Search Documents

By M. E. Lombardi

Discussion of the paper of AI. E. LOMBARDI, presented at the San Francisco meeting, September, 1915, and printed in Bulletin No. 105, September, 1915, pp. 2109 to 2114. C. D. KEEN, Shreveport, La.-Did Mr. Lombardi include in his figures the purchase price of the property? M. E. LOMBARDI, Berkeley, Cal.-No. C. D. KEEN.-Suppose I pay $1,000 per acre for it, and in four or five years it is worked out. M. E. LOMBARDI.-That is a question of depreciation and must be added to my figures. MARK L. REQUA, San Francisco, Cal.-You say it cost $35,000 to $40,000 a year to maintain 1,000-bbl. per day production? M. E. LOMBARDI.-Yes, 1,000 bbl: a day would cost $40,000 a year to maintain.

Jan 12, 1915

By John N. Dew, William L. Martin, `

This paper describes the results of a laboratory investigation conducted to obtain data for an evaluation of the in situ combustion process as a method of producing crude oil from reservoirs. Air and fuel requirements, rates of advance, com-bustion temperatures, and coke and fluid distributions are presented. The mechanism of oil recovery by in stiu combustion is discussed. Five crude oils ranging in gravity from 10.9 to 34.2"' API were prodrrced from a semiadiabatic, uncon-.solidnted sand pack by in situ combustion. Experimental conditions were varied over a wide range in order to determine the inter-relation-.ships of process variables. The mini-mum air flux requirement for self-sustained combustion was found to he less than 10 scf/hr-ft'l. The rate of advance of a self-sustained combustion zone was found to be nearly proportional to the air flux at the combustion front. The effects of presrure and injected air flux were studied in a series of experiments using a 21.2" API crude. A minimum air require-ment was observed at an air .flux of 20 scf/hr-ft'. The oil saturation con-sumed as fuel averaged 5.5 per cent of pore volume. The effect of air pressure was, found to be .small for experiments having high combustion eficiencies. This study should promote a better understanding of the problems and mechanisms involved in labora-tory investigations and field applications of the in situ combustion pro-cess. The data presented will be use- ful in the interpretation of results of field tests. When tempered with volu-metric sweep efficiencies, the data can be used in making preliminary economic appraisals of the process as applied to reservoirs containing high porosity unconsolidated media. INTRODUCTION The purpose of this work was to obtain laboratory data for an evaluation of the in situ combustion process as a method of producing crude oil from reservoirs. In situ combustion basically consists of (1) injecting air into a reservoir through selected input wells to create an air sweep through the reservoir, (2) igniting the crude at the injection well, and (3) propagating the combustion front through the reservoir by continued air injection. By this means, oil is swept toward producing wells in the area. The fuel for combustion is supplied by heavy residual material (coke) which has been deposited on the sand grains during distillation and cracking of the crude oil ahead of the combustion front. Recovery of petroleum by a combustion or heat wave process is not a new idea. F. A. Howard was granted a patent in 1923 on a process in which air and a combustible gas were pumped into an injection well and ignited.' Russian engineers reported on field experiments with a crude oil gasification process in 1935'. Other known early field tests include those conducted near Bar-tlesville and Ardmore, Okla., in 1942." More recently completed field tests include an inverted seven-spot by Sinclair Oil Co. in the Delaware-Childers field, Nowata County, Okla.'; a three-well and an inverted five-spot test by Magnolia Petroleum Co. in Jefferson County, Okla."."; and a test by California Research Corp. in the Irvine-Furnace field in Kentucky. The Worthington Corp. has completed a test in cooperation with the Forest Oil Corp. in Clark County, 111.l Several field tests are now in progress. Sinclair has acquired a 600-acre lease in the Humboldt-Chanute field, Allen County, Kans., and is under way with a large-scale operation. Three field tests are under way in California. The General Petroleum Corp. is conducting an inverted five-spot pattern test in the South Bel-ridge field in Kern County under a cooperative agreement with 11 other companies, including Continental Oil Co. California Research Corp. is conducting a four-well pattern test in Midway-Sunset field near Maricopa, and Richfield Oil Corp. is under way with a test in the Ojai field in Ventura County. Although the published information is valuable concerning results of field tests, little laboratory data other than that reported by Kuhn and Koch5 are available to aid in appraising the tests from a technical or economic standpoint. Engineering data needed to evaluate the process include the amount of air required per barrel of oil recovered, minimum injection rates which will support combustion, rates of advance, air required per unit volume of reservoir cleaned, amount of oil recovered, and amount of oil consumed as fuel. The present laboratory investigation was undertaken to provide these data for that portion of the reservoir swept by the combustion zone. The first phase of this investigation was exploratory in nature and was conducted at injection pressures less than 100 psig. Data were ob-

South Dakota State Geological and Natural History Survey, State University, Vermillion, S D. A list of publications will be sent upon request Many of the publications are out of print A series of Biennial Reports of the State Geologist will be sent upon receipt of three cents for postage on each, and are available as follows: 1918-20, 1920-22, 1922-24, 1924-26, 1926-28, 1928-30 Available Bulletins of greatest interest are: Bulletin 4, Pre¬liminary report of the geology of the Rosebud Reservation (1909), 10 cents; 10, Possibilities of oil in South Dakota (1922), 10 cents A series of Circulars (5 cents each) deals with the possibilities of oil and gas in various parts of the state, as follows¬ Circular 8, Eastern Pennington County (1921), 9, Western Dewey County (1922); 10, Northern Dewey County (1922), 12, Eastern Harding County (1923), 13, Northern Ziebach County (1923); 20, Western Ziebach County (1925), 23, Northeastern Meade County (1925); 27, Western Corson County Other Circulars (5 cents each) are: Circular 16, The natural resources of South Dakota (1924), 22, Structures ,in northern Haakon County (1925); 24, The Ragged Butte structure (1925), 25, The structure of western South Dakota (1925), 28, Structures in western Haakon and eastern Pennington counties (1926)

Jan 1, 1933

By W. J. Leas, L. A. Rapoport

As a preliminary, consicleration is given to the conventional definition of relative permeability and to the conditions governing the simultaneous flow of oil and gas through porous media. For the conditions of flow prevailing throughout most of a gas drive reservoir, the oil and gas can reasonably be supposed to be in capillary equilibrium with each other. Under these conditions, and these conditions only, the relative permeability to liquid can be expressed as a function of saturation. The relative permeability to liquid in that case is dependent upon the distribution of fluids which itself is shown to be related to the capillary pressure, and, in turn, to the saturation. As a consequence, relative permeability to liquid can be expressed in terms of the volume and surface area of a network of liquid channels bounded by the rock and the gas phase. While the volume of this network can be evaluated accurately, the surface area cannot. However, for any such volume, maximum and minimum values of the corresponding surface area can be calculated from capillary pressure data. It is then possible to establish for any saturation the limits within which the value of the relative permeability to liquid must lie. As a consequence of the theoretical development, the validity of an experimental method for measuring relative permeability to liquid which utilizes a stationary gas phase is demonstrated. In this method capillary barriers are cemented to the ends of the core sample to permit the maintenance of capillary equilibrium between the two phases. At the same time, this procedure eliminates undesirable secondary phenomena such as end effects, fissure effects, etc., the presence of which adversely affect the results of other laboratory methods. The results obtained by theoretical calculations, and experimentally, are discussed. In view of the overall precision that can presently be obtained in reservoir calculations, the agreement between the calculated and measured relative permeability to liquid data can be considered satisfactory. In conclusion, for reasons of economy and simplicity, the procedure of calculating limiting relative permeability to liquid curves from capillary pressure data is indicated for general engineering purposes. It is shown that the above procedure can easily be extended to the cases where connate water is present. Its use for reservoir studies is particularly recommended in conjunction with the method for measuring relative permeability to gas' which simultaneously yields the capillary pressure data necessary for the calculations. THEORETICAL Definition of Relative Permeabilities — Basic Equations for Heterogeneous Flow The equations by which the relative permeability concept is defined and upon which the formulation of all of the gas-oil flow problems rests at the present time are expressed as: V, = — Grad PL = — Grad PL ....(la) PL µL, k k KG VG = —K - Grad PG k- Grad Pc .... (lb) Mo where ,. and G refer to liquid and gas; V is the volumetric rate of flow per unit gross area. µ the viscosity, Grad P the potential gradient. and k the specific permeability of the porous medium.* (For horizontal flow, Grad P becomes the pressure gradient; otherwise, gravity must be included.) According to these expressions, each of the constituent phases is considered similar to a homogeneous system where the volumetric rate of flow is proportional to the pressure gradient, and for each of which the constants of proportionality, k, and kG, are termed effective permeabilities. by analogy to the specific permeability as defined by Darcy's law in its original form. In order to obtain a convenient basis of comparison, the effective permeabilities are referred to the specific permeability, k, of the considered porous medium, with the help of the relations: k1. = KI. k kQ = Kn k..........(2) K,. and Kr. are defined as the relative permeabilities to the liquid and to the gas phase respectively, and frequently expressed in per cent of specific permeability. It may be seen that Equations (1); which appear to be a direct generalization of Darcy's law, correspond to the assignment at any given time of a set of "local" permeabilities to each point of the porous medium, and represent in a differential form the two fluid flow system as a simple superposition of the individual single flow systems. The above interpretation implies that the effective or relative permeabilities are independent of pressure or rate of flow,

Jan 1, 1951

By L. A. Rapoport, W. J. Leas

As a preliminary, consicleration is given to the conventional definition of relative permeability and to the conditions governing the simultaneous flow of oil and gas through porous media. For the conditions of flow prevailing throughout most of a gas drive reservoir, the oil and gas can reasonably be supposed to be in capillary equilibrium with each other. Under these conditions, and these conditions only, the relative permeability to liquid can be expressed as a function of saturation. The relative permeability to liquid in that case is dependent upon the distribution of fluids which itself is shown to be related to the capillary pressure, and, in turn, to the saturation. As a consequence, relative permeability to liquid can be expressed in terms of the volume and surface area of a network of liquid channels bounded by the rock and the gas phase. While the volume of this network can be evaluated accurately, the surface area cannot. However, for any such volume, maximum and minimum values of the corresponding surface area can be calculated from capillary pressure data. It is then possible to establish for any saturation the limits within which the value of the relative permeability to liquid must lie. As a consequence of the theoretical development, the validity of an experimental method for measuring relative permeability to liquid which utilizes a stationary gas phase is demonstrated. In this method capillary barriers are cemented to the ends of the core sample to permit the maintenance of capillary equilibrium between the two phases. At the same time, this procedure eliminates undesirable secondary phenomena such as end effects, fissure effects, etc., the presence of which adversely affect the results of other laboratory methods. The results obtained by theoretical calculations, and experimentally, are discussed. In view of the overall precision that can presently be obtained in reservoir calculations, the agreement between the calculated and measured relative permeability to liquid data can be considered satisfactory. In conclusion, for reasons of economy and simplicity, the procedure of calculating limiting relative permeability to liquid curves from capillary pressure data is indicated for general engineering purposes. It is shown that the above procedure can easily be extended to the cases where connate water is present. Its use for reservoir studies is particularly recommended in conjunction with the method for measuring relative permeability to gas' which simultaneously yields the capillary pressure data necessary for the calculations. THEORETICAL Definition of Relative Permeabilities — Basic Equations for Heterogeneous Flow The equations by which the relative permeability concept is defined and upon which the formulation of all of the gas-oil flow problems rests at the present time are expressed as: V, = — Grad PL = — Grad PL ....(la) PL µL, k k KG VG = —K - Grad PG k- Grad Pc .... (lb) Mo where ,. and G refer to liquid and gas; V is the volumetric rate of flow per unit gross area. µ the viscosity, Grad P the potential gradient. and k the specific permeability of the porous medium.* (For horizontal flow, Grad P becomes the pressure gradient; otherwise, gravity must be included.) According to these expressions, each of the constituent phases is considered similar to a homogeneous system where the volumetric rate of flow is proportional to the pressure gradient, and for each of which the constants of proportionality, k, and kG, are termed effective permeabilities. by analogy to the specific permeability as defined by Darcy's law in its original form. In order to obtain a convenient basis of comparison, the effective permeabilities are referred to the specific permeability, k, of the considered porous medium, with the help of the relations: k1. = KI. k kQ = Kn k..........(2) K,. and Kr. are defined as the relative permeabilities to the liquid and to the gas phase respectively, and frequently expressed in per cent of specific permeability. It may be seen that Equations (1); which appear to be a direct generalization of Darcy's law, correspond to the assignment at any given time of a set of "local" permeabilities to each point of the porous medium, and represent in a differential form the two fluid flow system as a simple superposition of the individual single flow systems. The above interpretation implies that the effective or relative permeabilities are independent of pressure or rate of flow,

Jan 1, 1951

By T. Szaplonczay, D. E. Light

The auto-oxidation of sulfur dioxide to form sulfuric acid in commercially produced barren and recycle liquors, containing 1.66 and 4.56 gpl Fe respectively, from Elliot Lake was studied. A gas mixture, containing 3.5% SO2 and air was introduced into these liquors through a frit at a rate of 6.0g SO2 per hour per liter of solution. The barren and recycle were heated to 60°C. At the end of the first 24 hours of the process the concentrations of acid produced were 158 and 220 gpl H2SO4 for the barren and recycle respectively. Corresponding conversion efficiencies were 70 and 83%. In the period from 24 to 36 hours the rate of acid production decreased so that the H2SO4 concentrations at the end of 36 hours were 180 gpl for the barren and 260 gpl for the recycle; average conversions for the initial 36 hours were 55 and 68% respectively. Many investigators1'2'3 have considered the oxidation of sulfur dioxide to form sulfuric acid in aqueous solutions containing metallic ions. A summary of the work performed on this subject prior to 1946 has been presented by Keyes4 who described the auto-oxidation process as follows. Keyes also suggested that in this second reaction ferric ion serves as a catalyst for the conversion of sulfur dioxide to sulfuric acid. Neytzell-de Wilde and Taverner5 have reported on the use of auto-oxidation to produce a 4 to 5% sulfuric acid solution for use in a cyclic leach process at South African uranium plants. This paper describes investigations carried out to determine the feasibility of using the auto-oxidation process to produce sulfuric acid solutions of as high concentration as possible using commercially produced uranium plant barren and recycle liquors from the Elliot Lake region of Ontario. These liquors contained 1.66 and 4.56 gpl respectively of iron, chiefly in the ferrous state. This investigation is of particular interest to the uranium producers in Elliot Lake where the ores contain 3 to 4% sulfur, as sulfides. Flotation of these sulfides and roasting of same to produce SO, bearing gases have been successfully demonstrated using conventional methods.6'7 Barren and recycle solutions, as described previously, are also produced in large tonnages by these uranium producers. The experimental method and apparatus used to examine the auto-oxidation process will be described first. Then the tests carried out on laboratory prepared aqueous solutions containing ferric sulfate to determine optimum conditions will be presented. The next section will describe the tests using the commercial barren and recycle liquors. A final section will summarize the conclusions of the work. EXPERIMENTAL APPARATUS AND PROCEDURES Two types of solutions were used in the tests, a laboratory prepared aqueous solution containing definite amounts of ferric sulfate, and commercially produced iron bearing solution obtained from a uranium leaching plant in the Elliot Lake area. Two liters of a solution to be examined were placed in a 3 in. diam by 30 in. long glass cylinder with a cross-sectional area of 7 sq in. A mixture of air, and SO2 supplied from a lecture bottle for convenience, was introduced into the bottom of the vessel through a standard 30 mm glass frit, 700 sq mm in area. The temperature of the apparatus was controlled by a heating tape and variable transformer. Exhaust gases were vented to atmosphere. At the end of the test period the gas flow was shut off and the solution was analysed for H2SO4, Fe ++, and Fe +++, by conventional means. Four variables were examined using the laboratory prepared aqueous solution of ferric sulfate. First, the effect of SO2 concentration, from 1 to 1076, in the feed gas mixture was considered. Second, the temper-

Jan 1, 1964

By A. F. Witt, A. M. Gaudin, A. K. Biswas

Finite contact angles in the rutile-water-organic liquid system are traceable to contamination or are due to addition of a surface-active agent. Finite contact angles are invariably accompanied by hysteresis.1-7 Besides surfactant concentration and pH, the nature of the organic liquid is found to be a factor influencing the magnitude of contact angle hysteresis. In a recent paper the authors have reviewed principles and applications of measurement methods for contact angles and their hysteresis.22 In this paper, these methods are applied to a system consisting of rutile, an organic liquid (benzene, decane, or dode-cane) and water. Surfactant (dodecylamine hydro-chloride) was used at various concentrations and various pH values. MATERIALS A synthetic rutile crystal supplied by the Linde Co. was used. It is a cylinder 1/2 in. diam, with faces cut perpendicular to the c-axis. The crystal is stated to be alumina-free and to be 99.9% pure. Rutile is a high surface energy solid, its calculated average field strength being 2.7 x 105 e.s.u.,9 its dielectric constant10 is 114. The zero point of charge of rutile was measured11 and found to be at pH 6.0. The atomic distances and bond angles of the tetragonal crystal of rutile have been precisely determined.l2 The organic liquids were specially purified. Reagent grade benzene was repeatedly shaken with concentrated sulfuric acid to remove thiophene, then neutralized with sodium hydroxide solution, rinsed with distilled water, dried overnight over anhydrous calcium chloride and filtered. The refractive index of this chemically purified benzene was 1.4977 (at 25°C) - very close to that of pure benzene (n25 1.4979).13 Both n-decane and n-dodecane were washed with aqueous sodium hydroxide, concentrated sulfuric acid (repeatedly, until the acid layer was colorless) and again with alkali, to free the organic hydrocarbon from fatty acids and unsaturated hydrocarbons. The organic phases were subsequently washed with distilled water and dried over anhydrous sodium sulfate. The filtered hydrocarbons were then distilled under vacuum (9-10 mm pressure). Decane, thus purified, showed traces of unsaturated and of carboxylic compounds. On gas chromatographic analysis the purified n-dodecane showed the presence of two impurities. However, the relative retention times of these components did not change substantially when measured on a polar or a nonpolar column. This indicates that the compounds were probably in the same polarity class, i.e. the components were nonpolar like dodecane. Conductivity water has always been one of the liquids. Conductivity of the water used was 10-6 ohm-' cm". Dodecyl ammonium chloride was prepared from pure amine (supplied by Armour and Co., Chicago), by Li in the MIT Mineral Engineering Laboratory.14 The critical micelle concentration at 25°C is known, 0.0138 mol per liter15 or 3.06 gpl. All our experiments have been done at concentrations lower than the critical micelle concentration. The glass vessels, glass drop holder and the rutile crystal were all cleaned with hot chromic acid followed by distilled water, concentrated hydrochloric acid, and again distilled water, and conductivity water. During the experiments, a nitrogen atmosphere was maintained. For this purpose, commercially purified nitrogen was further purified by passing it over hot copper wire at 450°C, then through columns of acidic chromous chloride solution, concentrated alkali solution and distilled water. APPARATUS AND METHODS Hysteresis was produced by the "captive drop" or constant volume drop method as well as by the "expanding-contracting drop" or variable volume drop method. The image of the drop while it is expanding, contracting or moving is projected on a screen and photographed. The developed film is projected through an enlarger and the contact angles measured with a protractor.

Jan 1, 1964

Executive ERLE V. DAVELER. Chair u W. B. HEROY PAUL D. MERICA JOHN M. LOVEJOY WILLIAM WRAITH Finance H. G. MOULTON, Chairman H. T. HAMILTON HENRY KRUMB Admissions JOHN L. CHRISTIE, Chairman GEORGE D. BARRON, Vice-Chairman FRED H. KAY PHILIP KRAFT H. Y. WALKER

Jan 1, 1938

By C. H. Jr. Herty

IT Is well known that manganese will desulfurize molten iron through the formation of manganese sulfide, which, being only slightly soluble in the metal, rises to and enters the slag where it remains as such (mixer slag) or is converted partly or wholly to calcium sulfide (basic open¬hearth slag). The reaction by which manganese sulfide is formed is Mn + FeS = MnS + Fe. This reaction is generally considered to be reversible, although McCance1 states- that such is not the case. The experimental work was carried out to confirm the results of Rohl2 as to the reversibility of the reaction. Six trials are herein considered. In each 200 grams of electrolytic iron free from manganese and sulfur were melted in a pure zirconia crucible in a carbon resistance electric furnace. To the melted iron in runs 2, 3 and 4 metallic manganese and manganese sulfide were added to give 1, 2 and 4 per cent. manganese respectively, with 0.50 per cent. of sulfur in each. In runs 5, 6 and 7, metallic manganese andiron sulfide to give the same proportions of manganese and sulphur as in runs 2, 3 and 4, were added. The melts were held molten in the furnace for an hour and then cast into small ingots.

Jan 2, 1925

By N. C. Fick, R. L. Rickett

DESPITE the large volume of literature on alloys of iron and silicon,1 there is little published information dealing specifically with the constitution, at various temperatures, of the alloys containing less than 0.10 per cent carbon and from 0.5 to 4.5 per cent silicon that are used extensively in the electrical industry. Because such information was needed by those engaged in the production of these alloys in, sheet and strip form, the constitution was determined of a series of commercial silicon steels containing 0.05 to o.08 per cent carbon and 0.20 to 4.31 per cent silicon, over the temperature range 1300° to 2500°F. These alloys were all from regular production heats and of commercial quality. The results of, the tests are given in Fig. I and for comparison the constitution diagram of iron-silicon alloys with 0.01 to 0.02 per cent carbon, taken from the literature, is also presented. MATERIAL AND PROCEDURE All steels were hot-rolled to a thickness of 0.060 to 0.080 in. and used in this condition. Their chemical compositions, including over-all check analysis, and "center" analysis for carbon and silicon, are given in Table I. The so-called center analysis was determined on samples pickled to remove the outer surface and leave only the center third of the gauge thickness-the portion of the sample on which metallographic ratings were based. In most, but not all, of the alloys, slightly higher carbon was found at the center than when the whole strip was sampled; the two methods of sampling show relatively little difference in silicon. Two of the steels, A and E, contain relatively high phosphorus, while I and K are somewhat higher in manganese than the others. [ ] The procedure consisted essentially of heating specimens (about 1/16 by 3/8 by 3/4 in.), protected from oxidation or change in carbon content, at a temperature in the desired. range and for a selected period, after which they were quenched in iced brine; the degree of transformation that had then occurred was determined by metallographic examination. The soaking periods were selected after preliminary investigation had shown that a con-

Jan 1, 1946

By R. L. Rickett, N. C. Fick

Despite the large volume of literature on alloys of iron and silicon,' there is little published information dealing specifically with the constitution, at various temperatures, of the alloys containing less than 0.10 per cent carl~on and from 0.5 to 4.5 per cent silicon that are used extensively in the electrical industry. Because such information was needed by those engaged in the production of these alloys in sheet and strip form, the constitution nas determined of a series of commercial silicon steels containing 0.05 to 0.08 per cent carbon and 0.20 to 4.1 per cent silicon, over the temperature range 1300° to 1500°F. These alloys were all from regular production heats and of commercial quality. The results of the tests are given in Fig. I and for comparison the constitution diagram of iron-silicon alloys with 0.01 to 0.02 per cent carbon, taken from the literature, is also presented Material and Procedure All steels were hot-rolled to a thickness of 0.060 to 0.080 in. and used in this condition. Their chemical compositions, including over-all check analysis, and "center" analysis for carbon and silicon, are given in Table I. The so-called center analysis was determined on samples pickled to remove the outer surface and leave only the center third of the gauge thickness—the portion of the sample on which metallographic ratings were based. In most, but not all, of the alloys, slightly higher carbon was found at the center than when the whole strip was sampled; the two methods of sampling show relatively little difference in silicon. Two of the steels, A and E, contain relatively high phosphorus, while I and K are somewhat higher in manganese than the others. The procedure consisted essentially of heating specimens (about 1/16 by 3/8 by 3/4 in.), protected from oxidation or change in carbon content, at a temperature in the desired range and for a selected period, after which they were quenched in iced brine; the degree of transformation that had then occurred was determined by metallographic examination. The soaking periods were selected after preliminary investigation had shown that a con-

Jan 1, 1947

By N. C. Fick, R. L. Rickett

Despite the large volume of literature on alloys of iron and silicon,' there is little published information dealing specifically with the constitution, at various temperatures, of the alloys containing less than 0.10 per cent carl~on and from 0.5 to 4.5 per cent silicon that are used extensively in the electrical industry. Because such information was needed by those engaged in the production of these alloys in sheet and strip form, the constitution nas determined of a series of commercial silicon steels containing 0.05 to 0.08 per cent carbon and 0.20 to 4.1 per cent silicon, over the temperature range 1300° to 1500°F. These alloys were all from regular production heats and of commercial quality. The results of the tests are given in Fig. I and for comparison the constitution diagram of iron-silicon alloys with 0.01 to 0.02 per cent carbon, taken from the literature, is also presented Material and Procedure All steels were hot-rolled to a thickness of 0.060 to 0.080 in. and used in this condition. Their chemical compositions, including over-all check analysis, and "center" analysis for carbon and silicon, are given in Table I. The so-called center analysis was determined on samples pickled to remove the outer surface and leave only the center third of the gauge thickness—the portion of the sample on which metallographic ratings were based. In most, but not all, of the alloys, slightly higher carbon was found at the center than when the whole strip was sampled; the two methods of sampling show relatively little difference in silicon. Two of the steels, A and E, contain relatively high phosphorus, while I and K are somewhat higher in manganese than the others. The procedure consisted essentially of heating specimens (about 1/16 by 3/8 by 3/4 in.), protected from oxidation or change in carbon content, at a temperature in the desired range and for a selected period, after which they were quenched in iced brine; the degree of transformation that had then occurred was determined by metallographic examination. The soaking periods were selected after preliminary investigation had shown that a con-

Jan 1, 1947

By B. M. Larsen, L. S. Darken

SOME years ago we collated all laboratory data then available to us on the distribution at equilibrium of manganese and of sulphur between metal and simple slags, and used the results in setting up an equation, which proved to be in accord with determinations of the distribution ratio of manganese and of sulphur between liquid steel and open-hearth slag, over a wide range of operating conditions. We now present an outline of our calculations and inferences on these two closely related questions, which are of especial importance because of the advisability of conserving manganese wherever possible. In general. our results show that in the open-hearth furnace equilibrium between metal and slag, with respect to both manganese and sulphur, is substantially attained during the finishing period of the heat, or in about a half hour to an hour after any additions were made. This implies that the end result will be identical whether manganese is added as alloy or metal to the liquid steel or as oxide to the slag. The proportion of total manganese retained by the steel is favored: (I) by use of the minimum amount of lime, consistent with other operating limitations, required to give a lime-silica ratio of about 2.4, which usually corresponds to a minimum practical slag volume; (2) by a high concentration in the slag of MnO relative to FeO; (3) by high operating temperature. Absorption of sulphur by the slag from the liquid metal is favored: (I) by large slag volume; (2-by a high concentration of active (or "free") lime and of manganese oxide dis) solved in the slag; (3) by low concentration of silica, iron oxide, and phosphate dissolved in the slag. DISTRIBUTION OF MANGANESE BETWEEN SLAG AND METAL AT EQUILIBRIUM On the basis that the distribution of manganese between liquid steel and slag is controlled by the reaction [FeO + Mn ;7± MnO + Fe [A] slag metal slag metal] the distribution at equilibrium, at a given temperature, is expressed by the equilibrium constant for this reaction, which is defined as [K" aFPI OFeO ? aMn] where a is the activity of the molecular species denoted by the subscript. The activity of each of the several components, although it is not known precisely, is approximately equal to the concentration of each component expressed as its mol fraction; that is, as the ratio of the number of mols of the given component to the total number of mols of all the molecular species present in the metal or slag, as the case may be. Moreover, since the activity, or concentration, of iron in the liquid metal is in fact substantially constant, the term aFe may he combined with K" to give a new constant K'. Making these changes.

Jan 1, 1942

By H. S. Gibson

A PROCESS that has come to be known locally as "multistage stabiliza-tion" has been developed in the Haft Kel field of the Anglo-Iranian Oil Co. in southwest Iran, for the recovery of casinghead gasoline. It con-sists in releasing the dissolved gases from the crude by stages, a practice common in many fields, but which, so far as is known, has nowhere been carried to the extent to which it is employed in Iran. It has been in use there for nearly nine years, during which time some 200 million barrels of crude have been handled by the process. This process of gasoline retention consists in preventing the greater part of the casinghead gasoline hydrocarbons (the butanes and pentanes) from ever leaving the crude, instead of allowing them to be vaporized and then recovered from the lighter gases by the usual compression or absorption processes. Its efficiency is fully equal to that obtained by the absorption process; its disadvantage is that it increases the quantities of ethane and propane in the crude sent to the refinery, but with the growing demand for propane this drawback is vanishing. When casinghead gasoline is recovered as a separate liquid in the Iranian fields, it is blended with the crude, as the only outlet is through the refinery, and the crude-oil pipe line offers the cheapest means of transportation. It is under these conditions that the retention of the butanes and pentanes in the crude by multistage stabilization is a most attractive process, possessing as it does the following advantages: (1) extreme simplicity, (2) low first cost, (3) easy installation, (4) practically 100 per cent operating-time efficiency, (5) no operators required, (6) no water or other services required, (7) negligible maintenance, (8) once established, very little routine testing is necessary. The one essential for reasonably efficient multistage stabilization is that the flowing pressures of the wells should be relatively high; i.e., they should not be less than about one-third the saturation pressure of the crude in the reservoir. This is a very general statement, of course, and much depends on the type of crude and its temperature.

Jan 1, 1939

By William H. Spice

Drilling activities in South Central Texas for the year 1945 continued the steady increase over the past two years, while new fields discovered for the year included four new gas fields and one field extension. In the 30 counties included in this area, which comprises district No. 1, Oil and Gas Division, Railroad Commission of Texas, 141 exploratory wells were completed, compared with 61 drilled in 1944 and 29 drilled in 1943. Of these 141 tests, 55 were field well and 86 were wildcats; 38 were completed as oil wells, S as gas and gas-distillate producers, and 95 were abandoned as dry. Atascosa and McMullen Counties were the most active in the district, accounting for 73 of the wells drilled.

Jan 1, 1946

By J. H. Keeler

The tensile characteristics of Zr-Fe binary alloys containing up to 5 atomic pet Fe are reported for the temperature range —195o to 500°C. A linear relation between stress at constant strain and volume fraction ZrFe2 was found. The coincidence of data from unalloyed zirconium with zero volume fraction ZrFe2 indicated little or no solid solution in IL-zirconium, in agreement with Hayes, Roberson, and O'Brien.' The absolute increase in strength due to particle strengthening, although decreasing with increasing temperature, was a greater percentage at high temperature. ZIRCONIUM is of interest for use in nuclear reactors because of its low neutron absorption, good corrosion resistance, and high melting temperature. The alloying of zirconium with iron has been considered as a means of increasing the mechanical strength of zirconium without seriously increasing the neutron absorption " over that of unalloyed zirconium. The Zr-Fe system has a eutectic at 934°C and 23.7 atomic pet Fe and a eutectoid at 800°C and 4.0 atomic pet Fe. The zirconium-rich end of this system determined by Hayes, Roberson, and O'Brien' is shown in Fig. 1. The intermetallic phase coexisting with a and ß-zirconium has been reported as Zr2Fe3,1 with a,, - 7.04A, and as ZrFe2,2 face-centered-cubic, the phase being of the MgCu, type (C-15). It was more recently agreed to be ZrFe33 and face-centered-cubic. This intermetallic phase is essentially insoluble in a-zirconium, the hexagonal-close-packed modification; and the lack of solubility makes the system particularly interesting metallurgically. The system is strengthened almost exclusively by particles of in-termetallic phase, and there is very little solid solution strengthening to complicate the analysis. The Bureau of Mines, in its survey of zirconium-base alloys,' reported the tensile properties of Zr-Fe alloys made from chloride process zirconium, induction melted in graphite crucibles, and swaged at 850°C in iron sheaths. Additional data on these ZrFe alloys were given by Hayes, Roberson, and O'Brien.' Chubb and Muehlenkamp% have recently reported the strength of Zr-Fe alloys containing up to about 1.25 atomic pet Fe. These alloys were made from crystal bar zirconium, hot worked at 820°C, annealed at 700°C, and tested both at room temperature and at 316°C. Experimental Procedure The materials used in this investigation were high purity zirconium made by the iodide process and electrolytic iron. The composition of the zirconium as obtained by spectrographic analysis and the nominal composition of the iron are given in Table I. Alloy ingots weighing 100 g were made by are-melting under argon in water-cooled copper crucibles in a multihearth furnace."

Jan 1, 1957

By Michael B. Bever, John R. Anderson

Carbon may affect the alloys of copper in several ways. Provided an alloying element does not oxidize preferentially, even minute quantities of carbon dissolved in liquid alloys of high copper content will form insoluble carbon oxide gases under oxidizing conditions. Gas porosity in castings of high-copper alloys can originate in this way. In certain alloys of low copper content carbon may have considerable solubility and may be an effective deoxidizer. In these alloys carbon will tend to suppress porosity. Carbon that is dissolved in the molten alloy is likely to be retained in the solidified metal. The effects of carbon on the physical properties of the metal are determined by the form in which it is present. Depending on the alloying elements and also on the cooling rate, carbon may precipitate as graphite, may form a carbide or may remain in solid solution on cooling. As solid copper does not dissolve a measurable amount of carbon, a carbon-bearing solid solution can occur only if the copper is alloyed with a large excess of an element that forms such a solution. The effect of graphite or of carbides on the properties of an alloy will depend on the size and distribution of the precipitated particles. As Hensel pointed out in discussion,' the formation of an alloy carbide may interfere with the age-hardening properties of a copper alloy. One would also expect that the presence of carbides or of graphite will under certain conditions promote corrosion or high-temperature failure in nonferrous alloys. Since carbon has an effect on the soundness of castings and affects the structure and behavior of solid copper alloys, its solubility in the liquid alloys is of practical importance. The isothermal change of carbon solubility with alloy composition is of interest from a theoretical standpoint. The binary alloys of copper with manganese and with nickel are used industrially and serve as a base for more complex alloys. The solubility of carbon in each of these metals is known, but its solubility in their alloys has not been determined. Earlier Data The solubility of carbon in molten pure copper is about o.oooi pct at II00°C and 0.0004 pct at 1475°C.l Various authors2""6 have published data on the solubility of carbon in molten manganese. There is agreement on a value of about 6.7 pct in the temperature range r2170 to 1245°c This solubility value corresponds to the formula Mn3C. It increases very little with increasing temperature. Corson7 states that carbon is soluble in copper-manganese alloys and that the

Jan 1, 1947

By John R. Anderson, Michael B. Bever

Carbon may affect the alloys of copper in several ways. Provided an alloying element does not oxidize preferentially, even minute quantities of carbon dissolved in liquid alloys of high copper content will form insoluble carbon oxide gases under oxidizing conditions. Gas porosity in castings of high-copper alloys can originate in this way. In certain alloys of low copper content carbon may have considerable solubility and may be an effective deoxidizer. In these alloys carbon will tend to suppress porosity. Carbon that is dissolved in the molten alloy is likely to be retained in the solidified metal. The effects of carbon on the physical properties of the metal are determined by the form in which it is present. Depending on the alloying elements and also on the cooling rate, carbon may precipitate as graphite, may form a carbide or may remain in solid solution on cooling. As solid copper does not dissolve a measurable amount of carbon, a carbon-bearing solid solution can occur only if the copper is alloyed with a large excess of an element that forms such a solution. The effect of graphite or of carbides on the properties of an alloy will depend on the size and distribution of the precipitated particles. As Hensel pointed out in discussion,' the formation of an alloy carbide may interfere with the age-hardening properties of a copper alloy. One would also expect that the presence of carbides or of graphite will under certain conditions promote corrosion or high-temperature failure in nonferrous alloys. Since carbon has an effect on the soundness of castings and affects the structure and behavior of solid copper alloys, its solubility in the liquid alloys is of practical importance. The isothermal change of carbon solubility with alloy composition is of interest from a theoretical standpoint. The binary alloys of copper with manganese and with nickel are used industrially and serve as a base for more complex alloys. The solubility of carbon in each of these metals is known, but its solubility in their alloys has not been determined. Earlier Data The solubility of carbon in molten pure copper is about o.oooi pct at II00°C and 0.0004 pct at 1475°C.l Various authors2""6 have published data on the solubility of carbon in molten manganese. There is agreement on a value of about 6.7 pct in the temperature range r2170 to 1245°c This solubility value corresponds to the formula Mn3C. It increases very little with increasing temperature. Corson7 states that carbon is soluble in copper-manganese alloys and that the

Jan 1, 1947

By W. A. Forbes

OUR present-day geological surveys show that 36 of our States are underlain with bituminous coal, covering a total area of 496,709 square miles. The North American continent possesses 69 per cent of the world's coal reserves, with the United States alone having an estimated 55 per cent. The American coal reserves, in tons, are calculated to he about 3,500,000,000,000 tons, of which we have exhausted about 1 to 1 1/2 per cent. If this coal were mined at the rate of the 1918 production-a record output of 579;000,000 tons-it would not be depleted for 4,000 years. The more easily accessible and high-grade coals would obviously be consumed much before this; some estimates are 100 years. The natural progress of the nation's industries up to 1910 encouraged on every hand the development of new mines, especially where cheap and easy access to coal measures was coupled with short hauls to the consumer. Over-development resulted, which is perhaps today one of the fundamental causes for the many difficulties faced by the coal industry, which is highly competitive; about 70 per cent of the production cost is labor. Salient statistics for 1930, recently issued by the U. S. Bureau of Mines, follow:

Jan 1, 1932

By B. M. Larsen, L. S. Darken

Some years ago we collated all laboratory data then available to us on the distribution at equilibrium of manganese and of sulphur between metal and simple slags, and used the results in setting up an equation, which proved to be in accord with determinations of the distribution ratio of manganese and of sulphur between liquid steel and open-hearth slag, over a wide range of operating conditions. We now present an outline of our calculations and inferences on these two closely related questions, which are of especial importance because of the advisability of conserving manganese wherever possible. In general, our results show that in the open-hearth furnace equilibrium between metal and slag, with respect to both manganese and sulphur, is substantially attained during the finishing period of the heat, or in about a half hour to an hour after any additions were made. This implies that the end result will be identical whether manganese is added as alloy or metal to the liquid steel or as oxide to the slag. The proportion of total manganese retained by the steel is favored: (I) by use of the minimum amount of lime, consistent with other operating limitations, required to give a lime-silica ratio of about 2.4, which usually corresponds to a minimum practical slag volume; (2) by a high concentration in the slag of MnO relative to FeO; (3) by high operating temperature. Absorption of sulphur by the slag from the liquid metal is favored: (I) by large slag volume; (2) by a high concentration of active (or "free") lime and of manganese oxide dissolved in the slag; (3) by low concentration of silica, iron oxide, and phosphate dissolved in the slag. Distribution 02 Manganese between Slag and Metal at Equilibrium On the basis that the distribution of manganese between liquid steel and slag is controlled by the reaction FeO + Mn -& MnO + Fe [A] slag metal slag metal the distribution at equilibrium, at a given temperature, is expressed by the equilibrium constant for this reaction, which is defined as K,, _ aMnO' afe aFeO ' aMn where a is the activity of the molecular species denoted by the subscript. The activity of each of the several components, although it is not known precisely, is approximately equal to the concentration of each component expressed as its mol fraction; that is, as the ratio of the number of mols of the given component to the total number of mols of all the molecular species present in the metal or slag, as the case may be. Moreover, since the activity, or concentration, of iron in the liquid metal is in fact substantially constant, the term afe may be combined with K" to give a new constant K'. Making these changes, 7

Jan 1, 1942