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By Junnosuke Yamamoto

Substituting sodium hydroxide for sodium carbonate as a binder in a glass batch yields harder pellets with a lower melting point. This paper explores the degree of NaOH substitution that is feasible, and compares pellet hardness, and amount of dusting with the degree of NaOH substitution. The effects of the the amount of soluble silicate in the pellet and residual hydroxide concentration in the pellet on pellet hardness are also studied.

Jan 1, 1977

By Frank Julian

The determination of manganese by precipitation with potassium chlorate from a solution in concentrated nitric acid, filtration through asbestos, and solution in a reducing agent whose excess is estimated, is open to the objections that the filtration and subsequent solution of the binoxide are apt to be very slow, and that the asbestos may (according to Troilius), unless perfectly purified, affect the titration. In the following modification, filtration is avoided. I give the method as I use it for Bessemer steel. In an 8-ounce Griffen beaker dissolve 1 gramme drillings in 15 c.c. nitric acid (1.2 sp. gr.). Evaporate to 5 c.c.; add 20 c.c. concentrated nitric acid and precipitate with chlorate as usual, avoiding a large excess; then add about 60 c.c. warm water, and 10 c.c. of the oxalic solution; stir until of a clear light yellow color, and titrate with permanganate while the solution is at about 80' C. The binoxide should dissolve immediately when the oxalate isadded. The titration is rapid, and the end-reaction, though transient, easily caught after a little practice. The standard solutions used are: 15 grammes crystallized ammonium oxalate to a liter, and 1.6 grarnmes potassium permanganate to a liter. For standardizing the permanganate, to 10 c.c. of the oxalic solution is added 50 c.c. of hot water, and a solution of 1 gratnme of steel in concentrated nitric acid, from which the manganese has been removed by potassium chlorate and filtration through asbestos. I have made a large number of determinations in steel, pig-iron,

Jan 1, 1888

By Mark D. Zoback, Bezalel C. Haimson

INTRODUCTION A Workshop on Hydraulic Fracturing Stress Measurements was convened by the authors in December 1981 in Monterey, California under the auspices of the U.S. Geological Survey and the U.S. National Committee on Rock Mechanics. There are now over a dozen groups of investigators around the world who are actively using the hydraulic fracturing method for making in-situ stress measurements. Because of the extensive recent experience of these different groups, the Workshop enabled forty investigators from eight countries to comprehensively assess the status of the method. Based on the presentations and discussions at the Workshop, in this paper we briefly discuss the current status of the hydraulic fracturing stress measurement method concentrating on problem areas where further research needs to be done. A complete account of the presentations at the Workshop will be available through the Proceedings of the Workshop which will be published by the U.S. National Committee on Rock Mechanics in early 1983. The most exciting aspect of the Workshop was the discovery by the various groups of investigators that others were having very similar experiences with the method. The consensus among the different groups of investigators at the Workshop was that they were recording very similar pressure-time data in the field, they were able to interpret them in similar ways, and they were achieving results that were quite encouraging because of several factors. First, the results at various locales were found to be internally quite consistent. This was reported by investigators from Germany (Rummel, Baumgartner, and Alheid, 1982), Japan (Tsukahara, 1982), Australia (Enever, 1982), and the U.S. (see, for example, Haimson, 1978, 1982a; Zoback

Jan 1, 1982

By George W. Becker, Blair R. Benner, Ronald J. Roman

A computer model for the leaching of oxide copper heaps is developed and verified in laboratory tests. The model can be used to scale-up laboratory test data and to simulate the results of various operating philosophies on heap leaching. The model is applicable to leaching processes where the rate of leaching is controlled by a deficiency of reactant or diffusion of a reactant through the leached rock. Several examples are presented showing the sensitivity of the recovery vs. time curve to the variables in leaching.

Jan 1, 1975

By M. Gangal, B. Paul

It may be seen from Maurer's survey (Maurer,l 1966) that most of the common methods used in rock drilling today depend upon mechanical loading of the rock. In order to predict the behavior of rock under an imposed system of stresses, it is necessary to have a valid criterion which delineates those combinations of stress which cause macroscopic rock failure from those which do not. Admittedly, the conditions under which brittle materials fracture depend very much upon statistically variable local effects such as inclusions, grain boundaries, minute imperfections, etc. However, it is extremely desirable to be able to predict fracture under complex states of stress by means of a stress-criterion of failure, where, for a given material, the effects of the other variables mentioned are incorporated into a small number of experimentally observable parameters. One of the most successful of these "macroscopic stress criteria" has been the Coulomb-Mohr theory 2,3 (also see Jaeger 4 and Terzaghi 5), modified by the addition of tension cutoffs (Paul 6). At first thought it might seem rather odd that a macroscopic theory is capable of predicting fractures which originate at highly localized random imperfections at an atomic level (or more likely at the level of individual mineral grains in rocks). However, Griffith7 showed that fractures originating near the tips of randomly oriented elliptical cracks lead to the macroscopic stress criterion of failure indicated in Fig. 1 (a). Fig. I (a) is to be interpreted in the following way: P and Q represent the maxi mum and minimum principal stresses (compression is considered positive) in a macroscopically isotropic body; fracture will not occur for any combination of principal stresses lying within the 'fracture curve' shown, but

Jan 1, 1967

By Horace Pops, J. F. Libsch

THE discovery of SAP alloys (sintered aluminum powders) by lrmannl has stimulated investigations in other alloy systems.23 Not only do such alloys have good room-temperature properties, but they maintain high strength after prolonged service at elevated temperatures. In addition, they show high structural stability, including unusually high recrystallization temperatures. These characteristics are secured by dispersion hardening. For this investigation, Zn-ZnO alloys were selected. Practically, the fact that commercially pure zinc recrystallizes near room temperature prohibits strengthening and hardening by cold deformation and therefore limits the application of zinc where mechanical strength is important. Similarly, the poor

Jan 1, 1961

By D. M. Lewis, R. C. Emmett, B. C. Wojcik, F. A. Baczek

The ElectroSlurry™ electrowinning concept has been incorporated into a process flowsheet for recovering copper from smelter flue dusts. The process has averaged 96% recovery of the copper as high-grade electrowon cathode, while at the same time removing a majority of the impurities that degrade drawn copper as a result of recycling flue dust and liberator cathodes. The dust is processed through several stages consisting of leaching, copper precipitation, ElectroSlurry electrowinning, and waste liquor treatment. The process may be integrated into a smelter operation and become an effective and feasible means of maintaining good product purity.

Jan 1, 1981

By V. Rajaram, H. W. Earnest, A. W. Jenike

Mine backfilling is a desirable method for the disposal of retorted oil shale. Hydraulic, mechanical and pneumatic transport and stowing methods were investigated, and the mechanical transport and stowing method using conveyors was selected as the most promising system. Transport of retorted oil shale at the rate of 2700 t/h (3000 stph) to the backfill level, situated about 610 m (2000 ft) below surface, with skips or conveyors is uneconomic. Hence, borehole transport utilizing gravity flow was investigated. This Paper describes the theory of flow, flow properties of retorted oil shale, and the design of a borehole and hopper system.

Jan 1, 1980

By Y. L. Yao

A scale based on existing data for the mutual solid solubilities of metals in binary systems has been compiled. This scale is useful for estimating the relative magnitude of two solubilities, provided that these two metals do not form a continuous series of solid solutions. In his classic work on the theory of metallic solid solutions, Hume-Rothery proposed that, other things being equal, a metal of lower valency should be regarded as more likely to dissolve one of higher valency than vice versa. He called this the "relative valency effect". Later he found that the application of this general principle was limited to the three univalent metals: copper, silver, and gold. In dealing with alloys of these metals with metals of higher valency, Hume-Rothery stated, it is usually found that the solid solution of the univalent metal is of the greater extent.&apos; The question of whether there is a systematic trend in comparing the relative magnitude of mutual solubilities, if valency is not considered a criterion, naturally arises. The present paper proposes a "mutual solid solubility" scale on an empirical basis. The order of its arrangement is determined by the relative magnitude of mutual solid solubilities. Some applications of and inferences from this scale are given. ORIGIN AND SCOPE OF THE SCALE An extensive survey of over 400 binary phase diagrams shows that, with certain exceptions and within certain limitations, metals can be arranged in the following order: Na Zn Cd Ga Bi Ge Sb As Hg Sn Si Mg Li Ba In Tl Pb Al Ca Be Mn Cr Re W Mo Cu V Ta Fe Ru Cb Co Ti Hf Ni Os Zr Ir Pt Au U Rh Ce Pd Ag Th so that a metal higher on the scale tends to have a higher solubility in a metal lower on the scale than vice versa. some experimental solubility data are given in Table I. These data, unless otherwise specified, are taken from Hansen and Anderko.6 Throughout this paper, the term "solubility of A in B" is taken to mean the maximum solid solubility of A in B in atomic percent, while the maximum solid solubility of B in A in atomic percent is called "reciprocal solubility". The exceptions found in the above-mentioned survey are: Al-Ag system, 20.34 at. pct Al in Ag, 23.8 Ag in Al; Mg-Pb system, 5.9 Mg in Pb, 7.75 Pb in Mg; As-Sn system, vanishingly small amount of As in Sn, a large As primary solid solution; Cd-Hg system, Cd in Hg <Hg in Cd; Mg-T1 system, 5(?) Mg in ßT1, 15.4 T1 in Mg; W-Ti system, -21 W in ßTi, -25 Ti in W; Zr-Ag system, probably small amount of Zr in Ag, 20 Ag in ßZr.7 Considering the large number of examples, the exceptions are few. It is remarkable that metals may be so arranged without considering other factors such as size, crystal structure, electronic structure, and so forth. A limitation to the use of the scale is the fact that it cannot be tested for two metals forming a continuous series of solid solutions. It is interesting to point out that when the continuous solid solutions have a miscibility gap the critical composition is

Jan 1, 1961

By N. H. MacMillan, W. M. Mularie, R. E. Jackson, A. R. C. Westwood

The initial results of a study of the environment-sensitive microhardness and diamond rotary drilling behavior of granite and its constituent minerals quartz and feldspar (microcline)1 have established that many similarities exist between the environment-sensitive mechanical (chemomechanical) behavior of these materials and that of the simpler solids such as periclase, soda-lime glass, and alumina4 studied previously, at least as far as n-alcohol (straight-chain alcohol) environments are concerned. The results of this study (hereafter designated study I) also suggested that the rate of drilling of granite in these environments is controlled by the chemomechanical behavior of its quartz constituent, and is greatest in those environments which impart a zero l-potential to this phase, thereby maximizing its hardness. Now, cationic surface-active species strongly influence the l-potentials of silicate minerals. For this reason they are widely used in mineral separation operations. In particular, dodecyl trimethyl ammonium bromide (DTAB) was found in study I to produce f 0 for quartz at a concentration in water of 107 to 10-4 moles per 1. Accordingly, the influence of dilute aqueous solutions of this surfactant on the drilling behavior of granite also was examined in study I. This revealed that granite could be drilled three to four times faster in 10-° molar aqueous DTAB than in water, and confirmed by experiment the suggestion that granite is most effectively drilled with a diamond core bit in environments which impart a zero l-potential to quartz. According to O&apos;Connor and Buchanan&apos; however, the isoelectric point for quartz in aqueous DTAB solutions occurs at a concentration of .•.•2 x 10-° moles per 1, rather than [101 to 10-1] moles per 1. To confirm the results of study I, therefore, a more comprehensive investigation of the [ ]-potentials of quartz, microcline, and Westerly granite in aqueous DTAB environments has now been undertaken. At the same time an examination has been made of one of the basic assumptions of the current conceptual understanding of chemomechanical effects. In this view, although hardness changes occur essentially instantaneously following wetting of the solid, they are confined to a surface layer at most a few micrometers (µm) deep. Hence, to maximize the influence of chemomechanical effects on bit penetration rate only shallow cuts should be taken. Practical penetration rates are then obtained by increasing bit rotation speed. Experimental l-potentials were determined by the streaming potential technique using an automated rapid-cycling apparatus recently developed by Martin Marietta Laboratory from a design by Somasundaran and Kulkarni. The drilling studies employed 3.2-mm-OD 120-grit diamond-loaded core bits with a wall thickness of ~0.7 mm, and bit rotation speeds of 2200 and 25,000 rpm. The load applied to the bit was independent of the depth drilled in both cases. The 2200 rpm measurements employed the same drill press and puddle drilling technique as used in study I. The higher rotation speed was obtained using a water-driven dental turbine drill. In the case, the surface active fluid was pumped down the axis of the bit to ensure efficient wetting and flushing of the drilling debris from the hole. In both cases drilling rate was measured by the parameter D(200), defined as the average rate of bit penetration during the interval from 150 to 250 sec after drilling commenced.

Jan 1, 1976

By T. J. O’Neil, S. J. Kirk

In 1978, a multidisciplinary team from the University of Arizona, the Mines Project Group, conducted a study to examine reclamation alternatives for a proposed open-pit copper mine. The cost of a waste dumping plan designed by a mining consulting firm was determined as well as the cost of dumping configuration prepared by the Mines Project Group. The latter dumps were designed to be more socially acceptable and aesthetically pleasing, in addition to serving more creative end land uses than the dumps designed by the mining consultant. One dump configuration designed by the interdisciplinary team was the least expensive plan of all the alternatives considered.

Jan 1, 1984

By Clarence Fenner

THE manufacture of optical glass is a process that demands careful regulation and control at all stages in order that satisfactory results may be obtained. The product, to serve its purpose, must meet stringent requirements, which can be assured only by careful procedure in manufacture. During the greater part of the time that a pot of glass is in the furnace, temperatures should be kept within certain rather narrow limits; a departure on either side is likely to be detrimental to the glass and may result in total loss. If the temperature during melting and fining be low, the melt is likely not to fine properly and the glass will contain quantities of bubbles, or "seed," or it may become milky and unfit for use; too high a temperature, on the other hand, is severe on the pot and may cause it to leak or cast stones, or the increased solution of pot material in the melt may acid to the color of the glass and decrease its transmission. Moreover, variations in the working temperature will mean variations in the amount of selective volatilization and, consequently, variations in optical properties from pot to pot. Furthermore, in the closing stages of furnace treatment, the melt is cooled until a certain degree of stiffness is attained, when the pot is withdrawn. The quality of the glass-its freedom from striae and bubbles-will depend in large measure on whether the temperature to which cooling has been carried is suitable. For each type of glass there is a narrowly restricted range of temperature to which each pot of the given type should be cooled before withdrawal. A quick and reliable method of measuring temperatures is, therefore, of the first importance. In the optical-glass work conducted by the staff of the Geophysical Laboratory during the period of the war, much attention was given to the clatter of determining what methods would meet the requirements. This article will deal with these investigations and with the application of the results to actual practice at various plants. At the. time that the work of the Geophysical Laboratory was begun at the Bausch & Lomb plant, each melting furnace was equipped with

Jan 7, 1919

By W. G. Cornwell, R. J. Hisshion

The development of a process for the treatment of telluride concentrates at Emperor Gold Mining Co. Vatukoula, is discussed. The concentrate is produced by flotation in cyanide solution immediately after milling. Two stages of cleaning are employed and a high-grade concentrate is produced usually containing more than 50% of the precious metal. The process developed in the first instance involved batch roasting followed by batch leaching in strong cyanide solution, recovering gold and silver only. The procedure currently employed is chemical oxidation of the tellurides using hypochlorite as the oxidant in a basic solution of a caustic soda and sodium carbonate. After oxidation the gold and silver are recovered by cyanidation. The residue is then leached with sodium sulfide and elemental tellurium precipitated with sodium sulfite.

Jan 1, 1977

By T. P. Oxford, G. Y. Onoda, E. D. Whitney

Disposal of phosphatic clay waste slurry has been a problem since the advent of hydraulic processing of phosphate rock in Florida. Alternatives to the present practice of storing slimes behind earthen dikes have been earnestly sought for more than a quarter of a century. Seepage dewatering is a promising technique intended to increase waste clay solids content to a level sufficiently high to permit clay disposal in mine cuts, in lieu of above-grade impoundment. An experimental array of vertical seepage columns containing mine tailings sand was constructed. Significant improvement in waste clay dewatering relative to that occurring in a control test was observed when approximately 1800 m3 of waste clay was disposed of in the presence of the seepage aids.

Jan 1, 1983

By G. H. Tausch, J. R. Dublin, T. A. Huber

Simplified equipment and techniques have been developed to permit cementing a completion interval in a well and recompleting higher, lower, or at the same depth in such a manner as to: 1. Eliminate the need for a conventional drilling or workover rig. 2. Eliminate mud and other cement contaminants which have long interferred with ideal cementing. 3. Eliminate need for drilling out cement. 4. Provide a more satisfactory recompletion. 5. Provide a more economical recompletion. This technique involves the use of a small-diameter, lightweight, tubing extension which is run on a wireline and set in a landing nipple previously installed in the tubing string. Low squeeze pressure and small cement volumes, with their attendant cost reduction, are successfully used when wells are completed and reworked with salt water or other penetrating fluids. Relatively low-water-loss cement is an integral component of the technique which provides that excess cement be reverse-circulated from the well to leave the casing void of cement when recompleting lower or in the same interval. Substantial cost reductions are realized by using the simplified or low-pressure cementing technique, and the ratio of successful squeeze-cement operations has been increased. Squeeze-cementing or recementing is the act of filling a channel behind casing or filling holes purposely placed in the casing. To obtain a satisfactory squeeze-cement job, it is necessary only to fill the channel or the perforation holes with a cement filter cake and to allow it to harden in that position. In the past, the presence of mud in a well has been considered the chief deterrent to obtaining a good cement bond and satisfactory cement job; however, late developments in squeeze-cementing have made it possible to eliminate cement contamination or interference. Since it is possible to form a cement filter cake with a small pressure differential, squeeze-cementing with high pressures may not be necessary in most cases. The amount of cement needed to fill the annulus about the casing and even to fill part of the casing, if necessary, is generally small in quantity. Use of low squeeze-cementing pressures and small quantities of cement provides the following advantages: 1. Longer effective life of well tubing, casing, and other equipment; and less chance of costly equipment failure due to excessive pressure. 2. Monetary savings effected by elimination of retainers and specal squeeze-cementing tools. 3. Monetary savings effected by use of small quantities of cement and fewer squeeze-cementing operations. 4. Future surface squeeze-cementing equipment may be smaller and more economical to operate and maintain.

Jan 1, 1955

By S. A. Ford

A SHORT and accurate method for the estimation of manganese in iron and steel is of great advantage to Bessemer works, and I think it may be of interest to some of the members of the Institute to give in detail the process in use in the laboratory of the Edgar Thomson steel works. The process is based on the reaction first described by Beilstein and Jawein.* The steel, spiegel, or iron is dissolved in strong nitric acid, sp. gr. 1.4. Evaporation to dryness is not necessary, unless the amount of silicon is large, as in the case of certain pig irons. Then, as a clogging of the filter in the subsequent filtra¬tion is apt to follow, dissolve first in a dish in hydrochloric acid, quickly evaporate to dryness, redissolve in the strong nitric acid, boil, and while boiling throw in crystals of chlorate of potash from time to time. Violent action ensues, yellow fumes are given off, and binoxide of manganese is precipitated, since it is insoluble in strong * Berichte der deutschen chemisehen Gesellschaft, vol. xii, page 1528.

Jan 1, 1881

By S. C. Termes, R. L. Wilfong

As part of an effort to provide basic data on the fundamental scientific and engineering principles of minerals beneficiation, the Bureau of Mines is conducting research on the flocculation of mineral fines. This paper presents results of studies using cross-linked starches containing carboxyl, diethanolamine, iminodiacetic acid, and xanthate groups to flocculate hematite, goethite, chromite, manganite, pyrolusite, cuprite, and cassiterite fines. The carboxyl and xanthate derivatives flocculated all minerals except cassiterite; the latter was flocculated by only the diethanolamine derivative. The imlnodiacetic acid derivative flocculated hematite, goethite, chromite, cuprite, and pyrolusite fines. Zeta potential measurements were made to help define the reaction mechanism responsible for flocculation. These measurements indicate that electrostatic attraction probably is not involved, except possibly in the case of the diethanolamine derivative. The separation of hematite from quartz by selective flocculation with chelating crosslinked starches under two pH conditions and with two dispersing agents is described. Best recoveries and grades were found when either the carboxyl or xanthate derivatives was added at the natural pH of the pulp in the absence of a dispersing agent.

Jan 1, 1984

By C. M. Marquardt

Tramp iron and steel moving on a conveyor belt cause small currents to be generated in a coil situated in a strong magnetic field, which are converted to an alternating current and are amplified. The output voltage from the amplifier fires a thyratron with a relay in its anode circuit, which actuates a howler and simultaneously drops a spot of marker material on the belt. THE problem of tramp iron removal from moving ore belts is a long standing one. When heavy ore streams are carried on a belt, magnetic pulleys and strong surface magnets fail to remove tramp buried in the ore stream. Tramp iron buried in the ore stream cannot be pulled from the bed by surface magnets and is carried past the magnetic pulley by the falling ore stream. With the increased use of detachable bits the problem of the detection and removal of tramp has become more necessary and difficult. Several types of tramp detectors have been developed. It would serve no practical purpose here to review exhaustively the literature on the subject. Methods of tramp detection used are: (1) The magnetic method, wherein the small current generated by the magnetized tramp passing a Coil is used. (2) The unbalanced oscillator method wherein the tank circuit of a stable radio- or audio-frequency oscillator is unbalanced causing a change of frequency or a change in plate current due to changes in eddy currents, hysteresis, or dielectric because of the presence of tramp. (3) The bridge methods wherein the impedance of one leg of an alternating current inductive bridge is changed due to the presence of conducting tramp. Each of these methods of tramp detection has its field of usefulness. The second and third methods are excellent for oxide iron ores, coal, sand and gravel, grain, etc. However, these latter methods are not suitable for use on ores that contain rich conducting sulphides, since a large piece of pyrite or galena will cause the same detector response as a piece of tramp iron. At the Caselton, Nevada, plant of the Combined Metals Reduction Co., sulphide ores are treated; therefore, it was necessary that a tramp detector operating on only the magnetic properties of the tramp iron be used. Tramp iron detectors of this type operate on the principle that if a piece of tramp iron moves near a coil in a high intensity, steady magnetic field, the presence of the moving tramp iron causes the magnetic flux lines through the coil to change. This induces a mall current in the Coil. In series with the Coil is generally placed a relay sensitive to currents of 1 to 3 microamp. When the tramp iron passes near the coil the flux linkages change, causing this very sensitive relay to actuate. Since the contacts of such a relay are very small it must actuate a second relay capable of breaking a larger current

Jan 1, 1951

By C. M. Marquardt

Tramp iron and steel moving on a conveyor belt cause small currents to be generated in a coil situated in a strong magnetic field, which are converted to an alternating current and are amplified. The output voltage from the amplifier fires a thyratron with a relay in its anode circuit, which actuates a howler and simultaneously drops a spot of marker material on the belt. THE problem of tramp iron removal from moving ore belts is a long standing one. When heavy ore streams are carried on a belt, magnetic pulleys and strong surface magnets fail to remove tramp buried in the ore stream. Tramp iron buried in the ore stream cannot be pulled from the bed by surface magnets and is carried past the magnetic pulley by the falling ore stream. With the increased use of detachable bits the problem of the detection and removal of tramp has become more necessary and difficult. Several types of tramp detectors have been developed. It would serve no practical purpose here to review exhaustively the literature on the subject. Methods of tramp detection used are: (1) The magnetic method, wherein the small current generated by the magnetized tramp passing a Coil is used. (2) The unbalanced oscillator method wherein the tank circuit of a stable radio- or audio-frequency oscillator is unbalanced causing a change of frequency or a change in plate current due to changes in eddy currents, hysteresis, or dielectric because of the presence of tramp. (3) The bridge methods wherein the impedance of one leg of an alternating current inductive bridge is changed due to the presence of conducting tramp. Each of these methods of tramp detection has its field of usefulness. The second and third methods are excellent for oxide iron ores, coal, sand and gravel, grain, etc. However, these latter methods are not suitable for use on ores that contain rich conducting sulphides, since a large piece of pyrite or galena will cause the same detector response as a piece of tramp iron. At the Caselton, Nevada, plant of the Combined Metals Reduction Co., sulphide ores are treated; therefore, it was necessary that a tramp detector operating on only the magnetic properties of the tramp iron be used. Tramp iron detectors of this type operate on the principle that if a piece of tramp iron moves near a coil in a high intensity, steady magnetic field, the presence of the moving tramp iron causes the magnetic flux lines through the coil to change. This induces a mall current in the Coil. In series with the Coil is generally placed a relay sensitive to currents of 1 to 3 microamp. When the tramp iron passes near the coil the flux linkages change, causing this very sensitive relay to actuate. Since the contacts of such a relay are very small it must actuate a second relay capable of breaking a larger current

Jan 1, 1951

By Morris Muskat, J. M. McDowell

In both production and refining operations of the oil industry many processes are controlled by the gas-liquid phase relationships of the hydrocarbon mixtures of interest. The quantitative behavior of fractionating or distillation columns and stills depends on the changes in the equilibrium distributions of the hydrocarbon components between the gas and liquid phases as the pressure or temperature conditions may vary along the length of the column or as the gross operating parameters and compositions are varied. In oil producing operations the nature and amount of gas phase developed within an underground reservoir as it is being depleted and its pressure declines also involve the basic equilibrium gas-liquid phase interactions. The influence of surface conditions of temperature and pressure and various separation procedures on the nature and amount of stock tank oil and natural gas recovered from a given well stream is likewise determined by the same basic phase equilibrium characteristics of the hydrocarbon systems. Such equilibrium separation of the gas and liquid phases in a well stream is of importance both in establishing optimum separator conditions for obtaining maximum stock tank oil yields and in the general problem of crude stabilization. The phenomena involved in these problems and their quantitative aspects can, of course, be established in each individual instance by appropriate laboratory experimentation. It has been found, however, that by associating with the individual hydrocarbon components functional characteristics de- scribing their individual gas - liquid phase equilibrium behavior, the phase properties of the composite mixtures can be predicted by mathematical computation. These characteristics have been termed "equilibrium constants", or "equilibrium ratios"," and are defined by the general equation: where K, is the equilibrium ratio for the jth component, y, is the rnol fraction of that component in the gas phase, and xj is the corresponding mol fraction in the coexisting liquid phase. Considering the Kj as representing available and measurable properties of the individual components of a mixture, and as defined by Eq. (l), it is readily shown that in a coexisting gas-liquid system the rnol fraction concentrations of the individual components in the gas phase, y,, and those in the liquid phase, x,, are given by the expressions: where the nj are the corresponding rnol fraction concentrations in the composite system, and ng is the mol fraction of the whole which is in the gas phase. The basic unknown in Eq. (2) is n,: which gives the gross separation between the gas and liquid phases. This may be determined in principle by imposing the requirement that the sums of the mol fractions in both the gas and liquid phases are unity, i.e. by the equations: The solution of the equivalent Eqs. (3) lying between 0 and 1, when inserted into Eqs. (2), provides a complete description of the compositions of the coexisting gas and liquid phases. While the Eqs. (3) are essentially equivalent to polynomial equations, such transformations are of little value when dealing with multicomponent sys-

Jan 1, 1949