Search Documents

By Leo F. Reinartz

It was with humility that I accepted the invitation of the Board of Directors of our Institute to deliver the Twentieth Howe Memorial Lecture. Many previous lecturers could speak from personal experience of the great work done by Professor Howe. It was not my privilege to be one of his students but, indirectly, I came under the influence of his work many years ago. My mentor in Metallurgy at Carnegie Institute of Technology, Prof. Fred Crab tree, was an ardent admirer of Professor Howe and his work. Professor Crabtree taught me early to appreciate Professor Howe's love of truth and keen desire to find a scientific reason for every metallurgical phenomenon. In this early search, Professor Howe encountered many unexplainable facts. Nevertheless, in the classic text, "The Metallurgy of Steel," published in 1891, he indicated that he believed Research could light the way. Under the heading of "The Treachery of Steel" he said: "In the early use of Bessemer and Open Hearth Steel, many then unexplained and hence mysterious failures occurred. With our present knowledge, an easy explanation of most of them would probably have been seen. But even today certain unexplained and apparently inexpli- cable failures occur in steel; inexplicable in spite of full and intelligent investigation." Then Professor Howe continued to talk about "the trustworthiness of steel" in the following manner: First, the steel-maker has learned by experience. He knows today far better the effects of a high percentage of carbon or of phosphorus; of cracks, pipes and blow-holes; of segregation and imperfect mixing; of over-heating; of finishing too hot or too cold. Knowing, he guards against them more effectually, and keeps at home much steel that he would formerly have sent into the market. Those who would not, or could not learn and do, have been driven out of the business; the conditions necessary for producing good sound steel by the acid Bessemer and the acid Open Hearth processes have been mastered. By and by, the basic process came along with new conditions, new liabilities to unsoundness, a great hue and cry about mysterious fractures followed, and Lloyd's register provisionally forbade the use of basic steel. Much basic steel was irregular and brittle throughout; too much carbon, too much phosphorus, too cold teemings—imperfect mixing. Still there was little doubt that, with further experience, these difficulties of the basic process would be mastered as those of the acid process had been. This shows that Professor Howe could not take anything for granted. Believing that careful research would find the answer to all mysterious phenomena, he was several generations ahead of the practical acceptance and adoption of this principle.

Jan 1, 1943

By Leo F. Reinartz

It was with humility that I accepted the invitation of the Board of Directors of our Institute to deliver the Twentieth Howe Memorial Lecture. Many previous lecturers could speak from personal experience of the great work done by Professor Howe. It was not my privilege to be one of his students but, indirectly, I came under the influence of his work many years ago. My mentor in Metallurgy at Carnegie Institute of Technology, Prof. Fred Crab tree, was an ardent admirer of Professor Howe and his work. Professor Crabtree taught me early to appreciate Professor Howe's love of truth and keen desire to find a scientific reason for every metallurgical phenomenon. In this early search, Professor Howe encountered many unexplainable facts. Nevertheless, in the classic text, "The Metallurgy of Steel," published in 1891, he indicated that he believed Research could light the way. Under the heading of "The Treachery of Steel" he said: "In the early use of Bessemer and Open Hearth Steel, many then unexplained and hence mysterious failures occurred. With our present knowledge, an easy explanation of most of them would probably have been seen. But even today certain unexplained and apparently inexpli- cable failures occur in steel; inexplicable in spite of full and intelligent investigation." Then Professor Howe continued to talk about "the trustworthiness of steel" in the following manner: First, the steel-maker has learned by experience. He knows today far better the effects of a high percentage of carbon or of phosphorus; of cracks, pipes and blow-holes; of segregation and imperfect mixing; of over-heating; of finishing too hot or too cold. Knowing, he guards against them more effectually, and keeps at home much steel that he would formerly have sent into the market. Those who would not, or could not learn and do, have been driven out of the business; the conditions necessary for producing good sound steel by the acid Bessemer and the acid Open Hearth processes have been mastered. By and by, the basic process came along with new conditions, new liabilities to unsoundness, a great hue and cry about mysterious fractures followed, and Lloyd's register provisionally forbade the use of basic steel. Much basic steel was irregular and brittle throughout; too much carbon, too much phosphorus, too cold teemings—imperfect mixing. Still there was little doubt that, with further experience, these difficulties of the basic process would be mastered as those of the acid process had been. This shows that Professor Howe could not take anything for granted. Believing that careful research would find the answer to all mysterious phenomena, he was several generations ahead of the practical acceptance and adoption of this principle.

Jan 1, 1943

By W. A. Wood, H. M. Bendler

Cylindrical fatigue specimens of OFHC* copper were subjected to alternating torsion while under axial tension. The superimposed tension strongly influenced the fatigue life of the specimens as well as causing characteristic changes in the structure of the fissures that form and develop throughout the life of the specimen. A further effect of the superimposed tension is a continuous extension of the specimen throughout its life in a manner formally similar to creep at elevated temperatures. RECENTLY, studies of the structural changes leading to fracture of metals by fatigue have been made by a technique which reveals, in section, the lattice distortion arising from slip movements inside the metal and the disturbances built up by these slip movements at the metal surface.1'2 According to this approach, fatigue develops as follows: a) fine slip movements concentrate in bands, producing little strain-hardening and thus permitting abnormal totals of plastic strain before fracture and, therefore, abnormal amounts of lattice distortion along each slip band; b) both forward and backward slip movements occur in each band which, according to their distribution across the band, may build up surface disturbances that include sharp notches; c) these notches early in the life of a specimen penetrate the distorted slip zones and transform them into deep, fine fissures; d) the fissures on continued cycling locally saturate the metal and cause local collapse in the form of a microcrack. Thus, the significant consequence of fatigue or cyclic

Jan 1, 1962

By K. J. Gill, P. Chiotti

Thermal, metallographic, and vapor pressure data were obtained to establish the phase diagram for the thorium-zinc system. Four compounds corresponding to the stoichiometric formulas Th2Zn, ThZn2, ThZn4, and Th2Zn17 were observed. The melting points of these compounds under constrained vapor conditions were found to be 1055°, 1105°, 1095°, and 1015°C respectively. Four eutectics exist in this system with the following eutectic temperatures and thorium contents in wt pct: 1040°C, 89 Th; 945°C, 79 Th; 1045°C, 55 Th; and 995°C, 35 Th. The standard free energy, enthalpy, and entropy of formation for the compounds were determined from zinc vapor pressure data. ALTHOUGH the thorium-zinc system has been of technical importance in the commercial production of thorium and more recently of interest to some proposed pyrometallurgical separations processes for reactor fuels or blanket materials no detailed investigation of this system has been made in the past. Some previous work has been reviewed by Hanssen.1 The existence of four compounds, Th2Zn17, ThZn4, ThZn2, and Th2Zn has been established and their crystal structures have been studied by X-ray diffraction techniques.2-4 Smirnov et al.,5 determined the solubility of thorium in zinc and investigated the two-phase region between Th2Zn17 and zinc. They calculated some of the thermodynamic properties for these alloys from emf measurements on the cells Th/ThCl4(fused)/Cl2, C and Th2Zn17(s)+ Zn (l)/ThCl4(fused)/Cl2, C. The possibility of reaction between the anode materials and fused thorium tetrachloride to produce a lower valent thorium salt would have to be resolved in order to evaluate the results obtained. The purpose of the present investigation is to establish the phase diagram for the thorium-zinc system and to determine the standard free energy, enthalpy, and entropy of formation for the compounds formed. MATERIALS AND EXPERIMENTAL PROCEDURES The metals employed in the preparation of alloys were Bunker Hill slab zinc, 99.99 pct pure and Ames Lalboratory thorium. The major impurities in the thorium in parts per million were oxygen—1250, carbon—350, iron—100, nitrogen-75, and silicon—70. The metals in the form of several small massive pieces, total weight about 30 g, were cleaned with acid, washed with water and acetone, and dried just prior to their use for alloy preparation. Tantalum containers were found to be suitable for all the alloys studied and were used throughout this investigation. The metals were sealed inside of small 1-in.-diam tantalum crucibles by welding on preformed tantalum covers. A small thermocouple well made from 1/8-in.-diam tantalum tubing was welded in the bottom of each crucible. These crucibles were enclosed in

Jan 1, 1962

By F. W. Jessen, C. C. Patton

Adsorbed films were formed on polished stainless steel specimens from dilute benzene solutions of two crude oil distillation residua. Although the two residua were extremely dissimilar in composition, contact angle measurements showed that the two films increased the wettability of the steel specimens to oil by equal amounts. Furthermore, the wettability of the films was essentially unaffected by the desorption techniques used. Paraffin deposits were formed from heptane-wax solutions on the same stainless steel specimens. These deposits definitely adhered to the surface. Presence of an adsorbed crude oil film on the metal surface increased its free surface energy and resulted in increased deposition of paraffin. The addition to the heptane - wax solution of small amounts of the same distillation residua that were used to form the adsorbed films resulted in decreased cohesive strength in the deposits formed, which resulted in decreased deposition. The presence of a crude oil fraction both in the solution and as a preadsorbed film eliminated the adherence of a deposit of any kind. A mechanism of deposition is proposed which explains the results obtained. INTRODUCTION The natural formation of any predominantly organic accumulation in oilwell tubing, surface flow lines or other production and storage facilities is called a paraffin deposit. These deposits restrict the production of crude oil, causing a substantial increase in production costs because of decreased flow capacity, expense for periodic deposit removal and unproductive downtime. The conditions under which such deposits form, their physical characteristics and the nature and severity of the problem created are extremely varied. Over the past several years, much progress has been made in developing and utilizing methods to remove accumulated paraffin deposition. However, like so many other problems, the basic stumbling block appears to be a lack of understanding of the fundamental mechanism involved in the formation of such deposits. Crude petroleum is known to contain considerable quantities of polar, surface active substances which Doddl has shown to be present at the oil-water interface. Denekas, Mattax and Davis2 observed that the wettability of reservoir rocks was drastically altered by exposure to crude oil fractions; and Zisman, et a1.3 showed that the nature of the compounds adsorbed on a surface would determine its wettability characteristics. Cole and Jessen4 and Ehrig5showed that surface wettability can have a profound effect on the magnitude of paraffin deposition, and Parks6 demonstrated chat the presence of certain adsorbed films on a metal surface would reduce the adherence of paraffin to that surface. Zisman7 has since advanced the theory that the conditions for adhesion are the same as for wetting. Therefore, it was felt that there was adequate evidence to support the supposition that adsorption of compounds from a crude oil might play an important part in paraffin deposition. ADSORPTION-WETTABILITY EXPERIMENTS Initial experiments were conducted to determine the effects of adsorption from solution of crude oil residua on the wettability of a polished stainless steel surface. Distillation residua with initial atmospheric boiling points of 700F were used in preference to the whole crudes in order to concentrate on the molecular weight range of interest, and to eliminate the possibility of composition change due to evaporation of the light ends. Also, these high boiling materials would be expected to be adsorbed from the whole oil in preference to similar compounds of lower molecular weight.

Jan 1, 1966

By P. Sanchez-Mejorada

GEOLOGISTS who are acquainted with the mines of northeastern Mexico realize that the most important lead-silver replacement deposits of the province are confined to a single formation. But since the formation is several hundred meters thick, the author has determined the relative position of the lead mantos in the belief that this information will prove useful in the search for new mines. This article describes the stratigraphic location of lead-silver replacement deposits known in several mines situated in a region comprising part of the states of Coahuila and Nuevo Leon. The area studied extends for 200 km* (125 miles) from east to west and 70 km (45 miles) north to south. Metallogenic Province: The most important metallic deposits of the region have the following common characteristics: 1) The orebodies occur as manto replacements of calcareous sediments. 2) The horizons that have contributed large tonnages of ore are in similar positions in the corresponding stratigraphic columns (as it will be shown later on). 3) Lead is the most important metal in the ores. Silver is commonly present in small amounts. Occurrence of zinc is dependent on the degree of oxidation of the primary sulfides. 4) A large proportion of the total production has been in the form of oxidized ores. 5) The deposits are located on anticlines. Rocks of Cretaceous age crop out over large areas of the states of Nuevo Leon and Coahuila. forming part of a belt that extends to the south along the eastern Sierra Madre. The sediments are cut by a small number of intrusive stocks ranging in characteristics from rhyolite to diorite. The most prominent structural feature of the region is a series of folds trending northwest-southeast. Faulting is not conspicuous in the region, although a major fault zone is found farther East.' The physiography closely reflects structural features, with mountains formed by anticlines and valleys conforming with intermediate synclines. Narrow valleys have also been developed along the axes of many anticlines, where solution of limy sedi- ments and erosion have proceeded along axial tension fractures. Stratigraphy: Rocks of the Upper Cretaceous are exposed in only a small percentage of the total area. Generally they have been eroded away from the mountains and are covered by recent talus and alluvium in the valleys. Humphrey' has published an excellent paper describing the Cretaceous formations of the Sierra de los Muertos, a short distance west of Monterrey. A brief summary of these formations is given below to convey an overall picture of the stratigraphic sequence that prevails just south of the area under consideration. Upper Cretaceous Indidura: Essentially thin shaly sediments. Cuesta del Cura: Limestone in thin wavy beds

Jan 1, 1959

By Norman F. Schulz

The technical excellence of separation achieved in a mineral concentration process, or any other process where two constituents of any kind are physically separated from each other, is expressed uniquely and quantitatively by the separation efficiency (E,): E. = (R - R,), where R is the percentage of the valuable constituent and R, the percentage of the waste appearing in the concentrate. The separation efficiency meets all the usual requirements of a true efficiency and is independent of the nature of the process used. It can be visualized as the percentage of the feed material that, in effect, actually undergoes complete separation while the rest of the feed is distributed randomly and unchanged into the two separation products. The problem of quantitatively assessing the results of a mineral concentration process recurs whenever one tries to decide which of two similar test results is more desirable. Although economic factors may greatly influence the eventual choice of process, they usually have very little to do with the technical excellence of a separation and are, therefore, not a consideration at this point. Concentrate grade and recovery, used simultaneously are the most widely accepted measures of performance, and if both the grade and the recovery are greater for one case than for another, the choice is simple. However, when the results of closely competitive operations are compared, it often occurs that one set of test results shows a higher grade and a lower recovery than another and the choice is no longer obvious. Laboratory investigations of a mineral concentration process applied to a given feed material can often be designed to yield successive paired values of concentrate grade and recovery over the practical range of the course of a separation process.' These results may be plotted as some combination of the cumulative values of grade, weight recovery, or unit recovery in the concentrate. The resulting correlations for two slightly different sets of conditions can then be compared qualitatively, or even quantitatively in particular cases.2 Such comparisons are not applicable, however, to individual concentration test results. The reduction of a separation test result to a single efficiency figure, preferably as a percentage of ideality, would afford the simplest and most precise means for comparing the results of competitive tests. The effective proportion of feed material that undergoes complete separation in any real concentration process, hereafter referred to as "separation efficiency," is such a figure. It is essily calculated from the usual feed and product data and can even be evaluated, in many cases, from data in publications describing various concentration processes. Mineral Concentration Processes and Their Evaluation Mineral Concentration Processes: The overall concentration process may be subdivided into a liberation process which severs the bonds between unlike mineral species, and a separation process, which sorts the resulting liberated particles into two products—a concentrate rich in mineral A and a tailing lean in mineral A. A perfect mineral concentration process is represented by the idealized scheme shown in Fig. 1 in which liberation and separation are not differentiated. The feed mixture consists of two mineral types which are completely liberated early in the process and then sorted by type. All the mineral particles of type A which respond uniquely to the selection forces acting in the ideal separator, report to the concentrate, while all the mineral particles of type non-A report to the tail-

Jan 1, 1971

By F. W. Bowdish

A theoretical and experimental laboratory study has shown that the rate of breaking of oversized particles in a ball mill is proportional to 1) the concentration of such particles, and 2) the area of the balls, provided that the balls are larger than a certain size relative to the particles. If all undersized material were removed as formed, the rate of breaking would be almost independent of the quantity in the mill. Rate equations are given which are similar to those for zero, first, and second order reactions. Deviations of small balls from the equation for a second order phenomena are quantified by a factor called "nipping efficiency." Some data are correlated by a dimension-less equation, which is used to estimate nipping efficiencies from data not in the correlation. The investigation described here was undertaken after a literature survey revealed that little was known concerning the mechanism of breaking of particles within a ball mill and the effect of this mechanism upon grinding rates. One paper, by Roberts1 , offered a theory concerning the mechanism of breaking, and a rate equation for the breaking of particles larger than some size to particles smaller than that size. That paper provided the starting point for a theoretical and experimental investigation of grinding under carefully controlled conditions. THEORETICAL CONSIDERATIONS In his paper on the probability theory of ball mill grinding, Roberts theorized that "... a given expenditure of power leads either to a certain number of point to point blows per bp-hr or to a certain distance of line contact per hp-hr ..." He assumed that the balls touch each other during each blow or during moving contact. Then he said that a volume of pulp, dependent upon the size being considered, would be covered per minute within which all oversized particles would be crushed to particles smaller than that size. Naturally, the higher the concentration of oversized particles in the pulp, the higher the rate of which they would be broken. From this reasoning Roberts obtained the differential equation -dC/dt = k hp/ton C (1) where k is a constant for any size of particle, density of particle, and moisture content of pulp. C is the percentage of oversize in the material to be ground, t is the time, and hp/ton is the power input per ton of material in the mill. He then integrated the equation to log Co/Ct = k/2.3 hp/ton t , where Co and Ct are the percentage of oversize at time zero and t respectively. By always using the same quantity of material in a mill and assuming that it required constant power to run the mill, he was able to combine the horsepower per ton factor with the other constants to give an equation for a first order rate.

Jan 1, 1961

By Charles H. Jacoby

The solution mining of evaporites has a history of approximately 5,000 years. The insitu leaching of metalliferous ore will have many of the same characteristic problems which have confronted industry for years in the production of evaporite minerals. Basically we will be converting the less soluble forms of valuable metals into their more soluble salts and producing these in much the same manner as, for example, sodium chloride. There are a number of problems which we are faced with that are more complex and complicated and, therefore, will require a higher degree of sophistication than previously employed. One of our most important undertakings will be the clearcut definition of the problems involved. While a great deal of expertise can be drawn from the solution mining of evaporites and the oil industry, problems peculiar to the hydrometallurgical field will need to be solved. One of these is the introduction of permeability into an impermeable rock so as to expose the sought after values of metals which by volume are infinitesimal when compared with sodium chloride, potash or other type water soluble mineralization. After establishing this permeability which will be miniscule when compared to a solution cavity, there will be the maintenance of this permeability. In general, salt deposits are of a somewhat uniform chemical composition and thus their chemistry was relatively simple. Each metalliferous ore body is somewhat unique in its chemistry and will need to be treated accordingly.

Jan 1, 1974

By John Nunes, Frank R. Larson

Temperature-dependent functions of various ten-sile flour stress and fracture parameters were investigated on iron and low composition alloys of Fe-C, Fe-Cr, Fe-Mn, and Fe-Ni. Data were obtained over a range of test temperatures from 200" to -196"C at an initial strain rate of 0.01 min". It was found that the strain-hardening exponent, n, for the Fe-Ni alloys increased significantly at very low testing temperatures with increased alloy addition. Also, the stress and strain at fracture followed a predictable transitional type of behavior. The flour stress-temperature dependence was evaluated employing the relation: M where it is shown that composition can strongly influence the constant M. An empirical formula describing this effect is as follows: M = MI (equivalent at. pct Ni)-'" Some preliminay, tests were run on several commercial steels to test the generality of this relationship. One of the phenomenological explanations of the ductile-to-brittle transition encountered in bcc metals is based upon the difference in the temperature dependence of the flow and fracture stresses.' It states simply that the fracture stress is relatively insensitive to temperature and that the yield or flow stress rises rapidly with decreasing temperature so that, when the flow stress reaches the fracture stress, brittle fracture occurs without appreciable plastic deformation. This behavior is illustrated schematically in Fig. 1 where the ductile-to-brittle transition is shown to occur at two possible temperatures. The lowest temperature, TB, represents essentially completely brittle behavior while the higher temperature, TN, represents "notch" brittle behavior. Support for this theory is obtained when it is observed that fcc metals, which do not commonly have a ductile-to-brittle transition, also do not commonly exhibit any strong temperature de- pendence of the yield stress. This relationship of yield or flow stress behavior with the ductile-to-brittle transition has been generally observed for most metals representative of these two crystallo-graphic structures. One exception to this generalization appears in the case of tantalum where no apparent ductile-to-brittle transition has been observed. However, this may simply be an indication that this type of behavior is not directly related to the flow stress and that some other mechanism such as twinning must also be operative. A comparison of the typical temperature dependence of the yield stress of some representative metals is shown in Fig. 2. In the study of the temperature dependence of the strength of metallic materials, considerable ef-

Jan 1, 1963

By R. L. Whiting, H. J. Ramey

The basic study from which this paper was prepared was started as the result of the growing need throughout the world for increasing quantities of energy in all forms. Quite obviously, natural forms of energy that are readily available at low development cost are those in greatest demand. The underdeveloped countries — and particularly those having little or no petroleum resources — are the countries in which the most interest is being shown in the newer energy sources. One of the least expensive energy sources is natural geothermal steam.'-* Although this form of energy has been recognized for centuries, it has been only during the past 20 years that serious efforts have been made to harness it. Natural geothermal steam energy in Italy, New Zealand, Mexico, Japan, and California is now being produced through wells to drive turbines and generate electricity. Further, active exploration for natural geothermal steam is being conducted in Hawaii, Fiji, Taiwan, Chile, Russia, Greece, and Katanga. It is surprising to find that most geothermal steam exploration is in the "steam seep" stage. That is, surface studies are made and exploratory wells are drilled in the general area of steam seeps. However, in the larger geothermal steam areas, there have been efforts to apply the most modern geological and reservoir engineering principles in order to define the reservoir parameters, particularly those relating to estimates of reserves and future productivity. This paper is concerned with the development of appropriate equations and techniques to facilitate these estimates. Production of natural steam or hot water presents problems different from those experienced in the production of oil and gas. For example, steam or hot water systems may be essentially single-component systems, while hydrocarbon systems are most frequently multicomponent fluid systems. Heat effects are much larger for water than for hydrocarbon systems; and the natural steam production may or may not be isothermal, while production of petroleum reservoirs is considered normally to be isothermal. Petroleum reservoir engineering principles may be applied to natural steam or hot water reservoirs if the inherent differences in the systems are considered. The basic considerations involved in geothermal steam reservoir engineering are: thermodynamics, physical and thermal properties of water, materials and energy balances, fluid influx, and performance matching and predicting. Thermodynamics Fig. 1 is a pressure-temperature diagram for the liquid-vapor region for pure water, showing the critical point and five other points representing possible initial conditions for a geothermal steam reservoir. To generate a physical appreciation for the mechanics of natural steam production, it is helpful to consider

Jan 1, 1970

By E. H. Herron, J. H. Perry

Mathematical simulation of reservoir behavior may be used to help understand reservoir processes and to predict reservoir behavior, thereby leading to the most economically desirable form of exploitation. In addition, simulation can be used as a tool for reservoir description to learn more about the physical nature of the reservoir and the mode of primary recovery. This use is essential in most reservoir studies and represents one of the more significant applications of simulation. Prediction of reservoir behavior provides information concerning displacement efficiency, optimum well locations, and the comparison of alternative producing processes. Since oil, water and gas all commonly occur in many reservoirs, a simulation that takes into account the simultaneous flow of three immiscible phases is a prerequisite for obtaining such information. Furthermore, a simulation that describes this flow in two dimensions provides the capability of evaluating combination gas- and water-drive reservoirs with either an areal or a cross-sectional description. Many reservoir problems require such a simulation. The objective of the research described here was to develop a mathematical model and associated computer program for accurate, efficient, and economical prediction of the reservoir flow of three phases in two-dimensional geometry. Several authors have discussed multidimensional reservoir simulation of two phases.l-3 Gottfried et al.' presented an analy- sis of three-phase simulation in one dimension. Fagin and Stewart" and Garrett6 have discussed the simulation of three-phase flow in two dimensions, but their solution techniques were different from the method discussed in this paper. In particular, previous models and computer programs have usually involved either fewer capabilities or inefficient and less rigorous descriptions resulting in limited applicability. In the following sections, we present a description of the model, an evaluation of the method, and the application to reservoir problems. Additional and supporting material is presented in the Appendix. The Three-Phase Model General Description The three-phase model consists of the mathematical description of the flow of oil, water and gas in a reservoir. Conceptually this description considers flow in all three space dimensions, but in the subject simulator it is assumed that no flow occurs in the third dimension. The model includes the effects on reservoir behavior of fluid and rock compressibility, viscosity, gravity, capillary pressure, relative permeability and gas solubility. Within the two-dimensional restriction, the reservoir considered may be completely heterogeneous and anisotropic. The differential equations governing multiphase, multidimensional flow in a reservoir are too complex to be solved analytically, so they are approximated by a system of finite difference equations and solved

Jan 1, 1970

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 Charles Will Wright

The present struggle for economic and industrial supremacy by the Communist world is against the United States, its main target, and the other Free World nations. The basis of industrial power is minerals, so the Communist nations are building up mineral production within their borders, often regardless of costs, and are acquiring quantities of mineral products from Free World countries for future use. They are contracting for additional supplies and advancing funds for the development of these quantities. A number of the less developed mineral producing countries of the Free World are being infiltrated by Communists and Communistic influence. This situation is well known, but as yet little has been done to oppose these activities or to awaken the public to their seriousness. The Communist countries are still far behind the Free World Nations in production of many essential minerals. But, shortages are being made up from Free World nations in exchange for petroleum, manganese ore, chromite and other products. Restrictions on shipments of strategic materials to Communist countries have not been maintained.

Jan 1, 1964

By B. P. Nutter, M. Lebourg, J. A. McAlister

The Multi-Flow Evaluator (MFE) is a new system of tools providing an original approach in drill-stem testing. It improves control during the testing operation and gives a more accurate evaluation of the fluid recovered while providing additional pressure information for reservoir analysis. The tools are operated entirely by up and down motion of the drill stem. This up and down operation provides a positive means of control and offers easily observed surface indications of tool operating position. An unlimited number of shut-in and flow periods may be taken with this tool while in the hole. The key to the success of the MFE system of tools is the safety seal packer. Until this development, operation of the tools by up and down motion only had proven unreliable. The success ratio of the MFE now exceeds the ratio achieved by conventional tools. The equipment includes a 2,750-cc chamber in which a representative sample of the flowing formation fluid is trapped at the end of the last flow period and brought to the surface under pressure. The sample can be evaluated at the wellsite or transferred under pressure for laboratory analysis. The sampling feature of the tool allows a sample to be obtained from a reservoir which has suffered minimum influence from production. A representative sample can be obtained for laboratory or empirical analysis by employing a testing technique to minimize drawdown during flow periods. Interpretation methods to take advantage of this additional information are presented and supported by actual field examples. INTRODUCTlON The Multi-Flow Evaluator (MFE) represents the most recent technical advance in formation testing. Drill-stem testing techniques prior to the MFE have been limited in three areas—(1) operaiion, (2) recovery analysis, and (3) reservoir analysis. The tools in the MFE system allow maximum control during testing and provide test information superior to that obtainable with conventional tools. The system of tools and the operation procedures are described to illustrate the mechanical advantages over present tools. Methods of pressure build-up and fluid

Jan 1, 1966

By G. R. St. Pierre, A. J. Wilhelem

In connection with the reduction of hematite or magnetite to metallic iron, it appeared desirable to study the rate of reduction of each oxide to the next lower oxide under conditions which excluded all other condensed phases. For this purpose, pellets of Fe,O,, Fe,O,, and oFeOo were prepared. A gas train for the preparation of Ar-Hz-H20 mixtures was employed to establish a continuous flow of a controlled atmosphere over a pellet suspended on a balance. In this manner the following individual reduction steps could be studied: For example, pellets of hematite were reduced solely to magnetite by adjusting the gas atmosphere such that it was oxidizing to wustite. In other words, the reaction was complete when the hematite pellet had been totally converted to magnetite. The pellets were prepared from Baker Chemical ferric oxide. The ferric oxide powder was moistened and handrolled. Air sintering at 950°C produced Fe,0, pellets with a density of 3.65 g per cm3. The pellets ranged in size from 0.6 to 1.2 cm diam. The magnetite and

Jan 1, 1962

By William B. Hughes

The rubber-sleeve core barrel was developed to improve core recovery from unconsolidated sands, where it is most difficult to obtain cores with conventional barrels. The use of a rubber-sleeve core retainer, together with other departures from clsual design, has required a considerable amount of testing to prove its op-erability. Tests run in shallow experimental holes and in drilling wells in the U. S. and Vemzuela have, to a large extent, proved the operation of the barrel. Internal mechanism troubles, such as sandbinding of the sleeve, have been largely overcome. Cores have been recovered from completely unconsolidated sands where conventional coring has almost been abandoned because of poor recovery. In addition to retaining the core until brought to the surface, the barrel gives a "packaged-ar-cut" core, which is coilverzient for handling and transportatiorz. In the initial work, drag blade cutters, roller cutters, and tungsten carbide insert cutters were usrd for cutting unconsolidated sands. Further bit head development is presently being conducted using diamond heads in unconsolidated sands where shaler, hard sands, and limestones are encountered in adjacent formations. Thir work should render the barrel capable of cratting and recovering most types of formations, possibly including broken and frac- tured fornlations. This development is being carried on in cooperation with a diamond bit manufacturer. INTRODUCTIO N For many years the oil industry has needed greater recovery of cores from unconsolidated formations. Conventional equipment has been used to core unconsolidated sands with little success. Specifically, a core barrel was needed which would recover unconsolidated sands in a condition that would give useful reservoir information. DEVELOPMENT OF 'THE RUBBER-SLEEVE CORE BARREL Basic Requirements of Unconsolidated Sand Corino The basic need was defined as a core barrel that would obtain a continuous unconsolidated core with sand grains in place as deposited in the formation. A preliminary survey of coring equipment and search of the literature pointed out the weaknesses of conventional core barrels. Laboratory tests using unconsolidated sand in a metal tube simulated actual sand movement into the core barrel during conventional coring. In conventional barrels the core sometimes crumbles and bridges, or fails under compressive column action, becomes oversize, and wedges against the walls of the inner barrel. The core barrel requirements established by the surveys and preliminary tests are as follows. 1. The core should be held to- gether as it is cut so it cannot crumble and bridge against the walls of the coring tool, care being taken not to permit damage from fluid circulation. 2. The core should be continuously supported as it is cut so it will not have to support itself in compression. 3. The core should be packaged in the barrel to retain an undisturbed condition during the trip out of the well. The packaging should be such that the core can be removed from the barrel and shipped to the core analysis laboratory without physical disturbance or alteration of fluid content by exposure to the atmosphere. Operation of the Rubber-Sleeve Core Barrel The rubber-sleeve core barrel (Fig. 1) meets the basic requirements for the recovery of unconsolidated sands.

By E. J. Ripling, M. W. Toaz

Tensile tests were conducted on pure magnesium and on four commercial alloys over a variety of temperatures and strain rates. The high positive slope of the ductility vs testing temperature curves that is found over a short range of testing temperatures for these materaturerials was shown to result from the fact that the microstructure was not stable at these testing temperatures. Pure magnesium did not display a transition temperature, although its sub-room temperature ductility was low. This poor ductility resulted from a grain boundary weakness. The aluminum-bearing commercial magnesium alloys had a higher ductility than the pure magnesium. ness.Thealuminum-bearingcommercialThese alloys did exhibit a transition temperature and grain boundaries that were stronger than the grain material. Both pure magnesium and the commercial alloys began initiating cracks at strains equal to one half of their fracture strain. MAGNESIUM base alloys' enormous potential as structural materials lies in their high strength to weight ratios. At present, the high strength magnesium base alloys such as AZ-80, which will be discussed later, have about as high a tensile strength to specific gravity ratio as the highest strength wrought aluminum alloy, 75s-T6, and, of course, a much higher strength to weight ratio than structural steel. Further, since the magnesium base alloys develop their high strength to weight ratios with moderate strengths and extremely light weights, the ratio of load carrying capacity to the weight of many structures is relatively higher for the magnesium base alloys than their strength to weight ratios would indicate. This results because judicious increases in section size, such as increasing the depth of bending members or adding reinforcing ribs, can frequently increase the weight of a structure linearly while the strength and stiffness increase as the second or third power of the added weight. Strength and rigidity must be designed into lightweight structures by those techniques which establish multiaxial stress states. Consequently, strong, lightweight structures frequently also possess a greater propensity toward brittle failures. In order to insure against these catastrophic failures, an extra premium must be placed on ductility and toughness in light alloys. Current knowledge of the ductility and toughness behaviors—notched behaviors—of magnesium base alloys is limited.* Most of the magnesium base alloys * The state of present knowledge regarding the effect of testing temperature on mechanical properties has recently been summar-ized by Pritchard.' crystallize in the hexagonal system, so that they are expected to exhibit a tough and ductile to brittle transition temperature. Actually, a transition temperature behavior has been reported for commercially pure magnesium in the literature, but the characteristics of this transition temperatureh uggest that it may not be a transition in the usual meaning, but simply the onset of some thermal softening, a performance much like that which face-centered-cubic lead might exhibit slightly below room temperature. If transition temperatures do exist, such important questions as the manner in which they are affected by internal variables such as chemical composition and grain size, or the effect of external variables such as rate of straining or notch severity have never been investigated. The investigation reported upon herein was undertaken in order to define some of the mechanical behaviors of the magnesium base alloys better, to gain a better understanding of the influence of some of the above listed variables, and particularly to understand their effect on ductility and toughness better. Material and Procedure Material-—Pure magnesium and four commercial alloys were used in this investigation. The alloys were selected so that chemically they made up a series with approximately the same minor alloying

Jan 1, 1957

By R. P. Harvey, J. E. Walstrom, A. A. Brown

In view of the large number of wells directionally drilled from offshore platforms and urban drillsites, greater interest is being focused on the directional survey and on the uncertainty inherent in calculating the position of the bottom of the hole, or other benchmarks in the wellbore. Of the two methods presented here for evaluating this uncertainty, the first is analytical and uses the principles of probability and statistics. The second method uses Monte Carlo simulation to generate a pattern of the scatter of possible bottom-hole locations. Both methods are based on a model for which the usual assumption is made that the curvilinear axis of the wellbore is adequately represented by a large number, M, of linear segments joined end to end from the top to the bottom of the hole and closely following the course of the hole. The errors due to this approximation are assumed to be negligible and are not studied here. One form of the model is to consider that for a given hole there exists a perfect set of data describing it, of the above form. Each linear segment has an angle of inclination with the vertical 7, in radians, an azimuthal angle from true north xi in radians, and a length Si, in feet. The subscript variable, i, extends from 1 to M. Each of the M linear segments representing the axis of the wellbore has three components in the X, Y, and Z directions. These components are calculated from the equations: The bottom-hole coordinates as determined from the reference set of data for the wellbore are given by the following for i = 1 to M: X=SX, Y = Sy, Z=SZ; . (2) A directional survey instrument, lowered into the wellbore to the M segments, or stations, measures the values of the 7; and the 3,. In general, because of errors from various sources, the resulting angular measurements will not be precisely equal to the 7" and xi. Random variables l, and Ai are therefore considered with associated probability density functions fi(li) and gi(Ai), respectively, which represent the distributions of potential survey measurements for this hole. Since it is assumed that the values Si are accurately measured they are treated deterministically. The random variables corresponding to the surveyed bottom-hole coordinates are given, for i = 1 to M, by:

Jan 1, 1970

By J. F. Havard

The enterprises based upon the industrial minerals are diversified in geologic habit, mining systems, processing techniques and marketing methods. Nevertheless, in 1972 these enterprises faced many of the same frustrations and hopes and knotty problems and crucial decisions. Volume and profits were generally improved but were uneven in extent and effect. The U.S. cement industry, for example, was unable to meet demand in major markets. It was constricted by a frozen low-level price structure, faced expensive pollution control measures and watched heavy imports penetrating its markets from several European nations, Mexico and Canada.

Jan 1, 1973