifically to get answers to the following questions:

Jan 1, 1942

By John Hower, Frank J. Markewicz, William Lodding

Greensand, greensand marl, and green earth are names given to sediments rich in the bluish green to greenish black mineral known as glauconite by the mineralogist. The word glauconite is from the Greek word glaukos, meaning bluish green. The term "greensand" as a rock name for a glauconite-bearing sediment is more appropriate than "greensand marl," a term that has been doggedly perpetuated in the literature. Because of its potash and phosphate content, greensand was dug and marketed as a fertilizer and soil conditioner for more than 100 years. The advent of prepared fertilizers with adjustable nutrient ratios led to the decline of greensand for agricultural application. The material has since been recognized for use in water treatment. Unfortunately, in spite of large reserves and worldwide distribution, the mineral has not been utilized to any significant commercial extent because no major application has been found for a substance with its chemical composition and properties. This lack is probably due to a paucity of research on its potential commercial application. Extraction of potash received considerable attention during and just after World War I. Because of relatively high extraction costs and generally low potash content (up to 8% ), glauconite lost its appeal as a source of this commodity. Historical Background Greensand was used as a fertilizer in New Jersey in the latter part of the 1700s. During the early 1800s its use became more common; applications of up to 100 tons per acre were sometimes made, although recommendations for agricultural use suggested 20 to 50 tons per acre (Tedrow, 1957). Many crops, especially the forage type, were said to improve with greensand application; however, because of, slow release of potash, large quantities were required. Certain greensands that contain sulfur and sulfide minerals are harmful to plant growth, and these were classified as "poison," "burning," or "black marls." The availability of higher-grade potash salts from other mineral sources, and the manufacture of prepared fertilizers, displaced the agricultural use of greensand during the later 1800s. During the mid-1800s the domestic greensand industry, centered in a small section of the eastern United States, grossed more than $500,000 per year. Toward the end of the century, annual production had dwindled to less than $100,000. By 1910 there were only six or eight greensand producers, grossing less than $5000 (Tyler, 1934). There was a small revival in the industry during World War I because of the curtailment of foreign potash, especially from Germany. During the later 1940s and early 1950s greensand was again recommended as a food nutrient for plants and farm crops. Agronomic studies discussed its potential as a soil additive that gradually releases potash and many trace-element nutrients essential for plant growth (Tedrow, 1957). Greensand was sold with the idea that it would condition soil and absorb and hold water while its base-exchange properties would release trace elements. For a short time glauconite was utilized in certain parts of New Jersey as a binding additive in the brick industry, and in the 1800s for making green glass (Cook, 1868). In the early 1900s the base-exchange property of glauconite was recognized for water treatment, and the mineral gained acceptance as a water softener. Mansfield (1922) does not mention base-exchange; however, the base ex-

Jan 1, 1983

By S. Ramachandran, R. G. Woolery

INTRODUCTION Union Carbide is currently operating an in-situ leach project on the Palangana Dome area in Duval county. This deposit meets all the requirements for in-situ leach in that the ore (1) is below the water table, (2) is in a permeable horizon, (3) is amenable to chemical leaching, and (4) is confined by impervious layers. This project has been under commercial production since 1976, and its capacity has been expanded on three occasions since going on-stream. Recently, additional uranium reserves were discovered on the Rogers-Cardenas (R-C) property about 32 km north of the Palangana operation. The ore is located within the Oakville sands and its characteristics are quite similar to those of the ore at Palangana. Both are an unconsolidated Arkosic sand high in clay and calcium carbonate. The R-C ore, however, is somewhat coarser with a mean particle size of 0.15 mm as compared to a mean particle size of 0.07 mm for the Palangana ore. In all respects it would appear that this ore would be a candidate for in-situ leach as a satellite operation to Palangana. Unfortunately, R-C ore is above the water table and, therefore, not amenable to the Palangana practice. Because of the limited known reserves in this deposit, it is readily apparent that conventional mining and milling are out of the question. However, because of its proximity to our Palangana operation, it seemed worthwhile to consider other options. The most viable route based on our past experience was to heap leach the ore. Our recent success at our Gas Hills facility and our Maybell operation, in employing a heap leach practice to our marginal reserves seemed to be a logical approach for processing this ore. Our experiences at both locations are described in "Heap Leaching - A Case History" by R. G. Woolery et al., Mining Engineering, March 1978. In both instances the process is an acid leach circuit and acid consumption averages 20 kg/t H2SO4. A preliminary feasibility study showed that because of the high strip ratio required for the R-C project to be successful, additional ore reserves must be located and that a method of heap leaching with an alkaline circuit would have to be developed. As a result of this paper study, the decision was made to proceed with a program of additional exploration drilling to determine the total ore reserves that could be mined economically. The Mining Department will evaluate each ore zone for cutoff grade, strip ratio, and expected mining cost. At the same time, a laboratory program to evaluate the available core samples for amenability to heap leaching with respect to an estimate of uranium recovery and processing costs was developed. This program is currently in progress, and at this time, we are just completing our process amenability study. BENCH-SCALE EVALUATION OF THE R-C ORE The initial bench-scale slurry leach tests on the R-C ore showed an acid consumption in excess of 200 kg/t H2SO4. These data, of course, discouraged us from considering this process route. Not only would the acid cost be prohibitive, but the gypsum generated by the reaction of the sulfuric acid with the calcium carbonate of the ore would severely effect the percolation of the lixivant. For this reason, the laboratory program was directed toward an alkaline circuit compatible with heap leaching. Because of the proximity of the R-C property to our Palangana operation, it seemed advisable to integrate the processing of this ore into the production at Palangana. Doing so would enable us to bring the R-C property into production by merely enlarging our present facilities at Palangana; otherwise, construction of a grass roots plant would be necessary. Ideally, the simplest method would be to construct the heaps at Palangana and employ an ammonium carbonate/bicarbonate leachant compatible with the in-situ production liquor. The product liquors could then be co-mingled or processed separately as desired. To determine if this goal was practical, samples of the R-C ore were obtained, and a laboratory program initiated. Heap leach amenability testing consisted of preliminary bench-scale evaluation to determine optimum solution strength and ultimate uranium recovery, followed by small column tests to confirm the bench-scale metallurgy and to determine percolation characteristics. These bench-scale tests are being followed by pilot-scale testing approximating field conditions. As expected, the bench-scale tests showed that the dissolution rate is considerably slower for alkaline leach than has been our experience in acid leaching. Because of the slower reaction rates, product liquor grades will be lower than for acid, as greater volumes of solution are required for satisfactory uranium extractions. The greatest influence on reaction times found in the laboratory was the carbonate/bicarbonate strength and oxidant addition. However, the higher salt concentration reduced the efficiency of the IX resin circuit and about 25g/L salt proved to an upper limit compatible with subsequent IX treatment. The oxidant contributed significantly to the early extraction rate but seemed to have only minimal effect on the total practical U308 extracted or the time required to achieve it. This variable will require larger scale testing to determine if the added cost of the oxidant is actually justifiable. Thus, the small-scale laboratory slurry tests, based on the 0.088% U308 sample available, indicate that leaching at 25g/L ammonium carbonate/bicarbonate, with or without oxidant, we might expect an 80-85% U308 extraction on this ore.

Jan 1, 1979

By B. H. Sage, W. N. Lacey

The growing background of experimental information concerning the volumetric and phase behavior of binary and ternary hydrocarbon systems is used as the basis for a comparison of these systems with naturally occurring hydrocarbon mixtures under conditions representative of underground petroleum reservoirs. The qualitative and semiquantitative similarities and differences between the two types of systems are considered in reference to the possibilities and limitations of using experimental data on binary and ternary systems for predicting the volumetric and phase behavior of naturally occurring hydrocarbon mixtures of low molecular weight. The possible influence on such phase behavior of water, hydrogen sulphide, nitrogen, and components of relatively high molecular weight is discussed. INTRODUCTION During the past two decades much effort has been devoted to the study of the volumetric and phase behavior of pure paraffin hydrocarbons and of binary and ternary mixtures of these compounds. Many of these studies were carried out with the direct objective of utilizing a knowledge of the detailed characteristics of binary and ternary mixtures of the lighter paraffin hydrocarbons for predicting the behavior of more complex mixtures. The ability to make such predictions with accuracy would be of great value in petroleum production and refining. Although the behavior of the methane-propane system' served at one time as a qualitative illustration of the probable characteristics of the more complex hydrocarbon mixtures found in nature, it' fell far short of requirements for quantitative predictions. The present paper endeavors to indicate the relation of the more recently accumulated information concerning the behavior of binary and ternary hydrocarbons to this problem. In discussing binary and ternary systems as examples pointing toward the behavior of multi-component systems no effort is made to present new methods of predicting the characteristics of natural hydrocarbon mixtures. Preliminary proposals have been made elsewhere for the prediction of volumetric phase equilibrium and thermodynamic data for multicomponent mixtures, utilizing as a basis the behavior of binary and ternary systems. Numerous other proposals have been made. That based upon the concept of a pseudo-critical state" has proved to be of value to the petroleum industry. Concurrently with this study of binary and ternary systems investigations have been made of natural hydrocarbon systems. Of the many publications reporting such experimental information only a few examples will be mentioned. A number of studies of black oil and natural gas have been made and much attention has been directed to extended and detailed investigations of the behavior of fluids in condensate fieldS 16,17,18,19,20. This work has been supplemented by some studies of the separation of bitumen from natural hydrocarbon liquids The over-all behavior of such systems has been used in predicting the volumetric and phase behavior of naturally occurring mixtures This background of experimental and correlated information concerning the behavior of multicomponent hydrocarbon systems also permits a direct comparison of the characteristics of binary and ternary aliphatic systems with those materials produced from underground reservoirs. PRESENTATION OF DATA The primary limitation encountered in using binary and ternary aliphatic hydrocarbon mixtures as examples of the characteristics of the fluids encountered in underground reservoirs lies in the existing lack of knowledge of the quantitative effect upon behavior of the presence of several important constituents, notably hydrocarbons of high molecular weight, water, carbon dioxide, hydrogen sulphide, and nitrogen. The presence of substantial quantities of hydrocarbons of fairly high molecular weight serves to increase the complexity of the phase behavior of natural systems. No simple systems yet studied give adequate guidance in this regard. The influence of such materials of high molecular weight was indicated earlier",?' to an extent which serves to show that definite limitations now exist in the correlation of simple and complex systems. However, significant progress is being made in filling gaps in the information. For example, similarities in the behavior of fluids in condensate fields with that of binary and ternary systems are becoming more systematically evident. A few studies of the behavior of water in paraffin hydrocarbon systems have been made Results of investigations of mixtures of carbon dioxide and the lighter hydrocarbons also are available Limited work has been reported con-

Jan 1, 1949