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By Irving M. Symonds

COMPAÑIA Minera de Peñoles, S. A., at its Avalos unit operates a lead-zinc concentrator having a capacity of about 600 short tons per day. Lead and zinc concentrates are made by flotation methods. The concentrator is at Terminal de Providencia, in the state of Zacatecas, some 70 miles south of Saltillo, Coahuila. The Peñoles-Avalos railroad operating between the plant and Estacion Avalos, a distance of 6 miles, makes connections with the Coahuila and Zacatecas railroad, which in turn connects with the Nacionales de Mexico at Saltillo. The three railroads are each of different gauge, requiring the transfer of all supplies and concentrates at each junction. The mill operates on company ores, on ores from leased mines, and as a custom mill. The custom business is very small. The lead concentrates are shipped to company smelters at Monterrey, Nuevo Leon and Torreón, Coahuila. Since the European war, all zinc concentrates have been shipped to the United States. ORE TREATED The major source of ore supply is a group of four mines owned or leased by the company, some three miles south of the mill in the mountains, from which the ore is delivered to the mill by a gravity aerial tramway. Custom ore comes in by rail. The ores occur in chimneys. The upper levels contained oxidized siliceous ores of lead, copper, silver and gold, with varying amounts of zinc. These ores were direct-smelted. In the first two years of operation a good deal of the tailing loss was caused by the oxidized content of the ores milled. Much of the ore in the transition zones between the oxides and sulphides was not mined. The ores now being milled are clean, hard sulphides in a limestone gangue, with only occasional contamination of oxides. The lead and zinc sulphides are of coarse structure and are freed even above flotation sizes. The galena is usually "steel" colored, easily and quickly floated. When there is any oxidation, it is usually on the coarsest crystals. The zinc minerals vary a good deal in color; a resin sphalerite predominates but there are varying shades of brown marmatites. On an average, the zinc sulphides contain 64 per cent zinc. The only common copper mineral is chalcopyrite. Little is known of the occurrence of gold and silver. Waste minerals are mainly limestone and pyrite, both of which are barren. The ores vary from 20 to 35 per cent pyrite. Mill heads for the year 1940 and the first eight months of 1941 are given in Table I. [ ]

Jan 1, 1942

By V. H. Wilhelm

The year 1936 was a prosperous one for the oil industry in California. Increases in crude prices were posted in February and March. Re-establishment of voluntary curtailment in February was a factor in holding production at an efficient level throughout the year. Reduction of storage was effected through adherence to curtailment measures, aided by greater demand and smaller average well completions. During the first six years of voluntary curtailment, allotments were increased during the summer season and reduced during the winter season. This year, good results were obtained through a revised system of allocation, by which the California monthly quota was held constant at approximately 540,000 bbl. per day. After a 7-month period of practically unrestricted production (ending in January 1936), numerous operators found that curtailment was still necessary, as California and export market,s were not yet capable of absorbing the state's potential production, which was estimated to be in the neighborhood of 850,000 bbl. per day. Therefore, in February California operators again placed themselves under voluntary curtailment; with the result that state production dropped from around 700,000 bbl. per day in January to a low of 565,000 bbl. per day in April, and increased gradually to around 585,000 bbl. per day for December. Drilling activity during the year increased about 10 per cent over that of the preceding year, although the resultant production per well decreased. Field Discoveries As a result of a very active wildcatting campaign in California, aided by better interpretation of geophysical data, five new oil fields and two new gas fields were discovered. Oil Fields Greeley Field, Kern County.—The Standard Oil Co. added to its list of djscoveries by drilling and completing its K.C.L. No. 11-1 well at a

Jan 1, 1937

By R. F. Yap, N. Arbiter, C. C. Harris

A fully-instrumented driving mechanism has been constructed to study the power, aerating and solid suspension characteristics of several laboratory flotation machines. Machines operating over normal flotation speed ranges give substantially constant power numbers in liquid systems indicating that they operate close to fully baffled turbulent flow conditions. Owing to lack of geometrical scaling, power numbers for different sizes of cells of the same make are different. Even larger differences occur between cells of different manufacturers. For a given impeller, varying the tank size did not significantly affect the power consumption. Tank geometry and baffling has a slight effect on power consumption with shrouded impellers. For a given impeller speed, suspension height decreases while power increases with increasing mass of solids in suspension. While power consumption is hardly affected by particle size and clearance between the impeller and tank bottom, the suspension height significantly increases as clearance increases and as particle size decreases. Aeration was found to affect not only power but also the suspension characteristics of the machine. For closely sized particles, drastic sedimentation occurred when a critical value of the air flow number was exceeded. The critical air flow number decreased with increasing particle size. This effect was less marked with a wide particle size range. The self-aerating capacity of flotation machines increases with cell size at a given speed for the same impeller-shroud system, but decreases in the presence of frother and solids. Equations have been established for correlating all of the studied variables. Data taken from the literature were also correlated with these equations. The modern mechanical flotation machine has, over a period of 60 years, displaced other designs to become the dominant type. Once the correct chemical environmental conditions have been established, the major requirement, selective mineral-air adherence, is essentially a function of two operating variables — impeller speed and air rate. The special nature of this dependence is such that in the same apparatus, but under different operating conditions, adherence can be either prevented or destroyed. Another aspect of this observation is that flotation machines though differing in detail to a considerable extent can produce similar metallurgical results. It must be concluded that having determined the correct reagent levels, establishing the correct operating conditions are at least as important as machine design. Since about 1960, after 30 years of fairly stable circumstances, manufacturers have been developing new types of machines whose major feature is emphasis on pulp flow characteristics by virtue of new im-peller-stator designs. As far as can be ascertained, these new designs necessitate radical departures from accepted impeller speed-air rate values. Performance data are still awaited. Flotation machine development has been empirical, as is selection of operating conditions. The purpose of the work at Columbia University has been to elucidate the fundamentals of the subject so that the purely mechanical aspects of the flotation process can be understood in hydrodynamic terms.1-6 Hopefully, this might lead to intelligent selection of a particular machine and its operating conditions for a specific ore based on a minimum of testing, or even to new types of flotation machines. The present investigation is the most comprehensive to date.7,8 Earlier work, which was largely exploratory, has been repeated and extended and employes the most accurate measuring techniques available. Additionally, sufficient hydrodynamic data were obtained under flotation conditions to delineate the relevant operating ranges. Attention has been given to scaling in that several geometrically scaled tanks and impellers have been constructed and tested; it has been pointed out elsewhere that undistorted geometrical scaling rarely pertains in flotation machine design.5 This paper is divided into sections dealing with relevant combinations of the three phases: liquid, air and solid. Summaries of the literature have been given in previous publications2-4 and will not be repeated here. Recently, several reviews of mixing have appeared, which can be usefully referenced.9-11 It is of interest to note that flotation is not included

Jan 1, 1970

By S. Usui, I. Iwasaki

The effect of pH on the adsorption of dodecylamine at the mercury-aqueous solution interface was investigated by differential capacity and electrocapillary measurements. With dodecylammonium acetate, the differential capacity curves showed two desorption peaks in the cathodic branch with their relative intensities varying with the solution pH. With dodecyltrimethylammonium chloride, only one cathodic de-sorption peak was observed in the same pH range. Through thermodynamic analysis of the electrocapillary curves, the adsorption density of undissociated amine was evaluated separately from that of aminium ion. The adsorption densities of the un-dissociated amine and of the total amine increased with increasing pH. The ratio at the interface of undissociated amine to aminium ion was several orders of magnitude greater than the ratio in the solution and increased with increasing pH. The potential at the closest distance of approach of counter ions to the mercury surface was compared with values of zeta potential on quartz previously reported. The most important variable in the flotation separation of minerals is probably the pH of the pulp, and a number of theories have been proposed to explain its effect on the condition of the mineral surfaces, on the dissociation of collectors and of inorganic and organic species (accidentally present or intentionally added) in the pulp, and on the mineral-collector interaction. In the development of a theoretical background for oxide flotation systems, an experimental approach based on electrokinetic measurements has been of much value, although the effect of pH becomes confounded since it governs both the electrochemical conditions of the oxide surface and the dissociation of the collector. For investigation of the adsorption behavior of long-chain collectors on oxide minerals, however, electrokinetic potential measurements are the most widely used technique. Hydrogen and hydroxyl ions are found to be the potential determining species, thereby governing the interfacial electrical conditions. The electrostatic interaction between the charged mineral surfaces and ionized collectors is regarded as the driving force for the adsorption of the collectors. An association of alkylamine collectors adsorbed on quartz surfaces has been postulated from streaming potential measurements, and a term "hemi-micelles" has been proposed.' The possibilities of coad-sorption of undissociated amine along with aminium ion has been inferred from contact angle measurements? and from adsorption studies.~ Electrochemical titration as applied to silver sulfide provides a more quantitative approach to the analysis of the electrical double layer at an ionic solid-solution interfaceqG and the electrochemical evidence for the adsorption of amine at pH 4.7 indicates a specific affinity of dodecylammonium ion towards silver sulfide surfaces, whereas at pH 9.2 the adsorbed species might be free arnine." A combination of differential capacity and electrocapillary measurements on a dropping mercury electrode was reported to be a sensitive method of provid- ing reliable information on the adsorption behavior of dodecylammonium acetate (DAA) at a natural (near neutral) pH.? It was also shown that there were striking similarities in the properties of the double layer and in the adsorption behavior of the amine on mercury and on such ionic solids as quartz, silver sulfide, and silver iodide. The effect of pH on the differential capacity curves at a mercury-sodium fluoride solution interface has been investigated by Austin and Parsonss who reported that between pH 7 and pH 11 there was very little effect. In the present paper, the adsorption behavior of DAA was investigated as a function of pH through differential capacity and electrocapillary measurements and the information gathered was correlated with that available in literature on quartz and silver sulfide. Experimental The apparatus and the method used for determining the differential capacity and the electrocapillary curves were identical to those described previously.' The ionic strength of the supporting electrolyte was fixed at 0.1 M with potassium fluoride, and the pH of the solution with potassium hydroxide. Only the neutral to alkaline range was covered in order to avoid the dissolution of the glass vessel with hydrofluoric acid. Results In Fig. 1 the differential capacity has been plotted against the applied potential at a DAA concentration of 10-' M at three different pH values. The curves are characterized by one capacity peak in the anodic branch, by two capacity peaks in the cathodic branch, and by a marked depression in capacity between the peaks. The depression indicates an adsorption of the arnine in this potential range. One of the cathodic peaks appears at pH 7.3 near -1.4 v and decreases with increasing pH. The other appears at pH 8.9 near —1.2 v and increases with increasing pH. At pH 9.6 only the latter peak is observed. Beyond the cathodic peaks, all the curves tend to converge with the curve in the absence of DAA, implying that two different species are being desorbed in this potential region. The anodic peak near 0.0 v increases markedly with increasing pH. The well-defined anodic peaks at pH 8.9 and 9.6 were accompanied by an appreciable increase in the current flow (in excess of O.luA), and, therefore, is a "pseudo-capacity"'" due to a

Jan 1, 1971

By G. Austin Schroter

ALTHOUGH there is now an extensive literature on the bleaching clays, not a great deal of material is to be found concerning the geological fea-tures of these deposits and their bearing on problems of exploration and development. At the same time, chemical and crystallographic research on the clay minerals during the past few years has laid a suitable founda-tion upon which to base conclusions of economic value drawn from field observations. All of the criteria and deductions herein presented are based upon extensive field work by the senior author, both in the United States and Canada, and when subjected to the ultimate tests of development and exploitation they have held up remarkably well, despite the fact that many of these conclusions apparently have not been reviewed in the litera-ture heretofore. The nomenclature of the bleaching clays is rather confusing in the light of present-day commercial standards and has even led to litigation." The old term "fuller's earth" is largely based upon trade usage and the definition of the term therefore is dependent upon the changing standards of commerce. For statistical purposes the Bureau of Mines81 classes as "fuller's earth" all natural bleaching or filtering claylike materials that possess high adsorptive capacity without previous chemical treat-ment or activation. Conversely, the so-called activated or acid activated clays are now generally recognized as any clay mineral or mixture of the clay minerals whose adsorptive capacity has been developed to commercial standards by chemical or physical treatment. Therefore, without attempting to propose any additions to the nomen-clature of bleaching clays, this paper will refer to naturally adsorptive clays and activable clays, respectively, for the two types indicated.

Jan 1, 1940

By G. Austin Schroter

ALTHOUGH there is now an extensive literature on the bleaching clays, not a great deal of material is to be found concerning the geological fea-tures of these deposits and their bearing on problems of exploration and development. At the same time, chemical and crystallographic research on the clay minerals during the past few years has laid a suitable founda-tion upon which to base conclusions of economic value drawn from field observations. All of the criteria and deductions herein presented are based upon extensive field work by the senior author, both in the United States and Canada, and when subjected to the ultimate tests of development and exploitation they have held up remarkably well, despite the fact that many of these conclusions apparently have not been reviewed in the litera-ture heretofore. The nomenclature of the bleaching clays is rather confusing in the light of present-day commercial standards and has even led to litigation.76 The old term "fuller's earth" is largely based upon trade usage and the definition of the term therefore is dependent upon the changing standards of commerce. For statistical purposes the Bureau of Mines81 classes as "fuller's earth" all natural bleaching or filtering claylike materials that possess high adsorptive capacity without previous chemical treat-ment or activation. Conversely, the so-called activated or acid activated clays are now generally recognized as any clay mineral or mixture of the clay minerals whose adsorptive capacity has been developed to commercial standards by chemical or physical treatment. Therefore, without attempting to propose any additions to the nomen-clature of bleaching clays, this paper will refer to naturally adsorptive clays and activable clays, respectively, for the two types indicated.

Jan 1, 1940

By V. H. Whihelm

Since 1935 California has enjoyed a remarkable cycle of discovery, which has placed the state in a very satisfactory position in regard to oil reserves. Most ol the geophysical plays have been drilled and it is possible that new discoveries must be made by the application of careful geologic and stratigraphic studies. During 1940 only one new field was discovered, which, although not of major importance, may lead to additional discoveries. During the year, 113 wildcats were drilled. New discoveries, extensions and a reappraisal of discoveries made in 1939 will not approximate over 50,000,000 bbl., as against an estimated withdrawal during the year of 224,000,000 barrels. Demand in terms of crude for 1940 was 632,000 bbl. per day as against 626,000 bbl. per day for 1939. Demand for gasoline was the same as in 1939, but the demand lor fuel oil increased 3.8 per cent. Compared with 1939, Japanese shipments decreased from 75,786 bbl, per day to 61,000 bbl. per day, but the balance of Pacific foreign shipments increased from 59,409 bbl. per day to 61,304. Total with-drawals from storage during the year will approximate 7,000,000 bbl., almost all of which is fuel oil. Drilling activity was slightly greater than in 1939 and accounted for 890 new producing wells as against 851 for 1939 (Table 3). Production averaged 611,900 bbl. per day as compared with 614.,842 bbl. per day for 1939. The productive acreage figure of the state was increased by 4000 through discoveries and extensions. New Discoveries Los Angeles Basin District Del Vdle Field.—Northwest of Newhall, where the first oil well in California was drilled, R. E. Havenstrite completed his Lincoln No. I well, flowing 390 bbl. of 50" gravity oil together with 7000 M CU. ft. of gas. Later the well was recompleted, after cutting off the gas, for 950 bbl. of 34" gravity oil. The type of structure from which this production is coming is a plunging anticline, complicated by faulting. The Lincoln No. I well uncovered approximately 180 ft. of net sand. This field contains a gas cap and its indicated productive area approximates 500 acres. An intensive wildcat drilling campaign is expected during this coming year in the district in the vicinity of the Del Valle field. Extensions and Deeper Sand Developments Los Ange1es Basin District Athens Field.—On the northwest plunge of the Athens structure, the Thorley Oil Co. completed its No. 12-1 well, flowing 250 bbl. of 3 2" gravity oil from a depth of 8097 ft. The area in which the well is located is complicated by faulting and it is impossible at this date to determine the importance of this deep-zone discovery.

Jan 1, 1941

By V. H. Whihelm

Since 1935 California has enjoyed a remarkable cycle of discovery, which has placed the state in a very satisfactory position in regard to oil reserves. Most ol the geophysical plays have been drilled and it is possible that new discoveries must be made by the application of careful geologic and stratigraphic studies. During 1940 only one new field was discovered, which, although not of major importance, may lead to additional discoveries. During the year, 113 wildcats were drilled. New discoveries, extensions and a reappraisal of discoveries made in 1939 will not approximate over 50,000,000 bbl., as against an estimated withdrawal during the year of 224,000,000 barrels. Demand in terms of crude for 1940 was 632,000 bbl. per day as against 626,000 bbl. per day for 1939. Demand for gasoline was the same as in 1939, but the demand lor fuel oil increased 3.8 per cent. Compared with 1939, Japanese shipments decreased from 75,786 bbl, per day to 61,000 bbl. per day, but the balance of Pacific foreign shipments increased from 59,409 bbl. per day to 61,304. Total with-drawals from storage during the year will approximate 7,000,000 bbl., almost all of which is fuel oil. Drilling activity was slightly greater than in 1939 and accounted for 890 new producing wells as against 851 for 1939 (Table 3). Production averaged 611,900 bbl. per day as compared with 614.,842 bbl. per day for 1939. The productive acreage figure of the state was increased by 4000 through discoveries and extensions. New Discoveries Los Angeles Basin District Del Vdle Field.—Northwest of Newhall, where the first oil well in California was drilled, R. E. Havenstrite completed his Lincoln No. I well, flowing 390 bbl. of 50" gravity oil together with 7000 M CU. ft. of gas. Later the well was recompleted, after cutting off the gas, for 950 bbl. of 34" gravity oil. The type of structure from which this production is coming is a plunging anticline, complicated by faulting. The Lincoln No. I well uncovered approximately 180 ft. of net sand. This field contains a gas cap and its indicated productive area approximates 500 acres. An intensive wildcat drilling campaign is expected during this coming year in the district in the vicinity of the Del Valle field. Extensions and Deeper Sand Developments Los Ange1es Basin District Athens Field.—On the northwest plunge of the Athens structure, the Thorley Oil Co. completed its No. 12-1 well, flowing 250 bbl. of 3 2" gravity oil from a depth of 8097 ft. The area in which the well is located is complicated by faulting and it is impossible at this date to determine the importance of this deep-zone discovery.

Jan 1, 1941

By F. V. Lenel

Resistance sintering under pressure is a method of hot pressing in which a powder compact is subjected to pressure and simultaneously heated by passing a low voltage high amperage current through it. Equipment for this process is described. Its basic characteristics such as resistance requirements for powders and compacts, temperature distribution in compacts, and gas reactions during resistance sintering are discussed. Examples of the sintering process in compacts made of a single metal or an alloy powder and in compacts made of mixtures of powders are presented. Potential commercial applications of the process are evaluated. THE usual sequence of operations in commercial powder metallurgy is to compact metal powders in a die at room temperature and sinter the compact subsequently without applying pressure while the compact is in the sintering furnaces. In hot pressing, on the other hand, the compacting and the sintering are combined. The loose powder, or in many cases a cold formed compact, is inserted into the die which is held at the hot pressing temperature, the compact is left in the die until it attains its temperature, and then pressure is applied and maintained for a given length of time. The die may be heated by surrounding it with a suitable furnace, by high frequency induction heating, or by passing current through the die. In hot pressing, compacts of high density and good mechanical properties can be produced in a relatively short time. One of the principal difficulties in hot pressing is the lack of suitable die materials which will have adequate strength at the hot pressing temperature. This difficulty can be overcome at least partially by heating only the material to be hot pressed without heating the die directly. This can be done by passing a low voltage high amperage current through the material and simultaneously subjecting it to pressure. Either loose powders or compacts can be hot pressed by this method in which the desired temperature is produced by the power dissipated in the metal powder. This method of hot pressing has been termed "electrical resistance sintering under pressure." The most significant differences between this operation and conventional hot pressing are: 1—The sintering times are very short, usually a fraction of a second and at most a few seconds. 2—The powder and die are initially cold. 3—Heat is generated within the powder itself and not conducted in from the die. 4— The pressure used is high. 5—Cooling following sintering is rapid, amounting to a quench. Resistance sintering of metal powders under pressure has been suggested repeatedly. In 1933, G. F. Taylor' proposed an apparatus which consisted of an insulating tube made of glass, or a ceramic filled with the powder to be pressed, and plungers above and below the powder. The powder was to be heated by passing an electric current through it and pressure was then applied. The apparatus was intended principally for hot pressing cemented carbides. Although the principle of resistance sintering under pressure is clearly shown in this patent, few details are given. A sintering period of a second or a fraction of a second, which is terminated by the operation of an inertia switch, is mentioned but no values for current density are mentioned. Low pressures, such as atmospheric pressure or a somewhat higher pressure exerted through a lever, are suggested. W. D. Jones' discussed electrical resistance sintering under pressure and proposed using resistance welding apparatus for this purpose. In a patent issued in 1944, G. D. Cremera described a method of electrical resistance sintering under pressure using resistance welding apparatus which was to be applied mostly to nonferrous metals such as copper, brass, bronze, and aluminum. Current densities of 400,000 amp per sq in., sintering times of 1 and 2 cycles of 60 cycle current, and pressures of 5 to 10 tsi are proposed. Cremer suggested using an

Jan 1, 1956

By L. D. Wooddy, Robert Moscrip

The simultaneous solution of the volumerric balance and the unsteady-state equation has been used for several years to make performance calculations for combination drive reservoirs. This method makes possible the calculation of volumetric changes of fluids in the gas cap, oil zone, and aquifer which occur as a result of withdrawals and reservoir pressure changes. It does not provide a means for the determination of reservoir fluid distribution changes corresponding to these vollrmetric changes. A knowledge of the fluid saturation distribution in the reservoir at various stages of depletion is important for the determination of the efficiency of gas and water as oil-displacement media and, therefore, for the reliable predicrion of ultimate oil recovery. To provide this knowledge, the displacement equations are solved simultaneously with the volumetric balance and unsteady-state equations. The described calculation procedure has been used satisfactorily to analyze the past performance and to predict the future behavior of combination drive reservoirs under both primary and pressure-maintenance operations. INTRODUCTION The three basic mechanisms by which oil is displaced from a reservoir are: (1) dissolved gas drive—the displacement of oil by the expansion of liberated solution gas, (2) water drive—the displacement of oil by water which enters the oil zone from the aquifer, and (3) gas cap drive—the displacement of oil by gas which ex- pands into the oil zone from the gas cap. The action of gravitational forces may be effective in increasing the efficiency of the basic drive mechanisms. Gravitational forces favor the segregation both of gas and oil and of oil and water, thus tending to shorten the transition zone between oil and displacing fluids. Most reservoirs produce under the influence of a combination of these drives and are designated "combination drive reservoirs". Fig. 1 is a cross section of a typical combination drive reservoir. A calculation procedure for analyzing the performance of combination drive reservoirs has been developed by combining the displacement equations' with the volumetric balance equation' and the unsteady-state equations. The pressure-production performance and the positions of the gas-oil and oil-water contacts are calculated for several stages of reservoir depletion by solving these equations simultaneously, thus affording a basis for: 1. Determining instantaneous and ultimate oil, gas, and water production under various operating conditions. 2. 'Establishing a maximum efficient rate of production, 3. Determining the advantages of pressure maintenance and unitization, and 4. Designing surface installations necessary for primarv and pressure-maintenance operations. DEFINITIONS The calculation procedure for combination drive res-

Jan 1, 1957

By Harold Vagtborg

Equilibrium vaporization ratios were obtained for light hydrocarbons, nitrogen, carbon dioxide, and hydrogen sulfide in a reservoir fluid containing 35 mole per cent hydrogen sulfide. The data cover the range from 700 to 2500 psia at 154°F. The results of this study are compared with results obtained by other investigators on systems containing less hydrogen sulfide. When large amounts of hydrogen sulfide are present, the equilibrium vaporization ratios for ethane and heavier hydrocarbons are greater than the ratios for systems containing little or no hydrogen sulfide. Large amounts of hydrogen sulfide have the reverse effect on the ratios for methane. Routine PVT studies were performed on the reservoir fluid including flash and differential liberations of the dissolved gas. The pressure-volume relationships of the saturated fluid were also determined. It is shown that the use of published correlations on physical properties of reservoir .fluids can lead to gross errors when applied to systems containing large amounts of hydrogen sulfide. INTRODUCTION Equilibrium vaporization ratios for various components in naturally occurring crude oil and condensate systems have been reported in the literature.1,2,3,4 Recently, several papers have been published with emphasis on non-hydrocarbon components such as nitro- gen, carbon dioxide and hydrogen sulfide.5,6,7,8,9 The increased discovery of reservoir fluids having high concentrations of these non-hydrocarbon components, particularly hydrogen sulfide, has created a need for a further study of their phase behavior. Equilibrium vaporization ratios are known to vary with pressure, temperature, and overall composition of the system.'" It was anticipated that ratios for systems containing large amounts of hydrogen sulfide would differ from the ratios for systems containing small amounts of hydrogen sulfide. Therefore, the present work was undertaken in order to obtain reliable equilibrium vaporization ratios for the reservoir-fluid in question. PROCEDURE The procedure followed was evolved after considerable experimentation on methods of handling the very sour crude. It was found that drying agents (e.g. CaCl2 and CaSO4) absorbed an appreciable amount of hydrogen sulfide from the gas used to prepare the recombined samples. The concentration of hydrogen sulfide dropped as much as 10 mole per cent in a single pass through a 3-ft drying tube. It was also found that when undried gas was agitated with mercury in the PVT cell, a black scum, believed to be mercuric sulfide, was formed and the hydrogen sulfide content of the gas dropped several mole per cent. Because composition changes during a run could not be tolerated, separation of the mercury and sour fluid was necessary. In order to effect this separation, a stainless steel piston, equipped with Teflon O-rings, was placed in the PVT cell between the mercury and the sour fluid. This piston had to be constructed in three parts because

Jan 1, 1955

By K. Mukherjee

A quasi-thermodynamic calculation is presented for estirt~ating vacancy Parameters in fcc metals. For fcc metals the equilibrium vacancy concentration at the melting point can be approximated by a constant mole fraction. The Gibbs free energy of formation of the vacancies can then be expressed as a simple function of the absolute melting temperature alone. From this description the formation energy Ef, the vibrational entropy Sv, and the formation volume of a vacancy can be calculated in terms of known thermodynamic parameters. The calculated values are in good agree-rnent with available experimental results. IT appears that many of the physical parameters associated with lattice defects can be empirically related to thermodynamic melting parameters.'-7 Besides the implicit correlations between melting phenomenon and point defects, the melting temperature itself at atmospheric pressure can be used as a reference temperature for the purpose of comparison of vacancy concentrations in a given crystal class. The concentration at the melting point then corresponds to the maximum vacancy super saturation in the crystalline state at a fixed pressure. For pure fcc metals such as Au, Cu, Al, Ag, Pb, and Pt the mole fraction of vacancies at the melting point8 is of the order of 10*"3 to 10"1. The equation expressing the equilibrium vacancy concentration at the melting point contains three parameters: the formation energy, the vibrational entropy, and the absolute melting temperature, see Eq. [2]. Since these three parameters cover a wide range of values8 in the above-mentioned metals, it can be assumed that in other fcc metals, for which no reliable data are available, the mole fraction of vacancies at the melting point most likely lies in the range 10~3 to lO"4. This is then the basis of the calculations described in this article. Within this range the mixing entropy can be linearized and the vibrational entropy, the formation energy, and the vacancy formation volume can be calculated in terms of known thermodynamic constants. 1} LINEARIZATION OF MIXING ENTROPY The Helmholtz free energy of a crystal containing n vacancies at the melting point can be writteng as where Ef, T,, k, and S, are the formation energy of a vacancy, the absolute melting temperature, Boltz-mann's constant, and the vacancy formation entropy, respectively. After applying Stirling's approximation in Eq. [l] and minimizing with respect to n where (n/N), is the equilibrium vacancy concentration in mole fraction at the melting temperature at 1 atm pressure. If instead of setting (6~/6n) = 0 immediately after Stirling's approximation in Eq. [I], the configurational partition function is simplified, then some useful and significant results can be obtained by utilizing the experimental inforrnation After applying Stirling's approximation and rearranging is plotted as a function of (n/N) in Fig. 1. The points, not all of which are shown, are fitted by a straight line substituting from Eq. [5] into Eq. [I] and minimizing with respect to n combining Eqs. [6] and [2] It must be emphasized that Eq. [7] is only a crude approximation based on an oversimplified model of

Jan 1, 1967

By Hans Neuberger

In our everyday life, visual perception plays perhaps a more important role than any of the other senses with which we are equipped by nature. It is, therefore, quite understandable that the average person associates with the term ''atmospheric pollution," clouds of dust, palls of smoke or deposits of soot, phenomena which are so familiar to the residents of industrial cities. On the other hand, "air" is usually considered the prototype of the invisible, of the intangible, and any suspensions in the air which do not conform to this concept, are regarded as foreign to the atmosphere and thus as "pollution." According to Webster, the term "pollution" implies uncleanness, impurity, in short, something undesirable. Although the scientist often accepts popular concepts, he is generally inclined to suspect that apparently "obvious" phenomena imply, literally, "more than meets the eye." To show that this suspicion is also justified with regard to atmospheric pollution, is the objective of this discussion. It will be shown that what seems foreign to the air at first sight, is by nature an integral part of it, and that the more important aspects of pollution generally escape attention. The Atmospheric Constituents We can distinguish two classes of atmos-pheric constituents: the Permanent gases, chiefly nitrogen, oxygen, traces of argon, neon, and others, and the variable constituents which include water in its different states, carbon dioxide, ozone, and various suspensions, either in gaseous, liquid or solid form. These suspensions, known by the collective term "Aerosol,"20 will be considered in detail. Dust There are two general types of aerosols: the first type is represented by the socalled "neutral" particles,3 commonly known as dust and experienced by everyone, as it is the more conspicuous type of suspensions. It often represents a special problem to the mining engineer, the mechanical engineer, the industrial engineer, and many other professional men. Dust consists of finely divided solids derived from weathering, drilling, handling and preparation of rocks and coal. Dust may also consist of organic or inorganic particles resulting from manufacture of a variety of products such as flour, rubber, lime and steel, from traffic on land be it on the highways, on rails or in city streets, from decomposed vegetation or from volcanic eruptions. Perhaps the most reviled member of this class of suspensions is the soot and fly ashes from coal fires and other combustion processes. The cosmic source of dust, namely the injection of meteoric matter into the atmos-,,here, is of minor significance because the concentration of particles is exceedingly small despite the relatively large mass of material which invades the earth's atmos-phere from space.

Jan 1, 1949

By R. C. Palmer

THE testing of flotation oils has occupied a large part of the time of the testing departments of various companies using the flotation process in the beneficiation of their ores. The great differences in ores and iii oils has made such work necessary as it has not been possible to select the oil best suited for the purpose without trial of many kinds. In fact, individual shipments of flotation oils from the same manufacturer will often differ so radically that the mill men have been forced to test every lot of flotation oil before its use in the mills. Further, although almost every imaginable product of the distillation of wood, from alcohol to pitch, has been tested in a more or less perfunctory manner by various people, few companies have allowed the results of their tests to be made public. This work was undertaken for the purpose of obtaining reliable data regarding the value as flotation agents of a number of products that are obtained from the distillation of wood by different methods, and incidentally to determine whether some of the products not used at present could be used. Large quantities of such materials are being wasted or burned in the wood-distillation plants of the United States, and if some use other than fuel could be found for these materials, such a use would represent a distinct saving to the country as a whole, would increase the profit of wood-distilling plants now operating and perhaps make it possible for others to operate which at present cannot do so except at a loss. At the same time it was thought that if such products can be used as flotation agents, then their use would serve to increase the number of oils and other products available for flotation purposes. It was also hoped that it might be possible to discover a substitute for some of the most effective but comparatively high-priced oils which are now used for flotation

Jan 8, 1916

By R. C. Palmer

The testing of flotation oils has occupied a large part of the time of the testing departments of various companies using the flotation process in the beneficiation of their ores. The great differences in ores and in oils has made such work necessary, as it has not been possible to select the oil best suited for the purpose without trial of many kinds. In fact, individual shipments of flotation oils from the same manufacturer will often differ so radically that the mill men have been forced to test every lot of flotation oil before its use in the mills. Further, although almost every imaginable product of the distillation of wood, from alcohol to pitch, has been tested in a more or less perfunctory manner by various people, few companies have allowed the results of their tests to be made public. This work was undertaken for the purpose of obtaining reliable data regarding the value as flotation agents of a number of products that are obtained from the distillation of wood by different methods, and incidentally to determine whether some of the products not used at present could be used. Large quantities of such materials are being masted or burned in the wood-distillation plants of the United States, and if some use other than fuel could be found for these materials, such a use would represent a distinct saving to the country as a whole, would increase the profit of wood-distilling plants now operating and perhaps make it possible for others to operate which at present cannot do so except at a loss. At the same time it was thought that if such products can be used as flotation agents, then their use would serve to increase the number of oils and other products available for flotation purposes. It was also hoped that it might be possible to discover a substitute for some of the most effective but comparatively high-priced oils which are now used for flotation

Jan 1, 1917

By NATHANIEI HERZ

(Cleveland Meeting, October, 1912.) THE formula very frequently used for computing the economical size of pipe to transmit compressed air is that of D'Arcy, as follows: d5(p1-p2)/w1l D-c w11 Where, D = the volume of compressed air delivered in cubic feet per minute,-at the final pressure. c = an experimental coefficient determined for the various sizes of pipe. d = the diameter of the pipe in inches. 1 = the length of the pipe in feet. P1 = the initial gauge-pressure in pounds per square inch. p2= the final gauge-pressure in pounds per square inch. W1 = the density of the air, or the weight in pounds per cubic foot at the initial pressure, p,. The most common case is that in which the given quantities are: the quantity of air required, the length of the pipe, and the initial pressure. The method of solution is to assume a pressure-loss and to compute the remaining factor, c/d5, thus giving the size of pipe corresponding to the assumed loss of pressure. It is always desirable to try two or more pressure-drops, in order to find the combination that is most satisfactory, since often a small change in the size of pipe will reduce or increase the loss of pressure several pounds. An alternative method is to assume a size of pipe and calculate the corresponding pressure-drop. Each method involves a series of tedious calculations to arrive at the most economical solution, and also requires the use of tables giving the constant, c, the actual diameters corresponding to the nominal pipe-sizes, the density of the air, w1, and often, for convenience, a table giving the

Dec 1, 1912

By G. D. Monk, W. C. Krumbein

THE relation between permeability and the size parameters of unconsolidated sand is approached by considering sands as logarithmic frequency distributions having the basic parameters mean size and standard deviation. Sieve separates were mixed in accordance with the normal logarithmic probability law, so that the mean and standard deviation could be varied at will. Experiments were conducted in which one parameter was kept fixed and the other varied; in this manner the dependence of permeability on the individual parameters was evaluated. It was found that permeability can be expressed as the product of a power function of the mean size and an exponential function of the standard deviation.

Jan 1, 1942

By M. E. Prunty

Activity in coal preparation in 1967 was on the up-swing and all indications are that demands will be greater in the future. Feed tonnages to plants are increasing and a significant factor is that the top size being fed to plants is decreasing. This has been brought about by market demands, better cokability in some cases and emphasis on sulfur reduction in others. New plants are being built and some are in operation in the coal fields of southern Illinois. These plants are producing metallurgical coal in circuits that contain heavy medium cyclones and froth flotation on the - ½ mm x 0.

Jan 2, 1968

By J. E. Hilliard

Isobaric sections of the eutectoid region of the iron-carbon phase diagram have been exgerimentally determined at 35, 50, and 65 kb. The phase boundaries were located by metallographic analysis of specimens quenched after equilibriatwn at known temperatures and pressures. With increasing pres -sure a pronounced decrease in the solubility of FesC in austenite was observed together with a depression of the eutectoid temperature. These two effects resulted in a shift of the eutectoid composition toward a lower carbon content; at 65 kb the eutectoid was at less than 0.2 wt pct C. These results are in qualitative agreement with thermodynamic calculations. It has also been shown by calculations that Fe3C in contact with saturated austenite will be stable with respect to both graphite and diamond formation at all pressures above -3.5 kb. 1 HE investigation described in this article was part of a more general study of the effect of high pressure on transformations in Fe-C alloys. Thermodynamic calculations and exploratory runs made in 1959 at the start of the program indicated an appreciable change with pressure in the phase equilibria of Fe-C alloys. However, the calculations were not considered reliable enought to provide the quantitative information required for the interpretation of the effect of pressure on the kinetics of transformations. An experimental investigation was therefore made to determine a series of isobaric sections of the eutectoid region of the phase diagram at pressures up to 65 kb. EXPERIMENTAL PROCEDURE Materials. Seven alloys with analyzed carbon contents of 0.10, 0.20, 0.38, 0.60, 0.77, 0.93, and 1.20 wt pct C were prepared from Ferrovac" iron and high-purity graphite induction melted in magnesia crucibles under argon. The ingots were hot worked and swaged down to 0.19-in.-diam rod which was then centerless ground to a final diameter of 0.125 in. Samples for chemical and spectrographic analyses were taken from each end of the rods. The prin- cipal impurities were found to be Ni, Al, Co, and Si which were present in amounts up to 0.03, 0.02, 0.01, and 0.01 wt pct, respectively. Specimens were prepared by slicing the ground rods into pills 0.06-in. thick which were silver plated to reduce decarburization during the equilibration. Silver was chosen for this purpose because of its very low solubility for carbon and its mutual immisicibility with iron. High-Pressure Apparatus. The high-pressure runs were carried out in the "Belt" apparatus.' As shown in Fig. 1, this consisted of a cylindrical cell compressed between two Carboloy punches loaded by a uniaxle press. Radial support to the cell was given by the "belt" which was a Carboloy die heavily prestressed by a series of steel binding rings. Laminated gaskets of lava and metal separated the punches from the inner surface of the "belt". A cross-section of the high-pressure cell is shown in Fig. 2. Two specimen pills were located inside a resistance heater of 0.20-in.-diam Nichrome tubing. The ends of the tube were sealed with alumina and lava pills tamped in place after the

Jan 1, 1963

By Milton Williams

It is generally recognized that fluid is lost from rotary drilling muds to permeable strata during normal drilling operations;1,2-3 but that this fluid is the filtrate from the mud, rather than the mud itself, has been shown by various workers.1,4,5 The presence of this filtrate in oil-bearing or gas-bearing strata is undesirable and harmful. The decreased permeability of the stratum to oil effected by the presence of water has been pointed out by several investigators,6,7 and since, in the production of the reservoir fluid, the greatest pressure drop occurs immediately adjacent to the borehole, it follows that infiltered water is particularly objectionable in this region. Again, this filtrate tends to make electrical logs less reliable, since oil in the proximity of the borehole is probably flushed out to an appreciable extent by the water.8 Observation of side wall cores may be misleading for the same reason. Drill-stem tests in low-pressure areas may be of doubtful value where no oil is recovered, unless sufficient time is allowed for production of water lost from the mud. The infiltered water may hinder drilling operations by softening shales and causing sloughing; the ['tight hole" occasioned by excessive deposition of filter cake in the hole is a common occurrence. The filter cake remaining on the face of the producing formation may itself sometimes be detrimental to production.9 In view of these implications of the importance of filtration of mud, an investigation was undertaken to determine the factors involved in the infiltration process, and to correlate these in such a manner that the values obtained in routine filter tests employing a conventional filter of the "wall-building tester" type,10 together with data on size of hole, drill pipe, and rate of mud circulation, could be used to estimate water loss and distance of penetration of the filtrate into strata. Quantitative relations of filter-cake permeability, filtrate viscosity, and rate of filtration have been developed for filtration in the simple laboratory filter.4a,11,12,13 It is obvious, however, that the conditions

Jan 1, 1940