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By K. Leutwyler

The key to realistic casing stress analysis in thermal recovery installations is accurate knowledge of the temperatures involved. Much information leading to prediction of heat losses from tubing string to wellbore has been published. This .same information permits calculation of casing temperature under certain conditions. This paper reviews the basis for most of the published work, the line source solution to the diflusivity equation and examines some of its application criteria in the light of unsteady-state conditions. An alternate finite differences method is presented for correlation, and experimental data pertaining to the heat transfer mechanism in the annulus is reported. In the light of the information presented in the paper, it appears that the assumption of a line source for the tubing-wellbore system is valid even for reasonably short periods of heat flow, .such as "steam soak" operations. The empirically modified equation presented earlier matches computer derived results of the finite differences approach lor periods as short as 50 hours. Previously predicted cas ing temperatures and the associated stress levels are thus verified based on these correlative computations and the reported experimental information. Fall out from the computer output resulting in some studies of the influence of insulating cement properties on casing temperature, and experimentally studied effects of nitrogen placed in the annulus at various pressures., are described. INTRODUCTION Generally speaking, predictions of average casing temperatures have been based on an idealized model involving a centralized tubing string at uniform constant temperature radiating energy towards the casing under steady-state conditions.'. ' Heat is transferred away from the casing to the formation by unsteady-state conduction across thermal barriers consisting of cement and the mud sheath. Heat balances written on the casing permit prediction of instantaneous casing temperatures. During early periods of injection, casing temperature varies appreciably as a function of time; however, for long injection times this variation decays as heat flow from the wellbore to the formation stabilizes, and it becomes virtually negligible as conditions surrounding the wellbore become quasi-steady-state (Fig. 1). Carslaw and Jaeger -escribe a solution to the diffusivity equation for a line source (Fig. 2). A constant supply of heat is introduced into the medium from the line placed into the origin of the x-y coordinate system and parallel to the z-axis. Heat spreads outward in the infinite cylindrical solid and the temperature increase on a line going through point (x, y) parallel to the z-axis at a distance r can be predicted by: The following criterion must be considered: the Carslaw and Jaeger equation is obtained on the basis of a large

Jan 1, 1967

Jan 1, 1970

By R. F. Nielsen, R. G. Bentsen

Jan 1, 1966

By O. U. Bradley

THE extent of losses, due to evaporation, sediment, and water, in crude oil stored in steel tanks, is a very interesting question, and particularly so at this time, when every reasonable measure should be employed to eliminate all possible losses of this important natural product. Available information on this subject is incomplete; e.g., during the development of the Cushing Field, considerable surplus oil was stored in steel tanks, but from time to time, owing to changes in weather, somelosses by evaporation and short storage room on the leases, these tanks were topped out, thus rendering inaccurate any system designed to determine the average rate of evaporation or other losses of the oil over a given period. , Furthermore, the losses, as shown by the records at the time, as a result of hasty gages, failed to take into account the temperature and gravity of the oil. Losses may be classified roughly as occurring from evaporation, presence of sediment and water, and leakage. The coefficient of expansion and contraction of crude oil, in relation to temperature conditions, is of material importance; also, the rate of evaporation is dependent upon the gravity of the oil, as the escape of the lighter hydrocarbons in fresh Cushing oil, of from 40 to 42 gravity, on a warm day is considerable, and from available records of temporary storage, it is safe to assume that a loss of 1 to 13 per cent. in volume will easily occur in light crude oil of Cushing grade over a period of. 6 months, including the summer season. The presence of sediment, water, and other impurities, in the oil will also cause, more or less deterioration in quality, particularly when the fresh production is run direct from the. gage tanks, or from the wells on the lease to steel storage, as is often the case when an oil field is being rapidly developed. The bad oil will settle to the bottom of the tanks and may be determined by thiefing and running a centrifuge test on the sample. The amount of water in the oil depends entirely on the conditions under which it is produced. Sometimes in large producing wells, with heavy gas pressure, some water may come in with the oil, particularly if the well has been drilled to the top of a water sand. Under these conditions, cut oil is often produced, which, if not settled out, is carried over into the steel tanks.

Jan 7, 1918

By C. S. Samis, D. P. Seraphim

In the presence of oxygen, galena is oxidized in an aqueous medium containing ammonium acetate in accordance with the following reaction: PbS + 1/2 0, + 2 NH~Ac -» PbAc, + So + 2 NH: + H2O. This reaction was studied in an autoclave under oxygen pressure by polarographic measurement of the concentration of lead ion in solution. Oxidation rate is parabolic. The reaction products are lead acetote and elemental sulfur, the latter forming a film on the galena crystal. Reaction kinetics appear to be determined by the diffusion of lead from the galena phase to the solution interface through the film of sulfur. RECENT applications of pressure leaching on a commercial scale have emphasized the metallurgical importance of the oxidation of sulfide minerals in aqueous media by oxygen under pressure. Research experience has shown that sulfates, thio-nates, and metal oxides are the products of humid oxidation of sulfide minerals in basic solutions. The metal oxides may be solubilized in the presence of a complexing ion.' Certain oxide minerals are also amenable to treatment by this type of oxidation.' Several kinetic studies have been made of reactions of this type. Stenhouse' found that pyrite (FeS?) oxidized in a sodium hydroxide solution to produce a soluble sulfate and an insoluble layer of iron oxide and that the kinetics of the reaction were controlled by oxygen diffusion through the oxide layer. Andersen' studied the oxidation of galena (PbS) in a sodium hydroxide solution under oxygen pressure. He found the lead and sulfur to be simultaneously oxidized to produce plum bite ions and sulfate ions, and that the reaction rate was proportional to the surface area of the galena. The kinetics appeared to be determined by the reaction of oxygen and water with the galena surface. In each of the above reactions the metal and sulfur components of the mineral were oxidized simultaneously and at equal rates. In the present study the alkaline medium has been replaced by an approximately neutral solution of ammonium acetate in which lead sulfate is soluble. Under the conditions no sulfate was produced and no sulfur could be detected in the solution. The metal component of the mineral was solubilized and the liberated sulfur remained as a film of elemental sulfur on the surface of the galena crystal. A kinetic study of this reaction was undertaken to establish the kinetic mechanism and to determine the rate controlling step. Specific reaction rates were determined by oxidizing crystals of galena of measured surface areas in an autoclave maintained at the desired temperature and oxygen pressure. The rate of reaction was followed by measuring the concentration of lead in the ammonium acetate solution with a cathode ray polarograph, employing stationary platinum electrodes incorporated in the autoclave. Experimental Materials and Equipment Crystals of galena obtained from Violamac Mines, Retallack, B. C., were selected for oxidation because

Jan 1, 1957

By Edwin Higgins

SINCE the "Days of Forty-nine" California has been the premier gold producing state of the union. The greatest production was recorded in 1.852, during which year the state's placer and lode deposits yielded over 81 millions. This peak was followed by a steady decline to about 12 millions during the years 1888 to 189.3, a period marked by the cessation of gravel mining. After 1893, production increased to a new peak of over 22 million in 1915, thereafter decreasing steadily to something over 13 million in 1923. Today; California's gold production shows a decrease of 84 per cent. as compared with the output of 1852, and a decrease of 41 per cent, as compared with 1915. It is not a difficult matter to find the causes of this more recent decline. In 1916 there began an upward swing in the cost of labor, which represents approximately 60 per cent. of the cost of mining, and in the price of supplies, representing the remaining, 40 per cent. This rise continued until 1922 and since that year there has been no decided tendency either upward or downward. The increase in the cost of mining since 1916 is variously estimated at from 50 to 75 per cent.; the price of gold has remained fixed at $20.67 per oz. This condition resulted in wiping out the profits of the low-grade operations which, in recent years, have constituted California's main source of supply of gold ore. It is now predicted that there will be renewed activity in California- gold mining. What are chances for the materialization of this forecast? A boom or even a revival of gold mining must of necessity be brought about or accompanied by one or more of the following factors: 1. A decrease in the cost of mining. 2. An increase in the price of gold. 3. New capital for development. 4. The discovery of new deposits. 5. The revival of hydraulic mining.

Jan 1, 1925

By R. M. Waterstrat

X-ray diffraction and metallographic examination of binary Mn-rich alloys with Ti revealed the presence of intermediate phases in this system. A binary R phase has been identified and also a phase having an a-Mn type structure. The X-ray pattern of the phase TiMn3 is presented and a tentative phase diagram for the Mn-rich portion of this binary system has been constndcted. MANGANESE-rich alloys with titanium have been subjected to thermal analysis at temperatures down to 1100°C by Hellawell and Hume-Rothery.1 Their results indicate the existence of an intermediate phase TiMn3 in this binary system. This phase appears to coexist with the Laves phase TiMn2, and with terminal solid solutions based on the allotropes of manganese, at least down to 1100°C. The above investigators did not attempt to determine the crystal structure of this phase, however. Since, by analogy to the binary systems Mn-V and Mn-Cr3 one might expect to find a phase in this region of the diagram, it seemed desirable to obtain X-ray diffraction patterns of alloys in the concentration range in question, in order to ascertain whether the sigma phase or related structures occur. EXPERIMENTAL PROCEDURES Alloys were prepared by arc-melting electrolytic manganese and iodide titanium in a water-cooled copper crucible under a helium atmosphere. Excess manganese was added to each melt in order to allow for losses incurred during melting. The alloys were then wrapped in molybdenum foil and sealed in evacuated quartz tubes for annealing at various temperatures, as shown in Table I, followed by quenching in cold water. Although the inside of the tubes showed evidence for some loss of manganese from the specimen during annealing, there was no evidence of any reaction between the specimen and either the molybdenum foil or the quartz tube at these temperatures. It was later found that the manganese loss was considerably reduced by annealing these alloys in sealed quartz tubes containing one atmosphere of purified argon. As an added precaution the surface of each specimen was ground off before crushing the alloys to -270 mesh powder, using a hardened steel mortar and pestle. X-ray powder patterns were obtained using either FeKa or CrKa radiation in an asymmetrical focusing camera, which gave excellent dispersion of the closely spaced lines. Pictures were also obtained using a Debye camera of 5-cm radius which provided data in the angular region not covered by the focusing camera. The alloy specimens were polished and examined metallographically, using an etchant consisting of 60 pct glycerine, 20 pct nitric acid, and 20 pct hydrofluoric acid. The 10-g buttons were in each case broken in half and found to be well-melted and free of any gross segregation. One half of certain alloy buttons was submitted to chemical analysis in the "as-cast" condition. No appreciable change in composition seemed to occur during annealing . RESULTS The X-ray pattern of alloy Ti1.17Mn0.83 was found to agree well with that of the ternary R phase which was first found in the Mo-Cr-Co system,' and re-

Jan 1, 1962

By J. W. Givens, P. B. Crawford

A potentiometric model study has been made of the effect of vertical fractures existing in the matrix of the reservoir on the flooding or cycling performance. Fractures can have unusual flow characteristics. Fluid entering one side of a fracture can emerge on either the same or opposite side of the fracture, depending on the particular streamline. Fracture orientation has a great influence on the sweep efficiency. However, sustained fluid injection may still permit large areas to be swept. INTRODUCTION One can find considerable information available in the literature on the effect of fractures originating at the wellbore on sweep efficiencies of water-flooding or gas cycling programs.1-5 However, there arc few, if any, quantitative data reported in the literature on the effect of vertical or horizontal fractures existing out in the reservoir matrix on secondary recovery performance. Several papers have been presented on the effect of vertical and horizontal fractures on the productivity or conductivity of waterflood and gas injection patterns, but in all cases the fractures initiated at the well and simulated commercial fractures.6,7 It is believed that natural fractures may exist out in the reservoir matrix and would effect the displacement performance. The purpose of this report was to study the effect of a few isolated vertical fractures existing out in the reservoir matrix on the performance of waterflood or gas injection patterns. DESCRIPTION AND EQUIPMENT Since the potentiometric model was described by Lee8 it has been widely used to study numerous types of fluid displacement problems. The potentio- metric model can be used for fluid displacement studies when the following assumptions are valid: (a) steady-state conditions exist; (b) the mobilicy ratio is one; and (c) the capillary and gravitational effects can be neglected. Five-spot and direct line drive square patterns were studied using a copper strip of the desired length and orientation to simulate a vertical fracture in the reservoir matrix. The 20 x 20-in. model was considered to represent only one element of an infinite array of similar patterns. DISCUSSION AND RESULTS FIVE-SPOT PATTERN — ONE FRACTURE BETWEEN INJECTION AND PRODUCING WELLS Fig. 1 shows a quadrant of a five-spot pattem with the vertical fracture existing out in the matrix along a line connecting the injection and producing wells. Length of the fracture was equal to 35.4 per cent of the distance between injection and producing wells. In this particular pattern it is noted that fluid breaks through from the injection well to the producing well when the dimensionless time is equivalent to 26.9. Dimensionless time is defined as volume of fluid injected divided by the volume of displaceable fluid in the pattem expressed as a per cent. The cross-hatched areas of this

Jan 1, 1967

By Daniel T. Brian, O&apos

Exploration targets and results in the mining industry are commonly summarized in terms of tonnage and grade. Business appraisals require, as additional information, the expected profit or loss implied by the physical summay. The early incorporation of knowledge gained through financial analysis computations can provide a means for economically resolving many common exploration and development problems. Examples of such applications from the activities of exploration planning, reconnaissance, land acquisition, and development planning are presented. While prospecting for mineral deposits, geologists are frequently asked what they hope to find or have found. The response is usually descriptive, such as "50 million tons of 1% copper," and the economic implications are deferred until a capital investment decision is required. At that time, a financial analysis integrating the four analysis components is completed. These components are: 1) Tonnage and Average grade above cutoff grade 2) Capital and operating costs 3) Product value 4) Appropriate profit or loss accounting Close examination of these components reveals that there is no intrinsic reason for avoiding financial analyses at earlier stages in exploration, as long as the uncertainty of the estimate is realized. Tonnage and average grades are commonly estimated at early stages in exploration. For this component, the appropriate cutoff is the major uncertainty. Capital and operating costs are difficult to estimate before detailed quantitative information is available, but estimates useful for the types of applications pertinent to earlier exploration stages are possible. Product value estimates may or may not be difficult, depending on the pricing structure of the particular commodity. A simplified accounting procedure usually may be adopted without introducing any significant loss of validity. This paper describe some of the financial analysis applications which are pertinent during mineral exploration and deposit development. These applications lend additional insight during exploration planning, land acquisition, physical exploration, and development. The examples are oriented toward a hypothetical management investment policy which is based on a single criterion, a minimum 15% discounted cash flow rate of return. In reality, managements use multiple criteria. This simplification is convenient for purposes of presentation and does not invalidate the examples. Computers are useful, but not a requirement, for the applications described. The use of computers provides the results on a more timely basis at costs lower than equivalent manual computations. UNDERLYING PRINCIPLES AND ANALYSIS METHODS Data estimates are subject to uncertainty. The analyst may choose to assess this uncertainty by using one of two principles. Each principle has some advantages. The principle most commonly employed is "assumed certainty." Each financial analysis is based on one set of selected data, which may represent the average estimates, minimum expected conditions, etc. The critical data is identified by making successive calculations, varying the values used. Such studies, called sensitivity analyses, isolate the economic effect of various uncertainties, and guide the allocation of future efforts toward improving the overall accuracy of the analysis. A second principle, "assumed risk," examines the interactive effect of the current uncertainties by qualitatively assigning probability distributions to each data element. These probability distributions indicate the currently appraised chance that a given numerical value will prove to be true. The corresponding procedure, risk analysis, consists of processing many individual financial analyses, each analysis being based on randomly selected numerical values from the probabilistic distributions. The result is a numerical presentation of the uncertainty, but care must be exercised in the interpretation of results. The advantage of this procedure is the direct measurement of economic uncertainty caused by the interaction of uncertain estimates. Kennecott Copper Corp. has developed computer systems for accomplishing sensitivity and risk analyses.

Jan 1, 1970

By G. Thodos, D. E. Matschke

Cansiderable time and effort frequently are expended to establish, with a degree of confidence, the PVT behavior of pure substances. In particular, a great deal of experimental information contributed by a number of investigators is available in the literature. The data of each investigator, although significant in themselves, cannot be used with a high degree of confidence until they are compared with the continuum of information presented by others. Current interest in thermodynamic and transport properties, for not only the gaseous state but the con-densed state as well, requires that PVT infarmation be presented for both regions. The density dependence on temperature and pressure, when presented as a continuum, is of considerable value in itself, especially since the available equations of state fail to properly account for the PVT behavior in the condensed state. For this reason and to incorporate PVT data recently presented in the literature, this investigation was carried out. In their studies concerned with the thermodynamic properties of methane, Matthews and Hurd in 1946 utilized the data of Kvalnes and Gaddy and Olds, Reamer, Sage and Lacey to establish the PVT behavim of methane in the superheated region and the saturated liquid densities of Keyes, Taylor and Smithl in conjunction with the Clapeyron equation to develop the densities for the saturated envelope. Current activity sponsored by API Project No. 44 under the direction of F. D. Rossini has led to a tabular presentation of compressibility factors for gaseous methane in the superheated region.la These values were obtained by using smoothed residuals, developed from experimental data and the Ben edict-Webb-Rubin equation,' to establish internally consistent compressibility factors for the real gas. This approach offers probably the most precise presentation of PVT information for gaseous methane to date. The PVT behavior of methane also can be represented accurately by equations of state such as the Benedict-Webb-Rubin equation or the Martin-Hoa equation.' These equations, although valuable for analytically representing the PVT behavior, lack precision in the compressed-liquid region. The PVT data available in the literature for methane were utilized to obtain reduced densities that are presented in Figs. 1 and 2 as functions of reduced temperature with parameters of reduced pressure. The critical constants utilized for methane are those reported by Kobe and Lynn." These critical values, T, = 191.1°K, PC = 45.8 atm and p, = 0.162 gm/cc, produce a critical compressibility factor, z, = 0.289. The PVT information, as obtained from the literature, in many instances was not presented in an immediately

By George M. Fowler

EVERY year it becomes more difficult to find new mining districts and new ore deposits. Nearly all of the important discoveries so far can be attributed to surface manifestations overlying the ore deposit. In the future greater skill will be necessary to find ore deposits that give little or no indication of their presence. Mining geology is making progress by broadening its attack upon mineralized regions, by including in its investigations studies of the relation of physical-chemical processes to ore precipitation and various phenomena that heretofore have not always been looked upon as major factors in the problems. Such, for example, are petrographic peculiarities that will help determine structure, aspects of strata or formations favorable or unfavorable to structural deformation or mineralization, and renewed studies of chert and dolomite. This broadening attack is not necessarily being directed to the study of large areas, but rather by doing extremely detailed work in three dimensions in relatively small critical areas to find the key to the structure, reasons for the manner of rock deformation, composition and texture of the rock, and other con¬trolling factors in the larger areas.

Jan 1, 1935

By Chung Yu, Wang

CHINA can he roughly divided into three metallogenetic province: North China, the Yangtze Valley, and South China. In North China the old Pre-Cambrian schists and gneisses are represented by the abundance of quartz mines in which sporadic occurrences of copper, lead, zinc, gold, and silver are sometimes found in subordinate quantities. Along the Yangtze Valley and in Central China, extending eastward as far as Shantung, are found here and there intrusions of dioritic rocks, in which occur the famous contact deposits of iron ore, besides which minor quantities of copper. lead, and zinc are also found. In South China the igneous intrunsions are of granitoid type in which, or in the vicinity of which, occur in certain regions immense deposits of antimony, tungsten, tin, and mercury. Broadly speaking. most of the famous coal mines are now situated in regions north of the Yangtze River, in which occur also the sedimentary deposits of iron in contradistinction to the contact deposits of iron along the Yangtze Valley.

Jan 1, 1943

By James C. M. Li, J. Weertman

James C. M. Li (United States Steel Covp.)—The author has discovered a single analytical relation between the minimum, or the steady-state, creep rate and the applied stress confirming a statement made earlier by orn" that such relation should exist and should reduce to the power law at low-stress levels and to the exponential law at high-stress levels. However, as pointed out by the author, all the available theories of creep are not adequate to explain such a single relation. Inspired by such a statement, I have made a suggestion concerning a possible explanation13 of the new relation. This is based on the concept that the rate-controlling step is the cooperative motion of a short dislocation segment. The nature of and the reason for the cooperation have been discussed13 as well as the reason why the motion of the dislocation could be controlled by the mobility of the short segments. A natural short segment has been proposed13 to be the node formed at the intersection of two dislocations. The reason why the node may contain only a few atoms has not been discussed and the application of the proposed model to all the metals and alloys reported in this paper has not been attempted. It seems appropriate to include these in this discussion. The model was partly inspired by the substructure recently observed in the electron microscope on creep specimens. One such example is shown in Fig. 48 in Darken's Campbell Memorial Lecture. The substructure is a collection of dislocation intersections and irregular networks. No pileups have ever been observed in such specimens. A closer look at the network indicates that one set of dislocations is more straight than the other set sug- gesting that the other set may be mobile in the plane of the net. Since, for the network to survive the creep deformation, some dislocation reaction has to take place at the intersection of the two sets of dislocations, the mobile dislocation, even if it can slip in the plane of the net, will have difficulty in moving at these intersections. To illustrate, an idealized network is shown in Fig. 9. The thin lines represent the set of dislocations which are mobile and can slip in the plane of the net except at the nodes which are formed at the intersection of the two sets of dislocations. The other set of dislocations, represented by the thick lines, may have a Burgers vector which is not parallel to the plane of the net, and therefore may be immobile. Because of this nonparallel Burgers vector, the Burgers vector of the node, which is avectorial sum of the Burgers vectors of the two sets of dislocations, will also be nonparallel to the plane of the net. Therefore, the node cannot slip in the plane of the net and the set of mobile dislocations will have to drag the node along as indicated in Fig. 9. Now the problem is how many atoms could be involved in the nodes. Exact calculation of the length of the node is a difficult task especially since the length should be a steady-state length and not an equilibrium length. An estimate of the equilibrium length can be made by balancing the line tension of all the dislocations. The results would be a small fraction of the length 1 between nodes as shown in Fig. 10. In some instances such a calculation shows that the node will not be formed. But, since the calculation is only approximate, it does not rule out the possibility of the formation of a short node. In other instances the equilibrium length of the node is an appreciable fraction of I. Such a node would

Jan 1, 1963

By L. Moyd, P. Moyd

The first commercially available portable gamma ray-neutron beryllium detector, the Rerylometer, was developed by the same group that developed the first practical portable scintillation counter, the Scintillo-meter. This group includes Professor George Brownell, of the Geology Department of the University of Manitoba in winnipeg, and his associates, K. I. Roulston, R. w. Pringle, and R. L. Funt, of the Physics and Engineering Departments of the University of Manitoba. A prototype model was tested in the field by Dr. Brownell during the summer of 1958. Commercial production was undertaken shortly thereafter by Nuclear Enterprises Ltd., of Winnipeg, and a license for manufacture and distribution in the U.S. was granted to Isotopes Specialties Co., of Burbank, California, a division of Nuclear Corporation of America. Early in 1959, we were retained by the 'Mining Division of Minerva Oil Co. to Legin a search throughout North America for minable deposits of beryllium, and to train members of their permanent staff to continue the program. The project included literature sur-veys, interviews with members of various federal, state, and provincial agencies, scanning of our own collection of suites of specimens from various mineral occurrences, and the examination of deposits in the field. The value of a beryllium detector to this program was obvious and arrangements were made to procure one as soon as possible, which resulted in our obtaining and using the first instrument that was produced commercially in the U. S. In addition to the commercially available Berylometer, Mr. William Vaughan and his associates, of the U. S. Geological Survey Geophysics Division, in Denver, have developed and tested several experimental instruments based on the same principles. DETECTOR Principles The detection of beryllium is based on the fact that "hard" gamma rays (1.6 MEV and geater), such as those produced by Antimony convert ordinary beryllium (Be9) to Be8 , with the release of a neutron. The neutrons are counted by a scintillator designed to favor neutron responses while suppressing those of gamma rays. 'The instrument is completely selective for beryllium. No other element can interfere. Instrunlentation The Rerylometer itself, which is cylindrical, is about 8 inches in diameter, 13 inches high, and weighs about 11 pounds. (Figs. 1, 2). The principal components include: 1. A disc of wax to moderate (or "thermalize") neutrons. 2. A boron-enriched polyester-zinc-sulphide fluorescent screen. This material produces strong flashes when struck by thermalized neutrons but only weak flashes from gamma rays. 3. A photomultiplier tube. 4. An electronic circuit, complete with one srnall 71/2-volt dry battery. The photomultiplier tube and electronic circuit convert neutron flashes to electrical impulses, but gamma ray effects are almost

Jan 1, 1961

By . M. Muskat

A THEORETICAL consideration of the mechanics of various water-flooding systems with the viewpoint of comparing their relative merits involves the study of two fundamental properties of such systems. On the one hand, it is important to determine the efficiency of the flood as measured by the percentage of the total area that is swept out by the encroaching water before water actually reaches the output wells. This is really a measure of the regional tendency of the water to "bypass" the oil. On the other hand, the various systems must be compared from the viewpoint of their resistances which determine the rate of fluid production obtainable for given pressures maintained at the water input wells. The first of these questions has been studied and very definite answers have been obtained by means of simple electrolytic models.1 These models showed that, in an ideal system, the percentages of the areas flooded out before water reaches the output wells are about 57 per cent for the direct line-drive flood (the input and output wells being equally spaced and placed in alternate parallel lines), 74 per cent for the regular five-spot network, and 79 per cent for the seven-spot network. With respect to the efficiency of the usual flooding arrangements, they are, therefore, given quite accurately by the above numbers. With regard to the resistances of the flooding networks, electrical conduction models have also been used successfully2 and are well adapted to the problem of determining experimentally the pressure distribution and streamlines, or over-all resistances of specific flooding networks. However, such models do not permit readily a study of the effect of changing dimensions or configuration within a network, since a new model must be made up for each set of dimensions considered.

Jan 1, 1933

By C. F., Christopher

The purpose of any steel-making process is to convert the two raw materials iron and scrap into steel. The chemical analysis of the steel is set within certain limits which involve the physical proper- ties desired by the consumer. In addition to tensile properties a large number of other properties are at the present time desired, such as impact resistance, grain size regulation, specific degrees of hardenability, resistance to creep at high temperatures, resistance to expansion on heat treatment, the ability of the product to undergo extreme amounts of cold deformation without failure, and many other properties which are not directly related to the specified chemical analysis. Variations in many of the properties of plain-carbon steels are due to elements and compounds not included in the ordinary "five element"§ composition. Such variations result primarily from variations in oxidation of the metal in the furnace and from the deoxidation method employed. The steel-making problem therefore resolves itself into two distinct sections: (I) the elimination of certain elements from the charge (the iron and scrap entering the furnace) and the addition of materials to meet the chemical specifications for the heat; (2) the manipulation of the slag and metal and the process of deoxidation to give certain desired properties in the steel entirely apart from the chemical analysis specified. Each of 'these two ends must be attained

Jan 1, 1957

By A. E. Chute

The shortage of sulfur is not only continuing but appears to be worsening, attended by steadily rising prices. At the same time emphasis on air-pollution abatement is also increasing. These two factors, a rising market and the growth of environmental attention, have encouraged producers to carefully review all possible sulfur sources. As a result, production of sulfur from hydrogen sulfide occurring in petroleum is receiving greater attention than ever before. Until about a decade ago, the practice of recovering sulfur from hydrogen sulfide separated from gases (either found naturally or generated in desulfurization of liquid petroleum) was wide1y recognized but contributed little to total free-world sulfur production. However, during the past ten years, the production of sulfur from this source has increased so rapidly that it now accounts for a substantial portion of total production. This trend shows no signs of slackening, and current forecasts predict that recovered sulfur may become the dominant source of supply within ten years, exceeding mined sulfur production. This paper is intended to list sulfur sources and relationships, and to discuss the potential of producing sulfur from petroleum. The processing involved, in addition to product storage and transportation will also be discussed along with important economic aspects of sulfur recovered from hydrogen sulfide. For many years, most of the world's elemental sulfur has been produced from salt domes, predominantly by the Frasch process. During the past decade, however, another production source has developed so quickly that it is expected to surpass the Frasch production sources within a short time. This new source lies in the petroleum gases and liquids from which dramatically increasing quantities of elemental sulfur are being recovered. In the phraseology of the trade, the sulfur so obtained is know as "recovered sulfur," a term which does not, as one might expect, include sulfur recovered from other sources such as smelter gases. The growth rate of recovered sulfur compared to that of Frasch sulfur, total elemental sulfur, and total Free World sulfur in all forms is shown in Fig. 1 Since 1963, sulfur consumption has exceeded production,with the natural result that the price of sulfurhas continually increased. The posted price reported for f.o.b. Port Sulphur, La., has risen from as low as $18 per ton in 1962 to $32.50 per ton in mid-1967. With freight and other charges, delivered prices have of course run much higher, amounting to $45 or $46 per ton on the east and west coasts. In some cases, spot sales for as much as $60 have been reported. Although it is playing an ever-increasing role in the sulfur market, recovered sulfur was originally a by-product of the removal of hydrogen sulfide from natural and petroleum refinery gases. Today, however, it is often the most valuable product of a multi-product processing facility. Since there are two major sources of recovered sulfur—production and refining processes —natural gas is included with liquid petroleum for purposes of this discussion. Sulfur from these sources is produced in the form of gaseous hydrogen sulfide which is removed from a gas stream and converted to elemental sulfur. Gases in which hydrogen sulfide occurs naturally are natural gas and the gas produced from a high=pres-sure crude=oil or condensate field.

Jan 1, 1969

By R. F. Rolsten

VAN Arkel 1 prepared ductile tantalum by the thermal decompoiition of tantalum pentachloride on a resistively heated wire (2000° C) in an evacuated bulb maintained at 100°C. Burgers and Basart2'3 observed the formation of a mixture of tantalum carbide and free metal when a carbon deposition base was used. campbel14 suggested the thermal decomposition of the iodide if a lower decomposition tem- perature was desired. To date, the details for preparing high-purity iodide tantalum have not been disclosed. EXPERIMENTAL The tantalum to be purified was symmetrically placed around the clear quartz deposition surface centrally located within a 64 mm cylindrical Vycor bulb. The deposition vessel usually employed5 was modified6 by incorporating a reentrant fin,mer in place of the customary metal filament in the head

Jan 1, 1960

By H. L. Miaw, A. M. Gaudin, D. W. Fuerstenau

A quantitative method for evaluating density of slime coatings has been developed and applied to formation of iron oxide slime coatings on quartz and on corundum. Slime coating density is related to flotation recovery and to properties of the electrical double layer at mineral surfaces. IN spite of considerable study, the nature of slime coatings in flotation is still not completely understood. However, phenomena that control floc-culation and dispersion of colloidal systems are now interpreted in terms of electrical double layers.",' Colloids will flocculate even though the particles carry the same charge, but when two dispersed colloids of opposite charge are mixed. flocculation ensues even more rapidly. Analogous phenomena seem responsible for slime coating on minerals in flotation systems. To shed new light on the issue it was considered desirable to devise a tool that would measure slime coatings. The usual method has been to examine photographs of presumably representative surfaces, after. an intervening washing in running water. But such an examination is non-quantitative, and the changes in chemical environment represented by the washing may have removed the slime coatings that existed during flotation. To provide the possibility for a correlation with electrical double layer phenomena, the experiments were made with quartz, corundum, and iron oxide, for which elec-trokinetic data are available.'-" Since the properties of the electrical double layers of these oxides depend on the pH of the solution, pH will be the most important variable. Furthermore, because the zero point of charge for silica, iron oxide, and alumina occurs at pH 3.7, 8, and 9.5, respectively, the relative charge on the slime and mineral can be changed over wide ranges. Because of its practical importance in quartz flotation, iron oxide powder was chosen as the slime. Also, its uniform composition, contrasting color, and ease of analysis make experimentation simple. In this investigation, correlation was sought between the effect on flotation recovery of slime addition and slime coating density. Materials and Methods Details are available in a thesis by Miaw." The quartz was selected from pure Brazilian crystalline quartz, crushed, sized (65/150 mesh) acid-cleaned, washed, and stored in conductivity water. The corundum (synthetic alumina of high purity prepared by Linde Co., Chicago) was crushed, sized (65/100 mesh) deslimed, boiled in nitric acid, washed, and stored in conductivity water. The iron oxide slime, reagent-grade ferric oxide (—400 mesh) from Allied Chemical & Dye Corp., was heated to 160°C, cooled, and stored in a vacuum desiccator. In the electron microscope the slime particles appeared to be about 0.3µ in size, but their large specific surface (87,900 cm per g, by gas-adsorption method, using krypton) suggests that the actual particles are smaller than 0.3r. Had they been perfect nonporous spheres, they would have had a diameter of 0.13µ.

Jan 1, 1959

By T. R. A. Davey

The fundamental principles by which bismuth may be removed from lead by pyrometallurgical processes are enumerated. Qualitative discussion of the phase diagrams concerned is followed by presentation of quantitative diagrams. Brief mention is made of the practical aspects. Data presented show how chemical lead (<0.005 pct Bi) may be produced by the Jollivet, Dittmer, and Kroll-Betterton processes. BISMUTH is an element whose properties are very similar to those of lead, and its minerals are associated to a greater or lesser extent with nearly all the major lead ore deposits of the world. In consequence, the lead produced contains bismuth unless a special debismuthizing process is practiced. There does not appear to be any published comprehensive review of the effect of bismuth as an impurity on the properties of lead, and there is some uncertainty as to the beneficial or detrimental effects of small amounts of bismuth in lead used for particular applications. Standard specifications of most countries stipulate a maximum bismuth content of 0.005 pct for chemical lead. With one exception, this specification is met only by lead producers whose ores are relatively bismuth-free, or whose refineries are electrolytic. In lead for certain applications a higher bismuth content is preferred by some fabricators.&apos; In contrast to the refining for silver, copper, and antimony, the refining for bismuth does not usually result in a large overalil economic gain from the sale of byproduct. Thus, debismuthizing is customarily practiced only if market conditions demand a lead with a bismuth content lower than that produced by classical refining; i.e., softening, desilverizing, and zinc refining. Until this century, debismuthizing was carried out only a:; an incidental result of desilverizing, as later described. This century has seen the development of the Betts electrolytic process—the only successful one of many electrolytic processes proposed and patented —and a number of precipitation processes based on the pioneering work of Kroll,&apos; although only one of these, the Kroll-Better ton process,&apos; is in wide commercial use today. It is proposed in this paper to deal only with the pyrometallurgical processes, excluding those based on aqueous electrolysis. Historical Background Prior to 1833 silver (and incidentally bismuth) could not be removed from lead. To recover silver from rich bullion, the only course available to lead refineries was to cupel the bullion, forming a slag of litharge. The first slag tappings or skimmings, on reduction, yielded soft lead of very low silver and bismuth contents. Intermediate skimmings yielded a lead of somewhat higher silver and bismuth contents, which could if desired be recupelled. The last skimmings yielded a litharge very high in bismuth, which could by successive oxidation and reduction cycles be separated into high purity bismuth, and lead returns. This oxidation reduction process, with modern operating techniques, can still be used today to produce a portion of a lead refinery&apos;s output of very low bismuth content, as discussed later. In 1833 Pattinsone discovered that lead bullion could be purified of silver and bismuth by fractional crystallization, the primary lead crystals formed by partial freezing being purer than the melt. Repeated processing in pans produced a lead containing as little as 0.02 pct Bi. The simple explanation of this

Jan 1, 1957