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By A. G. Lyle, J. D. Runkle, G. A. Gillies

THE evaluation of data obtained by selective flotation from even a simple ore is a very difficult process, and when the ore tested is complex the process becomes extremely difficult and cumbersome. The authors, in the course of an investigation into the selective behavior of various flotation reagents on nonmetallic minerals§ were confronted with an aggravated form of this difficulty, owing to the large mass of data that had accumulated over a period of years. They finally devised a method whereby the results of the various flotation tests could be correlated and interpreted by means of graphs representing recoveries and rejections of the component minerals in the ore. This method of graphical analysis proved so useful in nonmetallic flotation that it was afterwards applied to sulphide flotation, where it yielded equally satisfactory results. Since this method of analysis leads to very definite conclusions as to the effect of changes in reagents and flotation procedure, it is felt that a wider application of the method might assist the industry by reducing the amount of test work required, and possibly increase the accuracy of the final analysis. GRAPHS In Fig. I, four curves are plotted on the same graph with cumulative percentages as ordinates and cumulative weights as abscissas. In this instance the four curves are named, respectively: the barite-recovery curve, the limestone-rejection curve, the silica-rejection curve, and the summation curve. In these tests barite was the mineral concentrated, therefore a barite concentrate was produced. Definitions Before explaining the curves in detail it might be advisable to define several new terms, such as "percentage rejection," "summation index," and "summation curve," as well as the word "test," which has been used in a special sense. A "test" will include all the operations performed upon a batch of ore from the time it is placed in the rod mill until the last product has been assayed. Thus a test may be a comparatively simple procedure producing only one concentrate and a tailing, or it may be a very complicated procedure producing five or more concentrates of a specific mineral as well as a tailing. The number of concentrates produced will depend entirely upon whether the collector was added to the pulp in the flotation cell in one lot or was added in five or more portions. Percentage Rejection.-The ability of a selective flotation collector to reject an undesired mineral is just as important as its ability to collect the desired mineral. The percentage rejection curves shown on the graphs give this factor due consideration and its value is calculated as follows: Suppose a concentrate contains 5 per cent of an undesired mineral. This indicates

Jan 1, 1942

President MRS. HARRISON SOUDER Smith Paramus Road Ridgewood, N. J. First Vice-president MRS. ROBERT HURSH 10 Kilburn Road Belmont, Mass. Second Vice-president MRS. ERLING L. JORGENSEN 95 Knollwood Rd. Short Hills, N. .1. Third Vice-president MRS. PERCY E. BARBOUR 1R(; Riverside Drive New York, N. Y. Fourth Vice-president MRS. C. B. MURRAY 2040 Stearns Rd. Cleveland, Ohio

Jan 1, 1938

By J. M. Campbell, T. S. Buxton

The most widely used methods of predicting the volumetric properties of gas are based on the principle of corresponding states, which asserts that the compressibility factor is a universal function of reduced temperature and pressure. Previous studies have shown that the acentric factor, as proposed by Pitzer, l is an important addition to reduced pressure and reduced temperature as factors affecting the compressibility factor. Results of this study indicate that, if the pseudocritical temperature and pressure used to determine the reduced conditions are adequately predicted, characterization of natural gas-carbon dioxide mixtures with the acentric factor will allow reliable determination of the compressibility factor. Comparisons of predicted and experimental compressibility factors have shown that the pseudo-critical constant rules of Stewart, Burkhardt and Voo 2 are satisfactory for hydrocarbon mixtures. However, these rules fail to predict the pseduo-critical constants for hydrocarbon-carbon dioxide mixtures. Based on graphically determined pseudocritical temperatures for binary hydrocarbon-carbon dioxide mixtures, a correlation which gives the required correction to the Stewart, Burkhardt and Voo rules was prepared and a compressibility factor prediction technique was proposed. To test the proposed technique, compressibility factors for live mixtures of methane, carbon dioxide and either ethne or propane were experimentally determined at 100, 130 and 160F and pressures up to 7,026 psia. The predicted and experimental compressibility factors for these live mixtures had an average absolute deviation of 0.55 percent. INTRODUCTION Two-parameter generalized correlations based on the principle of corresponding states (PCS) are presently available for reliably predicting the compressibility factor of lean natural gas, i.e., natural gas with low concentrations of hydrocarbons heavier than methane. When these same correlations are used for mixtures of natural gas and carbon dioxide, large deviations between actual and predicted compressibility factors are observed. This study was undertaken to provide a means for accurately predicting the compressibility factor for such mixtures. In the past, two avenues of approach have been employed to extend the applicability of the PCS. The first has been to introduce additional parameters. The second has been to develop combination rules for predicting pseudocritical constants which do not suffer from the limitations of the commonly used molal average constants. In this study, both of these approaches have been considered and employed to arrive at a method for predicting the compressibility factor of mixtures of hydrocarbons and carbon dioxide. SELECTION OF A THIRD PARAMETER Failure of the original PCS to predict the compressibility factor for all pure gases, regardless of their mass, shape or polar moment, has led to the introduction of additional parameters into the PCS. Parameters have been introduced to correct for quantum deviations,3-5 non-spherical or globular shapes6-9 and for polar moments.8-12 In addition to these parameters which are based on some microscopic property and intended to correct for some specific cause of deviation, more general parameters based on some bulk property have also been introduced.1913-16 To use additional parameters to correct for each of the possible causes of deviation among the individual constituents of a gas mixture would require a rather complex form of the PCS. To maintain the PCS in as simple a form as possible, it is more desirable to have a single third parameter which is based on some bulk property influenced by several of the factors causing deviations. The third parameter selected for use in this study is a factor originally proposed by Pitzer.9

By Edgar C. Bain

In studying the structural characteristics of martensite it is desirable that a clear conception of the material from which martensite is produced should first be obtained. Any theory of its formation and structure incompatible with the facts of its parent substance, austenite, can be eliminated with little consideration. Austenite is the name applied to solid solutions of carbon and other elements in gamma iron. At temperatures above about 900" C. (1650" F.), pure iron exists in a system of crystallinity1 entirely different from the crystal structure below that temperature. This high-temperature allotrope of iron is of an atomic structure associated with great ductility, having very manifold symmetry and an abundance of easy slip planes. The exceptionally ductile and malleable metals (gold, silver, platinum, copper, aluminum, and nickel) have this same atomic arrangement— the face-centered cubic. The low-temperature allotrope of iron, alpha iron, the solid solutions of which are known as ferrite, has a body-centered cubic arrangement of atoms. Like it, in crystal structure, are the less ductile and malleable metals, molybdenum, tungsten, titanium and chromium. Fig. 1 shows the two atomic arrangements known in iron; the diagrams are drawn to scale. Either of these modifications of iron may dissolve other elements in the solid state; by so doing, the temperature of the transformation is changed. In general 2-7, it appears that a solid solvent metal dissolves a metal solute by substituting foreign atoms in its own space lattice. Thus, iron may dissolve nickel in either of its crystalline forms by permitting an atom of nickel here and there to occupy the normal position

Jan 1, 1924

By J. Brian Eby

The Gulf Coast of southern Louisiana during the year of 1940 was subjected to an extensive exploration and development campaign, as a result of which 16 oil fields and about 38 new producing sands were found. Although this record of discovery appears in keeping with the rate of 1939 actually in amount of new proven reserves, it may fall short of that of the previous year. Only five or six of the discoveries rated as first-class or important fields at the close of the year. The most prominent new fields opened during the year were Neale field in Beaure-gard Parish, the West Cote Blanche field in St. Mary Parish, the Stella field and the West Bay field in Plaquemines Parish, and the Lake Salvador field in St. Charles Parish. There were many important oil-sand discoveries in proven fields, such as in the Bayou Perot field, the Golden Meadows field, the Iowa field, West Lake Verrett field, and the Venice field. During the year, 1047 weUs were drilled in southern Louisiana, of which 768 were completed as oil-producing wells, 17 as gas wells and 262 as dry holes. The Neale field in northwest Beauregard Parish is considered one of the most important discoveries of the year. The f~eld centers around the north half of sec. 26, 'Y.3 S., R.I I W., just north of the town of Neale. It was discovered by the Atlantic Refining Co., using reflection seismograph to locate the structure. Production was found in the second well drilled in the Wilcox sand on the downthrown side of a fault. The structure is known as the "Tepetate" type, being similar to that of the well-known Tepetate field. There were 12 oil wells and 3 dry holes drilled during the year. The Wilcox sand in this field occurs between 8350 and 8400 ft. and averages 30 ft. in thickness. The West Cote Blanche Bay field, in West Cote Blanche Bay, St. Mary Parish, is a 1940 discovery by the Texas Company, credited to reflection seismograph exploration. The oil is from two sands occurring at 3110 to 3140 ft. and from 4950 to 5020 it. Four wells were drilled during the year, three oil wells and one dry hole. The deepest hole drilled reached 9491 ft. without encountering salt or dome material. In Plaquemines Parish, south of New Orleans, the California company has a new field known as the Stella field. The sand was found at a depth of 7485 ft., and 5 ft. of perforations made a well capable of producing 486 bbl. of oil in 24 hr. through a 9.is-in. choke. The oil is 42" gravity. The discovery well was drilled to a total depth of 10,258 ft. and other producing sands were indicated. A good field appears assured, although only one well was completed within the year. The Lake Salvador field, in the center of Lake Salvador, St. Charles Parish, gives promise of being one of the most important discoveries of the year. The discovery well was perforated at 9775 to 9800 ft. making 850 bbl. of 33.7° gravity oil daily through a 1/4-in. choke. Three wells were completed in 1940 but few details have as yet been made available.he Gulf Oil Corporation apparently has a good field in its wildcat discovery in West Bay, Plaquemines Parish. This well found

Jan 1, 1941

By H.A. Schwartz

From time to time, one of the authors has had occasion to investigate the graphitizing reaction and has published the results mainly as discussion' of the work of other investigators. In view, therefore, of the diversity of both observations and interpretation, it seemed well to attempt, a revision of the entire subject in the Research Laboratory of the National Malleable Castings Co. The work consisted of a careful study of a single, impure, iron-carbon alloy. The material, which may be considered typical low-carbon white cast iron of the malleable industry, was an air-furnace iron of the following composit,ion: carbon 2.30 per cent., silicon 1.20 per cent., manganese 0.29 per cent., phosphorus 0.156 per cent., sulfur 0.048 per cent. The freezing range extended from 1213' to 1132' C., the latter figure agreeing with Gontermann's data.2 We have attempted to define the equilibrium diagram of this alloy, in the stable condition as related to the mctastable diagr,aui,- from a temperature somewhat below the euteetic freezing point to a temperature l>clow Arl and for a graphitic-carbon content from practically notliing to the original total rarbon of the specimen (see Fig. 6). More csp~c~ially we desired to locate the line in the stable diagra~n corrcspo~idi~lg to thc Ac, line of the metastable syst,ern, which is designated by analogy, thc At, line (t, from tcrnpcr carbon); also to dctermirle the locat'ion of A tm witah respect, to Acm t,o~vard their lowcr extremities at Arl in ordei to determine whether or not graphitization is completed by th~ separation of an iron-carbon entectoid analogous to pearlite in the iron-cementite system. This would involvc furthcr a colnparison of thc locations of Ihc stablc and met.astable 41 points. As the carbon concelltrations of thc solid solutions of the two syste~~ls are probably not, identical, an explanation of t>lieir differences and of thc,

Jan 1, 1923

By James A. Lewis

It is the purpose of this paper to show the importance of sand characteristics, when combined with other physical data, in evaluating production obtained by secondary recovery operations, and to indicate the benefits to be gained from the application of these principles to primary production. Introduction During the past 10 years there has been a growing interest within the industry regarding the movement of fluids through oil reservoirs. A number of research projects have been directed toward the development of the physical laws governing this movement. In the period 1933 to the present, correlations between laboratory analysis of cores, reservoir fluids and well performance have been established and have been applied to successful secondary water-flooding recovery operations; and to the completion, production, reconditioning and evaluation of wells in new fields. The application of these data to water-flooding, either natural or artificial, is comparatively new, but the principlcs involved were set forth in 1880 by John F. Carll,1 who said: The flooding of an oil district is generally viewed as a great calamity, yet it may be questioned whether a larger amount of oil cannot be drawn from the rocks in that way than by any other, for it is certain that all the oil can-not be drawn from the reservoir without admission of something to take its place. If one company owned all of the wells drawing upon a pool, and had accurate records of the depth and characteristics of the oil producing stratum in each well, it is quite possible that some system might be devised by which water could be let down through certain shafts, and thus the rocks be completely voided of oil and left full of water. As it is, however, no systematized plan of action can be adopted. The careless handling of one well. by which water is let down to the oil rock, may spoil several others belonging to different parties. A clashing of interests at once arises and is likely to result in disaster to the whole district. In judging of the probable effects of the intro-duction of water into any particular oil district several things are to be considered. (1st) The time of flooding—whether early in the progress of development, while yet a large percentage of oil remains unexhausted or at a later period after the supply has suffered from long continued depletion. (2nd) The structure of the rock—whether regular and homogeneous throughout, or composed of fine sand inter. bedding connected and irregular layers of gravel, sometimes lying near the top and at others near the bottom. (3rd) The shape of the area being flooded. (4th) The position of the point at which water is admitted. in relation to the location of the surrounding wells still pumping oil. (5th) The height (which governs the pressure) of the column of water obtaining admittance. (6th) The duration of the water supply. Although we may take exception to part of Carll's reasoning, particularly " and thus the rocks be completely voided of oil and left full of water," we must give him credit for pointing out the increased effectiveness of water encroachment in displacing oil from a sand and for his recording six of the present seven considerations necessary for evaluation of production of oil by water

Jan 1, 1942

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

The results of an extensive experimental program relating to the effectiveness of gravel screens have been correlated. The factors considered in some detail include gravel size and condition of packing, sand size and size distribution, fluid velocity, fluid viscosity, and thickness and arrangement of grave! screens. Good agreement between calculated values based upon probability considerations and experimental results relating to the influence of the thickness of the gravel screen was obtained. All of these factors are treated in the correlation in order that their influence may be taken into account in ascertaining the characteristics of an effective gravel screen for a particular set of conditions. The details of the experimental program are not given in the present paper but a description of generalized behavior and typical experimental results are recorded in graphic form. Introduction Gravel screens have been placed in water and oil wells for a number of yearsl,2,3 with the dual objective of increasing the productivity and decreasing the entrance of sand into the well bore. An understanding of the factors controlling the effectiveness of gravel screens in this connection is of industrial interest because it will lead to the proper selection of gravel. Some of the fundamental considerations involved in the migration of sand through a coarser body of porous materials were investigated by Coberly and Wagner4 and further experimental work has been carried out by Gumpertz.5 Apparently the pertinent phenomena are somewhat complex and are influenced by many variables. The present paper deals with the prediction of the behavior of gravel screens under the conditions encountered in practice but does not attempt to discuss the experimental methods or results that were obtained as a background and upon which the prediction is based. Influence OF Gravel Screens upon Productivity The use of a gravel screen may increase the productivity of a well by increasing its effective diameter, and this constitutes one of the objectives of its use. The permeability of most gravels and coarse sands that are employed in practice is so large compared to that of the sand in place that relatively little loss in production rate will arise from the use of material fine enough to cause the desired resistance to sand migration. For example, in Fig. I is depicted the approximate variation in the permeability of closely sized spherical gravels under the conditions of packing likely to be encountered in screens. The dotted lines indicate the variation that might be found because of differences in packing. It should be realized that the permeability is not a single-valued function of the average grain diameter but is related to a large number of factors, including the size, the size distribution and the shapes of the particles. However, Fig. I does permit a rough estimation of the permeability of closely sized spherical gravels and shows that the permeability with even the smaller particles is very large compared to that of most petroleum production horizons.

Jan 1, 1942

By M. C. Leverett, S. E. Buckley

The production of oil is accomplished as a result of its displacement from the reservoir by either gas or water, and the amount of oil recovery is limited by the extent to which the displacing gas or water accumulates. This paper describes the mechanism by which the displacement is effected and the advantages of water over gas as a displacing agent. In the light of the results of experimental observations of the flow of mixtures of oil and/or gas and/or water through sands, certain conclusions are drawn relative to the changing character of the displacement as depletion proceeds, and on the effects of the properties of the fluids and of producing conditions on the ultimate oil recovery. Introduction Crude oil has no inherent ability to expel itself from the pores of the reservoir rocks in which it is found; rather, it must be forcibly ejected or displaced by the accumulation of other fluids. Accordingly, a knowledge of the mechanism by which one fluid is displaced by another is essential to an understanding of the fundamental process by which oil is recovered. The displacing fluids normally available are gas and water, either or both of which may exist originally associated with the oil in a potentially usable form or may be supplied to the reservoir from external sources. Gas is present in most oil reservoirs. If the quantity is relatively small, it may exist originally completely dissolved in the oil, but if the quantity exceeds that which may be held in solution by the oil at the prevailing pressure, the excess will be found in the free state. Most reservoir sands appear to contain some water,l and in the majority of fields the oil is trapped in the structure and held over water. In certain conditions the entrapping water may advance into the oil zone and displace the oil therefrom. This paper describes in a qualitative manner some of the characteristics of the displacement of oil by either gas or water, with an attempt to elucidate somewhat the mechanism by which such displacement is effected. Role of Dissolved Gas When the pressure on an oil containing dissolved gas is reduced to the saturation or bubble-point pressure, gas escapes from solution and expands, imparting to the oil-gas mixture a high degree of expansibility and causing it to flow in the direction of reduced pressure. This expansibility has frequently been attributed to the oil; closer analysis, however, reveals that as gas escapes from solution the oil phase actually. contracts. Hence, it is the accumulation and expansion of the liberated gas that supplies the propelling force for the oil. It has been shown experimentally2-5 that within certain limits a sand containing oil, gas and water will permit the simultaneous flow of all three; the readiness with which they may flow depends upon the characteristics of the sand, of each of the fluids, and upon the relative amounts of the fluids in the sand. Thus, in the initial stages of production by the mechanism of dissolved gas drive, the liberated gas is present in the sand in low concentration and is unable to

Jan 1, 1942

By William M. Newton, John E. Sherborne

The relation between the properties of electric logs and the fluid used in drilling a well is briefly discussed in this paper, and the fact that the resistivity of the drilling mud and its filtrate can appreciably affect such logs is shown. Apparatus was designed and a procedure established to determine the effect of various factors on the resistivity of drilling mud. Five muds commonly employed in California were tested and the following observations were made: I. The effect of raising the temperature from 80°F. to 180°F. is to decrease the resis-tiviiy of the mud or filtrate approximately 50 per cent. 2. The resistivity of the mud in most cases closely approximates that of its filtrate. 3, The change in the resistivities of muds caused by the addition of chemical is not the same function of the amount of chemical added for each mud. 4. The effect produced by increased sodium chloride content is to reduce markedly the resistivity of the mud and its filtrate. 5. Weighting materials, such as Baroid and limestone, tend to increase the resistivity of drilling mud. 6, Cement and counteracting reagents reduce mud resistivity. Introduction During recent years, the practice of "electrically logging9' a geologic formation by means of a system of electrodes lowered in a well bore has provided data of inestimable value concerning the nature of the sediments penetrated. Thus, it is generally possible, by means of electric logs, to distinguish readily the differences between shales, sandstones, cherts, limestones, and other rock forms. The distinguishing characteristics recorded in this manner have made possible long-range and closely detailed mapping and visualization of deeply buried structures1-5 to a degree not to be obtained with a reasonable expenditure of money by any other means at present in use. Besides being of value in correlation work, electric logs have been found, in some instances, to be useful in estimating the nature of fluid contained within the pores of a rock. In special cases, even the relative permeabilities at different horizons have been determined.6 That electric logs should reflect in some measure such physical properties of rocks as porosity and permeability and, in addition, give rise to data pertaining to the fluid content of rock interstices, becomes evident when the conditions giving rise to the electrical phenomena measured are known. However, it is not the purpose of this paper to review the present status of electric logging; rather, the reader is referred to the papers cited on page 220 for the principles and practice involved. Importance of Drilling FLuid in Electric Logging Because the drilling fluid must be the medium through which the electric logging device is made to traverse the formations penetrated by a borehole, and since, in general, the drilling mud completely surrounds

Jan 1, 1942

By E. C. Truesdale, Gerald Edmunds

A few years ago H. M. Cyr, working in the Research Laboratories of The New Jersey Zinc Co., produced a few pounds of zinc1 of such purity that no other elements were detected in it by spectrographic analysis, using the facilities then available. This zinc contained less than one ten-thousandth of one per cent of metallic impurities.&apos; During the decade that followed upon the laboratory production of this "spectro-graphically pure" zinc, commercial developments brought about the production of large tonnages of zinc of purity exceeding 99.99 per cent, and today zinc of 99.999 per cent purity is produced and marketed as "chemically pure" zinc. Typical analyses of present supplies of high-purity zinc are given in Table 1. Table 1.—Typical Analyses Percentnge by Weight Sum of Zinc Fe, Ib1 Fe Cd 1A1 cd Special High Grade*.......... 0.007b 0.005b 0.005b none O.OIOb C.P. (chemically pure)......... < 0.0002 0.0005c 0.000052 S.P. (spectrographically pure).. <0.0002d <0.00005d a A.S.T.M. Standard Specification for Special High Grade Slab Zinc (A.S.T.M. Designation: B 637). b Maximum. &apos; Fe chemically determined. Pb and Cd are spectrographically determined. d Differences between composition of C.P. and S.P. zinc are discussed later in this paper. The availability of commercial tonnages of special high-grade zinc has been the basis for the development of the zinc-base die-casting alloy industry which, in the year 1936, consumed one-eighth of the zinc used in the United States for all purposes. This and the C.P. and S.P. grades have given impetus to scientific investigations into the properties of pure

Jan 1, 1939

By E. J. Duggan

The mine and mill of the Climax Molybdenum Co. are at Climax, Colorado. Climax is on Fremont pass directly on the Continental Divide, at an elevation of 11,400 feet. Description of Ore The Climax ore-bearing rock is essentially an altered and highly silicified granite, fully half of the gangue being quartz. Molybdenite is the only mineral of economic consequence and most of it is intimately associated with quartz in the form of fine veinlets and stringers. Other minerals are molybdite, pyrite, and chal-copyrite. While the molybdite may be readily extracted by hydrometallurgical methods, its content is too low to make such operations profitable. The pyrite content ranges from 2 to 5 per cent and that of the chalcopyrite from 0.03 to 0.05 per cent. There is not enough copper to make its recovery attractive and one of the metallurgical problems is the elimination of it and the pyrite from the product. On account of the close association of the molybdenite with the quartz and the necessity of eliminating the pyrite and chalcopyrite from the final product, fine grinding followed by flotation is the only feasible method of concentration. History Construction of the first milling unit was started in 1917 and it was operated during parts of 1918 and 1919. In the postwar years, there was almost no demand for the product and production was at a standstill until 1924. The Company&apos;s research campaign to develop the use of the metal began to show results in that year. From r926 to 1932 production ranged from 500 to 1200 tons per day. In 1931 an additional mill section was built and production was gradually increased until in 1934 and 1935 about 3000 to 4000 tons was milled per day. This tonnage overtaxed the milling facilities, and as the demand for inolybdenum was growing constantly, additional milling equipment was needed. In 1936 and 1937 another crushing plant, six additional mill sections and the necessary auxiliary plants were constructed and brought into operation. This plant was designed to mill I0,000 tons per day, but it was not long before 12.500 tons was being treated during periods of peak demands. During the summer of 1941, to meet defense needs, the mill has been required to treat 15,500 tons per day. This has been accomplished with little plant expansion and at no loss in recovery, as will be described later. TO increase capacity still further, one more primary section is now being built. This will bring capacity to 18,000 tons per day, which can be stretched to 20,000 tons at a small sacrifice in recovery. Crushing There are two crushing plants: No. I, of 5000 tons capacity (flowsheet in Fig. I) and No. 2, of 15,000 tons capacity (Fig. a).

Jan 1, 1943

By Robert B Sosman

The relative temperature distribution within a coke oven and among the ovens in a battery can be obtained automatically for the operator&apos;s guidance by sighting a total-radiation pyrometer on the face of the coke as it is pushed out, and recording the surface temperature. Keeping the instrument clean and keeping its view of the coke unobstructed by smoke and dust are the principal problems. Typical records from three plants are presented in this paper, showing that the temperature patterns are reproducible. Development OF Method The method of coke pyrometry described in this paper was introduced in 1936 by E. A. Lee, then Assistant Superintendent, now Superintendent, of the Coke Plant at Lorain Works, National Tube Co., Lorain, Ohio. At the request of the Coke Committee of the United States Steel Corporation, the Research Laboratory of the Corporation undertook to adapt the method to the somewhat different conditions met with at the Gary Works of the Carnegie-Illinois Steel Corporation, Gary, Ind., and at the Clairton Works of the same Corporation at Clairton, Pa. This work was done in cooperation with the Leeds and Northrup Co. of Philadelphia and later with the Brown Instrument Co. Division of Minneapolis-Honeywell Regulator Co., Philadelphia. We of the Research Laboratory wish to express our appreci- ation of the courtesies extended by Mr. Lee, by A. N. Cole, Superintendent of the Gary coke plant, and by D. P. Finney, Assistant General Superintendent in charge of coke-plant operations at Clairton. We are also indebted to the instrument companies for the loan of a part of the equipment. At Gary and Clairton the instruments were installed and various experiments were made by J. W. Bain, of the Research Laboratory of the United States Steel Corporation. Pyrometry of Coke The coke inside a by-product oven is almost completely inaccessible to pyro-metric instruments. The temperature in the walls can conceivably be measured with thermocouples, but the atmosphere is usually strongly reducing, a condition well known to be destructive to the accuracy of the customary high-temperature couples. In some plants, periodic readings are taken with an optical pyrometer sighted into the top of the combustion flues. This is a useful measure for safety and general control, as it tends to prevent the damage that would result from overheating of the ovens. It does not, however, tell much about the temperature of the coke itself, because of the continually changing gradient in the wall between the coke and the combustion chamber. The best indication of the temperature of the coke itself must therefore be obtained by observation of the product as it is pushed out of the oven. The human eye is very sensitive to variations in brightness of a surface, and particularly to differences in brightness over a continuous hot surface.

Jan 1, 1943

By Irwin Politziner F. M. Townsend, L. S. Reid

Recently published data indicate that the water vapor content of a gas, as determined by dew point measurement, is inaccurate when the gas has been dehydrated with diethylene glycol. Water vapor contents and dew point measurements of gases dehydrated with triethylene glycol have been obtained in this investigation in order to determine the magnitude of a similar error, if one exists. Experimental data show a very low concentration of triethylene glycol vapor in gases dehydrated at atmospheric ternperatures and pressures ranging from 500 to 2,500 psia and that the accuracy of dew point measurements is not impaired by the presence of triethylene glycol vapor. INTRODUCTION Nearly all natural gas transported by pipe line to northern and eastern markets must be dehydrated to a low residual moisture content in order to assure maximum transmission efficiency and continuous delivery under peak load conditions. Without dehydration, water vapor often condenses in pipe lines in quantities sufficient to restrict the flow3 and. under low atmospheric temperature conditions, gas hydrates may form and plug gathering. transmission and distribution facilities. Gas may be dehydrated to pipe line specifications by a number of methods. The most widely used methods are (1) adsorption of water vapor on a solid dessicant such as activated bauxite, alumina or silica gel,&apos; (2) by absorption of water vapor by either diethylene or triethylene glycol-water solutions of high glycol concentration,11,13 and (3) by simultaneous expansion-refrigeration of very high pressure gas in which gas hydrates are purposely formed and then quickly decomposed.&apos;"" Of these three fundamental methods, the adsorption and absorption processes provide the bulk of the dehydrated gas moving to market at the present time. The expansion-refrigeration process. a relatively new development, is gaining in favor because of its simplicity but is sharply limited in its application by available differentials between source and gathering system pressures. Where gas sale or purchase contracts contain a maximum water vapor content specification, the water vapor content is usually determined by measuring the dew point of the gas at system pressure. Knowing he dew point temperature and the system pressure, the water vapor content of the gas is determined from a graphical correlation of saturation, or dew point, temperature us the water vapor content of the gas which is customarily expressed as pounds of water vapor per million cubic feet of gas measured at 14.7 psia and 60°F. Dew points are usually measured with the U. S. Bureau of Mines Dew Point Tester. shown in Fig. 1, which is well suited for use at temperatures lower than 120°F and at pressurei; ranging from atmospheric to 3,000 psi. A number of correlations of dew point temperatures vs water vapor content are available,3,5,15 the most recent of which is that by McCarthy et al.4 Where natural gas is dehydrated by absorhing contact with concentrated diethylene glycol-water solutions. considerable difficulty is experienced in observing water dew points due to condensation of liquid hydrocarbon and glycol films on the mirrored surface of the dew point tester. Riesenfeld and Frazierl2 report that the dew point method for determining the water vapor content of a dietllylene glycol-treated natural gas is in error due to the glycol content of the condensate formed on the tester mirror, and that the water vapor content of the gas tested is actually lower than that indicated by the standard&apos; dew point-water vapor content correlation. Extensive experience in testing gases dehydrated by concentrated triethylene glycol-water solutions lias not revesled difficulties of the nature cited above for diethylene glycol. Water dew points are clear and sharp and condensation of

Jan 1, 1951

By David B. Reger

The expansion of the previously discovered gas pools and an intensified search for additional pools in the Oriskany and deeper sands were the principal petroleum activities in West Virginia during 1941. One small oil pool was discovered and another was considerably extended. One small gas pool was discovered, several isolated well discoveries were expanded into definite pools, and various recognized pools were substantially increased. The proved oil territory of the state was increased about 600 acres and the proved gas territory about 45,000 acres. The new discoveries of oil did not equal withdrawals but gas reserves added were greater than gas withdrawals. Oil activity, as in the past several years, was slight because of unfavorable crude prices. Most operators prefer to leave oil in the ground rather than to drill for it without a better return. Gas activity increased greatly because of better demand, even though the price of gas did not improve. The account of operations, as gathered from trade journals and other reporting services, shows that 838 new wells were drilled, resulting in 114 new oil wells with 2606 bbl. of daily new production; 558 new gas wells with 949,226,000 cu. ft. of daily open flow; and 166 dry holes. Also, 86 old wells were drilled to deeper sands with 9 bbl. and 56,030,000 cu. ft. of added production. On the new wells the oil average was 22.86 bbl. per well per day; and the gas average was 1,701,000 cu. ft. per well per day. On new wells the ratio of dry holes to completions was 13.61 per cent. On deeper drilling to other sands the ratio of failures was 15.12 per cent. From an exploratory standpoint one strictly new oil pool (Higginbotham Run) was opened in Kanawha County and one strictly new gas pool (Lost Run) in Taylor County. One entirely isolated wildcat gave commercial Oriskany-sand gas production and may open a pool. Various other wildcats greatly extended the boundaries of known Oriskany-sand gas pools and various others may have opened new pools in the shallow sands. On the other hand, various Oriskany tests in Harrison, Monongalia, Roane and Wood Counties were dry and all five tests to the White Clinton sand (Sil.) in Boone, Harrison, Kanawha and Wood Counties failed to find commercial production. The principal oil wells completed, by counties, were: Calhoun, 24; Clay, 7; Gilmer, 6; Hancock, 9; Kanawha, 9; Pleasants, 10; and Ritchie, 14. Production for the year was estimated by the Oil Weekly as 3,421,000 bbl., compared with U. S. Bureau of Mines final figures of 3,444,000 bbl. in 1940. The leading counties in gas-well completions were: Boone, 32; Braxton, 19; Cabell, 16; Calhoun, 46; Clay, 20; Gilmer, 37; Jackson, 94; Kanawha, 82; Lincoln, 17; Putnam, 46; Ritchie, 33; Upshur, 20; and Wayne, 33. Production for the year is estimated by the author as 210,000,000,000 cu. ft., as compared to the U. S. Bureau of Mines&apos; final figures of 188,751,000,000 cu. ft.* in 1940.

Jan 1, 1942

By G. Sachs, G. Espey

It is well known that high residual stresses are created in tubing by the sinking process, in which no internal tool or mandrel is used.l-4 In this process, the wall thickness is usually slightly increased.4,5 In tube drawing with a plug, the residual stresses are gradually reduced with increasing reduction of wall, and, by the conventional approximation methods of stress measurement, no stress is detected in tubing in which the wall reduction is over 50 per cent of the total reduction in cross-sectional area.l,6 It has also been observed that higher stresses are set up by the use of wide-angle dies than by acute dies.? &apos;he actual stress distribution in drawn tubing has been investigated by a few workers,7"9 but has not been related to the conditions of the drawing process. Some attempts have been made to correlate accelerated cracking tests for stresses in brass products with the magnitude of the circumferential stresses and the condition of the metal. l-10 Materials and Preparation The material used in this experiment was commercial cartridge-brass (70 per cent Cu, 30 per cent Zn) tubing in the straightened and annealed condition.† This tubing was of various outside diameters and had a wall thickness of 0.032 in. It was sunk to 1/2-in. outside diameter by means of an experimental 10,000-lb. hydraulic draw-bench, with a maximum drawing speed of 8 ft. per minute. All dies were of 1/2-in. diameter. Various die materials and contours were used in order to study the effect of die design on residual stresses in the tubing; the specifications for the dies are given in Fig. I. Castor oil was used throughout as lubricant. Chattering occurred in sinking some of the tubing, particularly when dies having the more acute angles were used, but the tubes showing chatter marks did not differ markedly from those with a smooth surface regarding the magnitude of residual stress. The source of the chattering has not yet been revealed. The wall of the tubing becomes thicker during s nking, as previously observed.4,5 The increases in wall thickness were 3, 7 and 9.5 per cent on the average for 6, 20 and 33 per cent reductions in diameter, no effect of the contour being noticeable. The reductions mentioned throughout this investigation do not consider this fact, but are reductions of the outside diameter. For the evaluation of the residual stress two fundamentally different methods were used. The approximation methodl,ll of splitting a certain length of tubing was employed to obtain a bird&apos;s-eye view of the effect of various drawing conditions on the circumferential stress measured by the diameter change occurring On splitting. For

Jan 1, 1942

By W. A. Johnson, F. N. Rhines, W. A. Anderson

The rate of the high-temperature oxidation of pure copper has been measured repeatedly by numerous investigators. It appears to be generally agreed: (I) that at constant temperature, after the initial stages of oxidation have been passed and the scale has attained a substantial depth, the film thickness increases in proportion to the square root of the time of oxidation; and (2) that for any given period of oxidation the logarithm of the square of the film thickness is proportional to the reciprocal of the absolute temperature of oxidation.&apos; These relationships are explained upon the basis that the rate of diffusion of copper to the external surface of the film is the controlling factor in establishing the rate of growth. Extensive studies have been devoted also to the mechanism and rates of the early stages of oxidation. There is thus available a reasonably well established theory of the oxidation of pure copper upon which to construct an explanation of the more complex oxidation of copper alloys. Few general principles have as yet emerged from the chaos of observations that have been reported in the field of the oxidation of alloys.2 It is evident, however, that the copper alloys may be divided into two main groups, whose oxidation characteristics are distinguish- able. The first group, composed of the alloys with the noble metals, forms substantially pure copper oxide scales; the alloying element is concentrated within the residual metal, and sometimes particles of almost pure noble metal are found in the scales completely surrounded by copper oxide. In the second group, composed of the alloys of copper with the baser metals, the alloying element appears as an oxide in the scale, often in greater concentration than in the alloy itself and sometimes to the exclusion of copper oxide. The oxide scales of the latter class have been found to be made up of one, two, and sometimes more distinguishable layers of which the innermost is often metallic in character, composed of particles of the oxide of the alloying element embedded in essentially pure copper and known as the subscale or zone of internal oxidation. The need for a thorough quantitative study of these modes of oxidation is evident. Since it is apparent that several mechanisms must be cooperating to produce the complex oxide scales found on copper alloys, the analysis of the process into its several simple operations should prove instructive. Fortunately, it is possible experimentally to produce internal oxidation in the absence of an external scale; this permits the isolation and intensive study of one of the steps in the oxidation process. In the present research the rates of internal oxidation of an extensive series of dilute solid solution alloys of copper have been measured and a theory has been developed to predict the observed

Jan 1, 1942

By Hugh S. Spence

The use of natural feldspathic rocks, as opposed to straight feldspar, for ceramic purposes is not new. "Cornwall stone," a semi-kaolinized granite containing fluorite, has long been used by the English pottery trade instead of feldspar, and "Carolina stone," a similar rock, is now being offered to the American trade. A recent report of the U. S. Bureau of Mines states that trachyte, a glassy volcanic rock, is being used in California instead of feldspar in ceramic bodies. In Germany, phonolite and basalt have been investigated, and possibly also used, as ceramic raw materials, and extensive research has been conducted in Russia in recent years looking to the utilization of the immense bodies of nepheline syenite of the Kola Peninsula, which is the host rock of the apatite deposits now being exploited on a large scale in the Murmansk region; the nepheline is recovered as a by-product of the concentration of the apatite. Long used principally as a raw material for the pottery and allied industries, where, in bodies, glazes, enamels, etc., it serves as a fluxing ingredient and forms, on firing, a glassy bond with the more refractory clay, flint and coloring particles, feldspar has been finding ever increasing employment in glass. In 1936, over half of the nearly quarter of a million tons of feldspar sold in the United States went to the glass trade. Its usefulness for this purpose is due to the resistance to thermal shock which it imparts to glass products, particularly bottles, containers and tableware, because of its alumina content, which averages from 16 to 20 per cent. Active search has been wade on the American continent during the past few years for other minerals of feldspathoid type, with comparable or higher alumina content, that, may be suitable for glass and other ceramic purposes. One of the most important results of this work has been the delimiting in central Ontario of large bodies of nepheline syenite of excellent, ceramic grade.

Jan 1, 1942

By J. D. Sullivan, Chester R. Austin, J. L. Nunes

It is characteristic of most shales and surface clays that a bloated or vesicular structure is produced by burning to a sufficiently high temperature, usually about 150° to 200°F. above the normal maturing temperature used when making common brick of the same material. Early investi-: gators recognized this phenomenon and attributed it to the release or expansion of gases in the vitrified piece. A number of theories have been advanced on the source of the gas and the manner in which it is evolved, but none has been proved conclusively. T. E. Jackson&apos;s1 early theory that bloating was due to oxygen evolved by ferric oxide in forming ferrous oxide or ferrous silicate was never substantiated by - experimental work. Orton2 thought this explanation unlikely, as all clays should bloat at the same temperature, if this were true. He found that clays bloated in the range from IIoo° to 17oo°C. Also, many clays containing iron did not bloat at all, but fused. Orton also stated that oxida- tion of different types of carbon was a source of gas during burning of clay and should be expelled before vitrification was reached. Seger3 said that he had dissolved ferric oxide in glass with no apparent evolution of gas. Matson4 came to the conclusion that ferruginous clays burned &apos; to vitrification in an oxidizing atmosphere did not have the iron in a ferrous form. According to Wilson,= the gases responsible for bloating might be entrapped air, water, sulphur dioxide, carbon monoxide, oxygen, and hydrocarbons. He spoke of two causes of bloating: (I) incomplete oxidation below the vitrification temperature, and (2) decomposition of compounds and evolution of gases above the vitrification temperature. Decomposition of calcium sulphate was given as the principal example of the latter. Bleininger and Montgomery0 stated that if any time after vitrification began the evolution of gaseous matter was rapid enough so that pressure was produced within the clay, bloating was certain to take place, and a vesicular structure would be formed. They recognized that initial structure, rate of heating, kiln atmosphere, and many other variables affected bloating. Work done by the Emergency Fleet Corporation7 indicated that clays suitable for bloating should be high in compounds of metallic oxides, carbon, sulphur, sodium, potassium, or other equivalent compounds, which either act as a flux or give off gas. Orton2 studied the chemical status of the carbon, iron, and sulphur in clays during various stages of burning, using a Huron shale that bloated under oxidizing or reducing conditions. He found that only a small amount of sulphur remained in the clay and that it could be detected only by dissolving the clay in hydrofluoric acid; i.e., the sulphur was in combination with the silica. orton said that this sulphur was probably in the form of iron sulphide dissolved in the glass phase. The iron sulphide was not broken down by heating, but was dissolved in the basic slag or glass,

Jan 1, 1942

By E. E. Donath

Application of the coal hydrogenation process for the production of chemicals is described. It has been estimated that a plant to produce 31,090 bbl per day of chemicals and fuels would cost $326,- 000,000. These products would consist of 6.1 pct by weight tar acids, 50.8 pct aroma tics, 16.4 pct LPG, and 26.7 pct gasoline. THE coal hydrogenation process is well known as a means for the production of liquid fuels from coal. In this paper the possibilities of the coal hydrogenation process as a source of chemical raw materials will be discussed. The recovery of chemicals from coal hydrogenation products necessitates some modifications and additions to the equipment used for the production of fuels. The conversion of coal into liquid fuels such as gasoline requires two steps: liquid phase and vapor phase hydrogenation. Intermediate oils obtained in the liquid phase contain oxygen and nitrogen compounds, especially aromatic compounds, since the coal itself is composed mainly of cyclic compounds. These oils are the raw material for the separation of high molecular weight aro-matics and of tar acids and tar bases. The relative amounts of heavy and middle oil—boiling above and below, e.g., 325°C—can be influenced by temperature, residence time, and catalyst of the liquid phase hydrogenation. In the vapor phase hydrogenation a solid bed catalyst is used to convert the intermediate oil from the liquid phase operation into hydrocarbons of the gasoline boiling range. Essentially pure hydrocarbons with a low content of sulphur, oxygen, nitrogen, and olefines are obtained. Depending mainly on the catalyst, the high ring compound content of the liquid phase oil can be preserved and gasoline rich in aromatics obtained. However, with other catalysts, these ring compounds can be split into gasoline with a high content of isoparaffins.&apos; Again, depending on the operating conditions, products of varying boiling range can be obtained. Selection of catalyst and operating conditions therefore makes possible the production of different grades of motor fuel and also variations in the relative amounts of benzene, toluene, and xylene when aromatic hydrocarbons are produced. The schematic flowsheet, Fig. 1, shows the main steps of the coal hydrogenation process, and the product streams used for the recovery of chemicals are indicated. In the liquid phase hydrogenation stage, coal is made into a paste with recycle heavy oil. The coal paste is mixed with hydrogen and preheated at a pressure of 300 to 700 atm in heat exchangers and preheaters. The coal paste and hydrogen enter high pressure converters where the liquefaction of coal, conversion of the high boiling liquid materials initially obtained, into intermediate oils is performed at a temperature around 470°C. The reaction products enter the hot catchpot in which lower boiling oil vapors are separated from the residue containing unreacted coal, ash, and heavy oil. This residue, usually called H.O.L.D. (heavy oil let down), is processed to separate solid and liquid material. By thermal treatment of the residue, e.g., a coking process, distillate oil is obtained, which can be recycled as part of the pasting oil. This stream is rich in polynuclear aromatics and can be, and has been, used for the recovery of such material. The oil vapors and hydrogen from the hot catchpot are cooled in heat exchangers and a cooler, and the condensed oil is separated from the recycle hy-

Jan 1, 1953