Search Documents

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

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

Jan 1, 1949

By W. L. Maxson

GRINDING is one of the major problems in present-day milling practice, and in many cases, it represents one of the main items of expense. It becomes necessary from time to time, to compare grinding practice in one plant with that in another plant, and in making such comparisons, it would be very desirable were there available accepted standards of grinding resistance for the materials involved. Such a set of grinding constants would also be of considerable value in planning new grind-ing installations. There have been some tests published, notably those of Lennox,1 which have been generally cited as a basis for such comparisons. Most of the tests made have been based upon open-circuit grinding, in which a weighed sample of the ore was crushed to pass a certain mesh, and was .then ground under certain conditions, either wet or dry. Grinding was continued until a certain desired fineness was attained, and the compari-sons based on the grinding time, or the samples were all ground for a certain specified length of time and comparison based upon the screen analysis of the products. Such methods have been acceptable where the ore was to be ground in open circuit. However, in modern milling practice, many grinding problems involve closed circuits wherein the oversize returns to the mill and a large circulating, load builds up. A method of testing that does not take the circulating load into consideration might yield results quite different from those to he expected in practice, because the minerals in the ore that offer maximum resistance to grinding will accumulate in the circulating load up to an equilibrium value. Thus the nature of the ore charge in the mill at any instant may differ greatly from that of the new feed, with a consequent error in the rate of grinding determined by such a method.

Jan 1, 1933

By E. H. Lee, F. J. Fayers

Problems in reservoir analysis can usually he cupressed in terms of a system of nonlinear partial difjerential equations. A rnethod for .setting physically reasonable boundary conditions for these systerrls by ayplication of the theory of characteristics is discussed. A short description i.c. given of the technique for finding chnmcteristics of general first order and second orrler equations. Specific examples are quoted jrorn eqrrations occurring in theoretical reservoir studies. The princip1e. ossocicred wit11 the use of chnracteristic to set physically realistic boundary conditions me developed, and thr method is discussed in terms of boundary condition for the noncupillary, compressible, two-phase flow problen: jor the cupillary, ir~cowlpressible, two-phase flow problems for the tlrtergent flooding prohlenl; as for the compressible. noncapillary, two-phase flow pro11letn. INTRODUCTION In most problcms in reservoir analysis the physical situation is described by a system of nonlinear partial differential equations. The general solution to the set of equations usually comprises a wide range of functions ancl a particular solution is normally selectetl by applying suitable boundary conditions to the problem. In some cases it is clear from the physical situation what form the boundary conditions should take, but it is usually desirable to have an independent mathematical check of the suitability of the chosen conditions. From the mathematical standpoint, a system of partial differential equations with boundary conditions is said to be properly set if the combination determines a unique solution which is continuously dependent on the equation and the boundary conditions. Such a solution is sometimes termed "reasonable". In investigating the properties of the mathematical representation, it is useful to determine the structure of the system by the application of the theory of characteristics. This theory determines in the space of the independent variables, lines or surfaces which play a special role in thc system's behavior. The characteristics determine the possibility and nature of the propagation of discontinuities in the derivatives of the dependent variables. Along the characteristics certain differential relations hold which for some problems allow a so- lution to be obtained analytically. In the case of hyperbolic equations the characteristics can bc used as 3 basis for a numerical solution. If a complicated nonlinear system is to be solved, a study of behavior of the characteristics will indicate what boundary conditions should be chosen. By using the method of characteristics, several advances have rccently been made in solving reservoir engineering problems. Sheldon, Zondek and Cardwell' have discussed how the the method may be used grap-phically to solve the incompressible two-phase displaccmerit problem when the gravity term is included in the equations. Fayers and Perrine' have applied the method to study the equations representing detergent flooding. When compressibility and solution-gas effects are introduced into the two-phase flow problem, the equations and their characteristics become more complicated. It will be seen that in this problem the characteristics are useful for indicating a reasonable set of boundary conditions but cannot readily be used to compute a numerical solution. This problem has been solved on the IBM 701 using normal finite difference methods hy West, Garvin and Sheldon." The material to be prcscntcd in this report is divided into three sections. The first discusses the determination of the characteristics of first and second order partial differential equations; the second describes the selection of suitable boundary conditions by the application of the principle that the future cannot affect the past; the third discusses the use of characteristics for setting the boundary conditions of the two-phase solution-gas flow problem. A useful introduction to the method of characteristics has been given by Hildebrand.' A summary of the method will be given in this section of the paper. The First Order Equation The quasi-linear equation of first order is It is linear in the partial derivations of z. The properly linear equation has the form The characteristics of are curves along which the

By W. F. Hosford

A quantitative explanation is offered for the peculiar curled grain shapes found in the microstructures of drawn wires of bcc metals and compressed aluminum specimens. It is shown that once an [011] fiber texture is developed, the slip system are so oriented that further slip tends to produce plane strain rather than axially symmetric flow of individual grains. With plane -strain flow, however, compatibility of neighboring grains can be maintained only by a bending of grains about one another. PROBABLY the most obvious microstructural feature of heavily worked metals is the distorted shapes of grains. In the course of deformation, the shape change of each grain must be compatible with that of neighboring grains; otherwise holes would be formed at grain boundaries. In analyses of poly-crystalline deformation by Taylor and subsequent workers it was assumed that grain boundary compatability was maintained by each grain undergoing the same shape change as the polycrystalline aggregate in which it is imbedded. According to this assumption, when simple tension or compression is applied to a random polycrystal or to one with a fiber texture, each grain ought to deform with axially symmetric flow. Initially equiaxed grains should become cigar-shaped during wire drawing and pancake-shaped during compression. While microstructural observations of deformed metals are generally in accord with such a picture, certain striking exceptions may be noted. Peck and Thomas5'8 found that grains in heavily drawn tungsten, iron, and niobium (columbium) wires become shaped like ribbons curled about the wire axis, Fig. 1. At a suggestion from the author, they rationalized the development of these micro-structures by considering the orientation of the slip systems in the [011] texture formed by the wire drawing. It is shown in this paper that marked departure from axially symmetric flow of grains is also observed when polycrystalline aluminum is severely compressed. Again the explanation must lie in the orientation of the slip system in the [011] texture, which is formed in fcc metals by compression.' THEORY A simple quantitative argument will be presented to show that the development of these microstructures is a result of flow on the combination of slip systems for which the minimum amount of mechanical work is expended in producing a unit tensile (or compressive) strain. First it must be realized that the macroscopic strains of a crystal resulting from slip are given by: where d dy, and dc, are normal strain increments parallel to the x, y, and z reference axes; are crystallographic shear-strain increments on slip systems

Jan 1, 1964

By K. S. Krishnam, A. G. Guy

VOLUME 6 of the Transactions of the Baikov Institute of Metallurgy, Moscow, is devoted to the subject of "the experimental and theoretical study of the physical characteristics of dilute solid solutions,11 and summarizes work that has been done largely in the years 1958-9. In view of the attention that Soviet investigators have given to this subject, it seemed useful to carry out an independent experimental investigation in an effort to judge the scientific basis and practical significance of this field of study. The present note is a preliminary report of this investigation. The first property studied by the Soviet group was X-ray spectra of solid-solution alloys.' An anomaly observed at low concentrations (--0.05 at. pct) of the alloying element led to the theory that each impurity atom in a transition-metal base alloy is the center of a "block" of affected atoms with a radius of about 10"7 cm. This theory was further developed in a later paper.2 By this time similar anomalies had been found in diffusion coefficients3 and in thermal expansion.4 The entire development up to 1959 was reviewed in a comprehensive paper, and further theoretical ideas were also published at this time. Finally, the volume mentioned above was published in 19607 giving new experimental data on anomalies in optical properties and Hall constant, and a new theoretical treatment also appeared.' Although western scientists have done both theoretical work, summarized recently by Friedel,9 and considerable experimental work on dilute solid solutions, there is little support for the marked anomalies reported in the Soviet papers. Of the physical properties studied by the Soviet investigators, thermal expansion was chosen for the present investigation because of the relative ease of obtaining the necessary precision of measurement. A Leitz dilatometer was used for this purpose, and a special technique involving interchanging of the two specimens being compared permitted a precision of 0.05 x X in average thermal expansion over the range 27° to 600°C. The specimens were heated and cooled in vacuum or in a protective atmosphere at a rate of 50 °C per hr. Ferrovac E iron was used as the comparison specimen and in every case had a coefficient of expansion higher than (or equal to) that of the alloy. Since unintentional impurities are an important factor in studies of dilute alloys, special attention was given to the purity of the iron and the alloys used. The alloys were the same of those used by Abrahamson10 and by Michalak," and their preparation is described in these references. Chemical analyses of the Ferrovac E iron and of typical Fe-W and Fe-Mo alloys are given in Table I. The purity of the iron and alloys is undoubtedly higher than in the

Jan 1, 1962

By M. Gensamer

IN applied mechanics and in metallurgy the transition from elastic to inelastic action is a matter of considerable interest and importance. Often the first inelastic deformation is apparently quite homogeneous; that is, uniformly distributed throughout the specimen. Sometimes this deformation is heterogeneous; that is, localized; inelastic deformation proceeds to some definite amount in restricted regions before adjacent regions of the specimen are inelastically deformed. In such cases the deformation does not become homogeneous until the whole specimen has been deformed the amount corresponding to that for each localized deformation. If the test is stopped before uniform extension sets in, the heterogeneous character of the deformation is apparent on the surface of the specimen through characteristic markings, which have been called "Lüders"' lines, "Hartmann's" lines, the "Piobert effect," or simply "flow figures." These markings are the source of considerable trouble in fabricating operations, particularly in the deep drawing of steel sheet. In many cases where the transition is of this nature, the stress developed at the upper limit of the elastic range is greater than the stress during the period of heterogeneous deformation, giving rise to the familiar "drop of the beam" effect in testing. The amount of the yield-point elongation, as well as the value of the stress at the lower yield point (the value to which the stress drops when yielding begins), are functions of the temperature and the testing speed. Lower temperatures and faster rates of testing increase both the yield-point elongation and the yield-point stress. These matters have been ably discussed in a recent paper by Winlock and Leiter1 though, as brought out by the discussion of that paper, the phenomena are but little understood. The purpose of the present paper is to clarify the problem through the application of a simple principle, and to show that, through the application of this principle, a number of phenomena in the plastic deformation of metals become more readily understood. The principle is this: During homogeneous flow, the rate of work-hardening is greater than the rate of change of stress resulting from change

Jan 1, 1938

By John V. Beall

As Mother Nature arranged it, the hottest potential mineral target in the country today, the Stillwater complex had to occur in a spectacular natural setting-the north margin of the Bear Tooth Mountains of Montana. What more appropriate backdrop for the August 17-18 field hearings of Senator Frank E. Moss (D-Utah). His subcommittee, on Minerals. Materials and Fuels, heard 37 witnesses ponder the value of minerals vs esthetics or other uses of federal lands. On August 17, four Army Hueys swept the senatorial party, the press, Forest Service Officers and such distinguished witnesses as Montana Governor Forrest H. Anderson over the Custer-Gallatin National Forests, besting the thin air of 10,000 ft p1us, they set down on Iron Plateau.

Jan 1, 1971

By A. B. Young

The difficulties encountered in the preparation of the lead smelter charge for the blast furnace and in the roasting and sintering of the ores, and the expert means taken for the preparation of these materials since the introduction of flotation concentrates into the lead smelter charge, have been described by W. H. Eardleyl and R. A. Wagstaff.² Function of Roasters and Blast Furnaces The lead smelter has first its roasters and its sintering devices, of which the primary object is the removal of sulfur from the ore or from the charge. The blast furnace follows; its function being the elimination of the gangue material left in the charge—the elimination of the insoluble, the iron, the zinc and the lime from the metallic lead. The secondary object is the separation of copper from the lead. A lead blast furnace is a sensitive apparatus. The materials composing the charge must be marshalled in certain proportions before they will make a fluid slag which will separate from the metallic lead. The silica, iron, lime and zinc must be put together in proportions that usually do not mist naturally in the ores, therefore fluxes are necessary. Function of the Flotation Cell The flotation cell—-speaking from the standpoint of a lead concentrate—has taken over part of the work hitherto performed entirely by either gravity concentration or the lead blast furnace. It has eliminated gangue from the concentrate and separated waste products from the lead. In so far as it has done that, it has usurped some of the function of the lead blast furnace; and it is much cheaper to run a flotation cell than a lead blast furnace. The effect in Utah, and it will be similar to effects in other districts. has been to remove a great deal of the gangue by means of flotation, whereas in the old clays it was eliminated by means of sme1ting. In this district, as in others, the insoluble content of the ores has been greatly out of proportion to the iron and lime content to make a proper slag

Jan 1, 1928

By C. H. Reynolds, Robert C. Pruess

Late in 1954 exploratory drilling indicated a substantial orebody on the Rattlesnake claims of Woodmont Inc., a Continental Uranium Inc. subsidiary. Woodmont holdings are located about 35 miles southeast of Moab, Utah. Only a few miles north of Big Indian Valley and other Chinle-sand uraninite deposits, the claims are in an entirely different geologic environment. Detailed development drilling continued until the Deep North orebody was outlined, covering an area approximately 300 x 450 ft. All exploratory drilling and about 80 pct of development drilling was wet core. Chemical assays for each hole sample, applied at 1-ft intervals against the measured core length, were put into a conventional ore calculation formula. Forty-six holes were drilled to delineate the Deep North orebody.

Jun 1, 1956

By William Kent

In a paper by Mr. Frank Firmstone, published in vol. iv, of the Transactions of the Institute, on " Comparison of Results from Open-topped and Closed-topped Furnaces," the regularity of the average grade of pig iron procluced by the furnace under different conditions is expressed by means of a curve or diagram. The object of this note is to show that the graphic method, or that of representing variations by plotted curves or diagrams, is capable of a much more extended application to blast-furnace records, making a valuable auxiliary to the " furnace hook," and that by it the practical metallurgist may obtain at a glance information concerning the variations of the furnace during long periods, which could be found in the furnace book only after a tedious search. Plate XII is a graphic record of an anthracite blast furnace for one month. The table on page 554 gives the figures obtained from the furnace book, together with a record of temperature of the atmosphere, barometric pressure, and moisture in the air, which was obtained from a meteorological observatory not far from the furnace. In the records of a furnace, two of the variable qualities are final results, viz., the quantity of pig iron produced, and its grade; all the other variables are antecedent causes which produce the final results. Of these variable callses which contribute to the quantity of product and its grade, some are partially under the control of the furnace manager, others depend upon the state of the atmosphere, and still others are accidental. Of the first class are the character of the materials charged, and their relative proportions, their mechanical conditions, as wetor dry, large or small pieces, etc., the revolutions of the engine, the heat and pressure of blast, and the distribution of the charge. Of the second class are the number of pounds of air blown into the furnace for each stroke of the engine, the amount of moisture in the air, and the condition of the chimney draughts. These vary largely with the season of the year. Of the third class is the leaking of a tuyere or a temporary stoppage. To keep a record of this kind for a whole year, it is only necessary to procure a sheet of common profile or cross section paper, about 38 inches long and 8 or 10 inches wide, with cross lines ruled about 0.1 of an inch apart. The vertical lines, or those in direction of the

Jan 1, 1879

We regret to advise that, owing to unusual pressure of business at our printers, Volume TAX will not be ready for distribution so early as was announced in the last Bulletin. It will probably be distributed in November. Volumes LVII and LVIII were mailed during the month of August to all members whose dues were paid on Aug. 1; members who failed to receive their Transactions within a reasonable time are requested to notify the Secretary. In the case of members who have recently changed their addresses, the Transactions Were sent-to addresses on record on Aug. 19; those who did not notify .us of change of address until after Aug. 19 will find their Transactions at the old address.

Jan 10, 1918

By J. R. Linney

Demand for eastern magnetite in 1948 necessitated practically all eastern magnetite industries to operate on a six-day week, with the result that over 11,000,000 long tons of crude ore were mined, and the shipping products amounted to approximately 5,000,. 000 long tons. Reports indicate that operating on a six-day week and doing maintenance work on the seventh day was satisfactory and resulted in excellent continuity of operation. In the Port Henry district, Republic Steel Corp. once again set new all-time records for the production of crude ore and total shipping product; 1,868,000 long tons of crude ore were mined, 945,000 from the Old Bed mine, 408,500 from the Harmony mine, and 514,500 from the Fisher Hill mine. Of the 969,000 long tons of shipping products, 663,800 long tons were sinter, 181,000 lump ore, and 115,200 con¬centrates.

Jan 1, 1949

By Richard M. Foose

FIVE miles southwest of Mt. Holly Springs, Cumberland County, Pennsylvania, the Philadelphia Clay Co. has been mining and milling a white clay since 1896; for use in white cement, as a filler in rubber, pigment and paper, in the manufacture of insecticides, and for other minor purposes. Until late in 1942, when the mine was abandoned because of labor shortage, combined underground mining and surface stripping produced approximately 30,000 tons of clay a year, of which 10,000 tons were refined in the mill. GEOLOGY Lower Cambrian Antietam quartzite and the Montalto quartzite, stratigraphically older, trend N.55°E. and make a sharp 1600-ft. anticlinal ridge of the South Mountains. The Tomstown dolomite overlies the Antietam quartzite on the southeast flank of the anticline, which is displaced near its crest by a steeply dipping oblique fault. Erosion of the less resistant Tomstown formation has resulted in a narrow valley at an elevation of 700 ft. Directly on top of the Antietam quartzite and at the base of the Tomstown formation is a zone of sandy white clay, lenticular along the strike of the formations, ranging in thickness from 10 to 300 ft. within a mile. All of the formations dip steeply to the southeast, from 65° to vertical. The clay crops out at an elevation of about 1000 feet. ORIGIN AND CHARACTER The uppermost part of the Antietam formation is sericitic and schistose at many places, and at all these places weathering is in an advanced stage. The clay is the residual product of weathering of this sericitic quartzite or sandy schist. The crude clay has the physical aspect of a sandy kaolin, but there are large areas in the clay formation that are low in free silica, and commonly the 30 ft. adjacent to the Antietam quartzite is notably free of silica. The overlying Tomstown dolomite has been weathered almost completely to a mixed yellow and brown clay, which carries a zone of nodular and chunky limonite and manganese ore, 4 to 12 ft. thick, about l00 ft. from the contact with the white clay. In mining, this zone is an important "marker," indicating where the white clay may be expected in an advancing tunnel. The contact of the white clay formation with the yellow and brown clay of the Tomstown formation is relatively sharp, although the line of contact is irregular and therefore responsible for the lenticular character of the white clay formation. Following is an analysis of the refined clay containing less than one per cent of moisture when dried at 212°F.: Si02, 67.05 per cent; A1203, 22.27; Fe203, 0.40; CaO, 0.00; Ti02, 1.05; MgO, 0.52; Na20, 0.04; K20, 0.88; ignition loss, 7.65; total, 99.86.

Jan 1, 1944

By Richard F. Miller

The investigations of large-grained specimens carried out by Polanyi and Schmid,l Sykes,2 Goucher,3 Yamaguchi,4 Gough, Cox, and Sopwith,5 Carpenter and Elam,6 Aston,7 and others have shown qualitatively that grain boundaries restrain the deformation of adjacent crystals. But whether or not the influence of the grain boundary is confined to the glide planes intersected by the boundary has not been demonstrated in any of these investigations, nor has there been carried out any quantitative analysis of the influence of a boundary on the deformation of a crystal. Indeed, the specimens employed in the previous work contained so many complicating factors that it would have been difficult to observe any variation of the extent of the influence of the grain boundaries in relation to their sizc. The specimens were small, the grain boundaries irregular and at no particular angle to the specimen axis or the

Jan 1, 1934

By L. C. Morganroth

Discussion of the paper of L. C. MORGANROTH, presented at the New York meeting, February, 1916, and printed in Bulletin No. 110, February, 1916, pp. 475 to 481. DAVID B. REGER, Morgantown, W. Va.-I notice in the third paragraph of the first page of the paper, that in mentioning the clays of the Pottsville series, the author says: "The bed of clay found in the latter formation is unique in that flint clay is practically restricted to it. (A variety of flint clay is occasionally found in these upper deposits but this is in such small amounts as to be negligible."). If the author wishes to confine himself to the fire clays of Pennsylvania, as the title seems to indicate, I have nothing to say, but if he wishes to include a discussion on fire clays of the adjoining States which the. subsequent paragraphs of his paper seem to indicate, then I wish to call attention to the fact that there are large and extensive deposits of fire clay in the Allegheny series, immediately overlying the Pottsville in the northern counties of West Virginia. These fire clays have been studied carefully, and described in several reports of the West Virginia Geological Survey, first in the report on Ohio, Brooke, and Hancock Counties, in the northern part of the State; described later ,in the report on Monongalia, Marion, and Taylor Counties, and in the report on Preston County, which followed. In these latter counties (Monongalia, Marion, Taylor, and Preston) there are some beds of fine fire clay, varying in thickness from 6 to 10 or 12 ft., with a content of only 2 or 3 per cent. of fluxing ingredients, and these are of the typical Savage Mountain appearance and also have the typical Savage Mountain fracture. They have been prospected, but not mined a great deal. Several of them have been tested in blast furnaces and furnaces for other purposes, in glass-manufacturing plants, also for firebrick, arid have been found to be very good. They are simply awaiting development, and I merely want to call attention to the fact that there are plenty of them in the Allegheny series still above the Pottsville in West Virginia. There are two or three valuable seams which I have seen in person and have had analyzed in our laboratory.

Jan 5, 1916

By G. A. Guess

THIS investigation was started with the idea of determining whether copper-nickel mattes might not have a lower flowing temperature than copper mattes, and thus perhaps aid in accounting for the difficulty so far experienced in attempts at pyritically smelting copper-nickel ores. We have used the term flowing temperature to avoid confusion with the usual melting temperature. The idea at first was that there might be a greater viscosity range in the one matte than in the other. In the early experiments it was in our minds to determine the relative fluidity of the mattes at a given temperature. Looking to this end we tried pouring equal quantities of matte at the same temperature down an inclined graphite slab, and comparing the distances traveled. Results from such experiments were not satisfactory. We next tried pouring equal quantities at the same temperature through a drilled hole in an Acheson graphite crucible, timing the flow with a stop watch, the whole operation being carried out in the muffle. The flowing temperatures of the mattes tried in this way appeared to be about the same, and there was no marked difference in their fluidity when well fused. Oxidation gave some trouble. These experiments finally led to the adoption of the following apparatus which we thought at the time was wholly original with us, but which we have since found was described by W. McA. Johnson.' The tray used was a slab of graphite 8 in. long, 2 in. wide and ¼ in. thick. It had six holes, into each of which sat a cup of Acheson graphite. Centrally in the bottom of each cup was a vertically drilled hole 3/16 in. in diameter and ½ in. long. The mattes to be tested were put into the cups, in a solid piece. The cups were covered with inverted Battersea "A" cups. The tray was put into the muffle of a gas-fired furnace. Supports on .each end held the tray about 2 in. from the floor of the muffle. Udder

Jan 6, 1916

By J. Y. Oldshue

INTRODUCTION The field of fluid mixing involves many different kinds of process objectives. In order to classify these objectives, Table 1 gives a listing of five basic application categories, gas-liquid, liquid-solid, liquid-liquid, miscible liquids, and fluid motion. However, each of these areas can be broken up into two different concepts one involved with uniformity of solids or liquids as a criteria, and the other involved with chemical reactions or mass transfer. The things that we would do to design a fluid mixing for solid suspension are quite different from things that we would do to design a mixer for heat transfer or gas-liquid mass transfer. Therefore, there are really ten separate mixing technologies. Each of these areas has its [ ] own principles of fluid mechanics, scale-up techniques and application experience. We will take a look at each of these areas and look at some of the ways that we can handle fluid mixing applications which.

Jan 1, 1979

By Donald L. Katz, Leslie J. Noaker

Experimental data are presented for hydrate formation conditions for mixtures of hydrogen sulfide and methane. Vapor-solid equilibrium constants for hydrogen sulfide are also presented. Equilibrium constants, defined here as the ratio of the mole fraction of hydrogen sulfide in the vapor phase (dry basis) to the mole fraction of hydrogen sulfide in the solid phase (dry basis), were calculated using the vapor-solid equilibrium constants for methane presented in an earlier paper. The conditions at which a natural gas will form gas hydrates with water may be computed from its composition, when hydrogen sulfide is present in addition to carbon dioxide and the paraffin hydrocarbons. INTRODUCTION Many gases are known to form solid hydrates in the presence of liquid water at temperatures above 32°F. This hydrate formation is of importance to the natural gas industry inasmuch as most of the constituents found in natural gases will form hydrates. The attention of the industry was called to hydrates by Hammer-schmidtl0 in 1934. A number of papers have been written giving the temperatures and pressures at which these hydrates will form3,4,5,6,7,8,9,10,13,14,15,18,19 and a bibliography on the subject has been compiled13. Deaton and Frost4,5,6,7,8 report work for various pure gases and for some natural gases. Katz and co-workers3,4,13,14,18,19 have reported data for various gases at high pressure. They developed a method of predicting conditions for hydrate formation from equilibrium constants3,19 and from gab gravity." The effects of anti-freeze agents on the formation of hydrogen sulfide hydrate were reported by Bond and Nelson.' The hydrogen sulfide-water system, including hydrate, has been the subject of recent investigation by Sage and co-workers." Mixtures of hydrates behave as solid solutions and an equilibrium exists between the vapor phase and the solid phase that appears to be comparable to the equilibrium between vapor and liquid phases.3,10 By means of the vapor-solid equilibrium constants which have been published for methane, ethane, propane, iso-butane, and carbon dioxidel6 it is possible to determine the temperature and pressure at which hydrates will form for a specific gas mixture when water is present. Hydrogen sulfide which is frequently found in natural gases has a very strong tendency to form hydrate and must enter the solid solution when present in a natural gas forming a hydrate. To determine the effect of hydrogen sulfide when computing the conditions for gas hydrate formation, it is necessary to have the equilibrium constant giving the ratio of the concentration of hydrogen sulfide in the gas phase to the concentration in the solid phase. This paper presents data on hydrate formation for mixtures of hydrogen sulfide and methane and presents the equilibrium constants which were calculated from these data. EXPERIMENTAL PROCEDURE The apparatus used to determine the conditions of hydrate formation for the methane-hydrogen sulfide system was similar to that employed by previous investigators.3,18,19 A charge gas cylinder was used to supply the hydrogen sulfide-methane mixtures, called the charge gas, and to supply the pressure up to 1.000 psia. This

Jan 1, 1955

By J. W. Halley, G. L. Plimpton

Because of the two distinct stages in the solidification of rimmed steel, segregation in the rimmed ingot is more complex than that in the killed or semikilled ingot. In the earlier stage, chemical reactions, resulting in evolution of gas and vigorous stirring of the metal, effect a degree of negative segregation unique to rimmed steel. The composition of this zone constitutes the principal quality advantage of this type of steel. In the later stage of solidification, after the evolution of gas has ceased, the segregation follows the general pattern of a more completely deoxidized steel. However, the composition of the liquid remaining after the first solidification stage varies markedly from that of the original melt, some constituents having been partially removed as reaction products while the concentration of others has been intensified by rejection from the metal solidifying in the first zone. The aim, from the standpoint of segregation, in rimmed steel of high quality is to effect a maximum negative segregation in the rim zone without excessive concentration of undesirable elements at the center of the ingot. To achieve this aim, the composition of the melt may be varied and the furnace and pouring practice may be adjusted within certain limits. It is the purpose of this study to discuss segregation in rimmed steel from the standpoint of the mechanisms that produce it and to survey the phases of open-hearth practice that influence those mechanisms. Mechanisms Producing Segregation The mechanisms that determine the degree of segregation in the rimmed ingot are closely interrelated, making it difficult to select the primary factors and to determine a satisfactory order for presenting them. For instance, the question of sulphur segregation is relatively simple, since sulphur is not directly involved in chemical reactions in the ingot; but its concentration in the rim zone is dependent not only on its original analysis in the melt, its segregation coefficient, and the freezing rate, but also on the rate of its removal from the impure film on the solidifying surface. This washing action involves all the factors (such as freezing rate, the carbon-oxygen product, pressure, etc.) that determine the rate of gas evolution and hence the efficiency of film removal. Sulphur distribution between the rim and core is affected by the volumetric ratio between the two zones, and its segregation in the core is a function not only of the freezing rate of the core but also of all the foregoing factors that determine its concentration in the metal when solidification of the core starts. To simplify the presentation, it is proposed to treat the mechanisms affecting segregation independently in this section, reserving a discussion of their over-all effects for the section in which actual segregation data are given. The factors affecting segregation will be treated in the following order: (I) differential solidification, (2) removal of constituents as

Jan 1, 1945

By R. D. Reiswig

An increasing amount of high-temperature metall~?~gical research is carried out in resistively heated tube furnaces in which a bare specimen is suspended by a fine wire at the midpoint of the tube. It is shown that the assumption of near-blackbody conditions on the surface of the sample may give rise to errors in optical pyrometry of 50°C or more. A number of papers published in the metallurgical literature in recent years have described the use of high-temperature tube furnaces for heat treatments, melting-point determinations, and other work. Typically, the tube is of a refractory metal with open ends, is heated by the passage of an electric current, and has concentric cylindrical radiation shields outside it. In at least one of these,' the specimen is contained within a crucible having a small hole in its lid through which optical-pyrometer measurements are made under essentially blackbody conditions. In another design,* the specimen is inside a muffle which is concentric with the heater tube and which contains a number of washerlike longitudinal radi- ation shields to reduce axial temperature gradients and to give conditions near the specimen closer to those of a black cavity. Yet another design3 employs a wire specimen coaxial with the heater tube. Blackbody conditions are simulated by passing current from a separate supply through the wire until it "disappears" against the background (the inside of the heater tube) as seen through a radial spy hole in the tube. Good agreement with known melting points is achieved when an optical pyrometer is used under such disappearance conditions as the melting point is approached. That this latter method works so well is due, evidently, to considerations such as those mentioned by Dike4 and others.5-8 A more common method than the above, however, has been the suspension of an uncovered specimen by a fine wire in a resistively heated tube with open ends. A radial spy hole about midway between the ends of the tube permits optical-pyrometer observations on the specimen, the inside of the tube, or both. So observed, the specimen typically appears to differ but little in brightness temperature from the inside of the tube. According to De vos9 the radiation from such a spy hole in an empty tube of reasonable 1ength:diameter ratio (e.g., 10 or greater) should be essentially blackbody radiation. For these reasons, apparently, descriptions of work carried out in such furnaces usually include a statement to the effect that conditions surrounding

Jan 1, 1964