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By G. L. Oldright

THE economic manufacture of sulfuric acid by the ordinary chamber process usually involves production on a large scale and a plant that is costly to construct. The nature of sulfuric acid makes it costly to transport any great distance. For these reasons, the metallurgist has not found it feasible, at times, to beneficiate ores amenable to leaching, and a. need exists for a local process that will produce acid cheaply on a small or large scale. To leach ores containing residual sulfides, an oxidizer, such as ferric sulfate, is needed in solution. Precipitation with scrap iron is one of the cheapest methods of removing some metals from solution, giving a plant of low first cost and supplying a source of cheap ferrous sulfate. The other ingredient needed for the process is SO2 roaster gas; the addition of which, as, described below, will give both ferric sulfate and sulfuric acid. Where roaster gas is a waste or obnoxious, product, the expense. for materials is still further lessened. The use of ferric sulfate and sulfuric acid as a solvent lends itself, well to the utilization of scrap iron as a precipitant, and the stages of the process fit in well together as an economic whole.

Jan 8, 1925

By N. Schapiro, R. J. Gray, G. D. Coe

A petrographic and chemical investigation was conducted to determine the occurrence and distribution of the organic and inorganic forms of sulfur in various size and specific gravity fractions of a high volatile, A-rank, Pittsburgh seam coal. The investigation was conducted to aid in the resolution of the problem of how metallurgical coke of lower sulfur content can be produced from high sulfur coals. The Pittsburgh raw coal contains about 2.4% S in two dominant forms: pyritic and organic. Pyritic sulfur constitutes about 57% of the total sulfur in the raw coal and occurs in macroscopic and microscopic-size particles. A plant cleaning process mechanically separates between 50 and 60% of the pyritic sulfur, mainly the macroscopic particles. The organic sulfur constitutes 41% of the total sulfur in the raw coal and 55% of the sulfur in the washed coal. Thus, organic sulfur is not reduced by physical methods of separation. Organic sulfur occurs in all the coal entities, but in general, increases as the exinoid content of the coal increases. In this study, it was found that carbonizing certain selected low gravity coal fractions containing an average of 0.45% pyritic sulfur and 1.01% organic sulfur produced cokes containing an average of 0.22% pyritic sulfur and 0.91% organic sulfur. However, the organic sulfur in the coke is probably derived in part from the heating of pyrite in the presence of carbon. Thus, the total sulfur in the coal carbonized is the most important factor affecting the sulfur content of the coke produced. Concentration of microscopic pyritic and organic sulfur in the middling-type coal indicates the necessity for rejecting as much of this material as is economically feasible. Most of the sulfur introduced into the blast furnace originates from the coke. Although the sulfur content of the hot metal can be controlled by the addition of flux, the flux used restricts the productivity of the furnace by displacing ore and requires first to be smelted; therefore, low sulfur coke is highly desirable. Since the sulfur content of coke is dependent upon the sulfur content of the coals from which the coke is produced, low sulfur coals are required to produce low sulfur coke. In the western Pennsylvania area, large quantities of good coking coal are available from the Pittsburgh seam, but this coal unfortunately contains relatively large quantities of sulfur. To provide information that might be useful in reducing the sulfur content of this coal in the cleaning process, an investigation was conducted to determine the physical and chemical forms in which this sulfur occurs and with what petrographic components it might be associated. The Pittsburgh seam coal, like most other coals, contains two dominant forms of sulfur: one occurs as the minerals pyrite and/or marcasite and is referred to as pyritic sulfur; the other is combined with the coal substance and is called organic sulfur. Pyritic sulfur is amenable to physical methods of separation, whereas organic sulfur is not. Pyritic sulfur particles must be freed from the surrounding coal if they are to be removed in the washing process. Generally, this requires crushing; the required degree of crushing being a function of the size and distribution of the pyrite. The present investigation was conducted to 1) determine the size, distribution and association of sulfur-bearing minerals in the coal and 2) to determine whether the organic sulfur has a preferential association with specific coal entities. If a preferential association exists, this knowledge may be useful in devising a method for organic sulfur reduction. In addition, a study was made to determine the extent to which pyritic and organic forms of sulfur in the coal contribute to the sulfur in the coke produced from this coal. A representative 3%-ton sample of raw coal was crushed to —3 in. and screened into square-mesh sizes: 3 to 1 in., 1 to % in., % to % in., % in. to 10 mesh, 10 to 35 mesh, and 35 to 200 mesh. Separate samples of the -200-mesh fraction and the all-size composite were also collected. Each size fraction (except the -200 mesh) was fractionated on heavy liquids of the following specific gravities: 1.280, 1.300, 1.325, 1.350, 1.375, 1.400, 1.425, 1.450,

Jan 1, 1963

By A. A. Bauer, M. S. Farkas, F. A. Rough

An investigation of the d-phase relationships between the uranium-zirconium and uranium-molybdenum systems was conducted. A ternary cut joining U-31.5 at. pct Mo to U-74 at. pct Zr is presented on the basis of differential thermal analysis, metallographic and X-ray diffraction data. HyDothetical isothermal ternary sections, inferred from the determined d-phase relationships, are presented for the uraniztm-zirconium-molybdenum system. A ternary eutectoid, at 454ºC, was found in zirconium-rich alloys. Its composition, based on metallography and electron-beam micro-analysis, is estimated as U-61.7 at. pct Zr-7.1 at. pct Mo. URANIUM binary systems have been studied extensively in the past to supply basic information needed in reactor-fuel development. Alloys of uranium with zirconium, molybdenum, and titanium are of particular interest because, in these binaries, extensive or complete solid solubility between the body-centered-cubic forms of these elements and y uranium exists. In addition, an intermediate phase of limited solid solubility forms in each of these systems by transformation of the high-temperature ?-uranium phase. Previous investigation of the phase relationships existing between the intermediate 6 phases in the uranium-zirconium-titanium and the uranium-molyb- denum-titanium ternaries have already been reported.1,2 The results of an investigation of the phase relationships existing between the 6 phases in the uranium-zirconium-molybdenum system is reported here. The phase equilibria that occur in the solid-state portions of the pertinent binary systems are shown in Fig. 1. Phase nomenclature appearing throughout the report is as shown in these diagrams. The crystal structure of the phases in this system are given in Table I. EXPERIMENTAL PROCEDURES Alloys were cast and fabricated to 1/4-in.-diam rod. Specimens were heat treated and examined by metallographic and X-ray techniques. Thermal-analysis data were obtained.

Jan 1, 1960

By J. N. Sicking, F. H. Brinkman

A new method for obtaining equilibrium vaporization ratios (K-values) for reservoir fluids has been developed and tested. By application of the method, complex experimental measurements of liquid and vapor phase compositions are eliminated. This simplified technique reduces the cost of experimental equilibrium-ratio data for reservoir studies of condensates and volatile crude-oil systems. The method is designed for systems of constant composition and, therefore, is best suited for depletion studies where compositional changes at high pressures are minor. The basic data required, in addition to the composition of the initial reservoir fluid, are the relative vapor-liquid volumes and densities at reservoir temperature and variom reservoir pressures. Tests demonstrated that the method predicts equilibrium ratios accurately for condensates. A single test on a crude oil was not conclusive; further testing will be necessary before the accuracy of the method can be determined for crude-oil systems. In addition to determining equilibrium ratios, the calculation method provides information on the physical properties of the "plus" component in the vapor and liquid phases. The "plus" component is that mixture of components heavier than the least volatile fraction analyzed. This information is useful in studies of both natural depletion and cycling operations for condensate reservoirs where the heptanes-plus component in the gas phase is produced from the reservoir. INTRODUCTION As more volatile oil and condensate reservoirs are found, the use of phase behavior techniques to predict their performance is increasing in importance. These techniques have long been used for condensate fields and have more recently been applied to crude-oil fields containing oils of medium-to-high volatility. In these phase behavior methods, equilibrium ratios (K-values) are used to predict compositional changes in the reservoir fluids—thereby accounting for the recoverable oil that exists in the gas phase. The reliability of the predictions depends to a large extent on the equilibrium ratios used. These values must be obtained for each component for the entire pressure range being investigated. Unfortunately, because of the complex nature of hydrocarbon mixtures, accurate K-values are hard to obtain. The equilibrium ratios for a particular component will vary not only with the temperature and pressure, but also with over-all composition of the system. The importance of composition is quite critical at elevated pressures, but becomes negligible at pressures below about 300 psia. Therefore, because most phase behavior problems involve the high-pressure region, each fluid system becomes a special case. Experimental programs to determine characteristic K-values are quite difficult and time-consuming. Thus, it is often necessary to resort to approximations of the K-value data. Charts giving K-values for various mixtures and classes of mixtures are available in the literature. However, there are two major difficulties in using them: (1) the K-values of the "plus" component (that mixture of components heavier than the last one analyzed) must be obtained by extrapolation from the K-values of the other components; and (2) the K-values obtained must finally be adjusted by trial and error to agree with observed volumetric data. To eliminate these difficulties, a new method of determining equilibrium ratios was developed. Briefly, after the composition of the system as a whole has been analyzed, the method uses empirical correlations and the gross fluid properties of the system (relative vapor-liquid volumes and densities) to calculate K-values. Because the calculative procedure is long, it is best solved on a digital computer. About one hour of machine time on an IBM 650 computer is required to develop a K-chart for the fluid being examined. DEVELOPMENT OF THE METHOD OF OBTAINING K-VALUES Equilibrium ratios are defined as the ratio of the mole fraction of a component in the vapor phase to its mole fraction in the liquid phase. This statement is expressed in Eq. 1. A typical plot of equilibrium ratios for a particular system is shown in Fig. 1. It should be noted that, at pressures near the saturation pressure, the K-values appear to converge to a common point. This apparent convergence point is called the convergence pressure and is a characteristic of the system involved. Various empirical correlations of K-values have been noted. It has been observed that an isothermal plot of

By A. S. Malicsi, I. Iwasaki

The removal of hydrophobic coatings of flotation collectors from iron ores becomes of interest when a duplex flotation process is considered for upgrading, when a pelletizing process is considered for a concentrate floated with a fatty acid or a soap collector, or when a disposal of froth products from cationic silica flotation is of environmental concern. Ozone can oxidize organic compounds rapidly, thereby removing the hydrophobic coatings of flotation collectors. Ozone is widely used for treating and purifying drinking water, waste water treatment, and for chemicals processing (Murphy and Orr, 1975; Rice et al., 1980). Its uses in metallurgical operations, however, are very sparse (Allegrini et al., 1970; Chernobrov and Rozinoyer, 1975; Ishii et al., 1970; Iwasaki and Malicsi, 1985; Matsubara et al., 1978). Yet, its high reactivity and the absence of potentially hazardous byproducts become of interest in destroying flotation reagents adsorbed on mineral surfaces or remaining in mill water for recycle or for discharge. Duplex Flotation A duplex flotation process, as applied to oxidized iron ores, would involve a fatty acid flotation of iron minerals followed by an amine flotation of the siliceous gangue from the rougher iron concentrate. Such a process has been used in the Florida phosphate fields. Fatty acid coatings cannot be removed as readily with a simple acid or alkali treatment from iron oxide surfaces as from Florida phosphates. A combination of reagents, such as lime and quebracho, lime and alkali phosphate, or sulfuric acid and oxalic acid, has therefore been proposed. In a previous article (Iwasaki et al., 1967) , the use of activated carbon was found to be effective in removing fatty acid coatings both in the duplex flotation and the pelletizing processes. The use of ozone offers another approach to the removal of fatty acid coatings from iron oxide surfaces. To investigate the possible application of the duplex flotation process, a specularite ore from Michigan analyzing 36.5% iron was used. A 600-g (1.3-1b) sample was ground in a laboratory rod mill together with 250 g/t (0.5 lb per st) of sodium silicate to -150 µm (-100 mesh). This was transferred to a Fagergren laboratory flotation cell, and deslimed four times at 20 µm (quartz equivalent). The deslimed pulp was transferred to a laboratory conditioner, diluted to 40% solids, and conditioned with 250 g/t (0.5 lb per st) of soda ash and 250 g/t (0.5 lb per st) of oleic acid. The conditioned pulp was then transferred back to the Fagergren cell, floated until barren of froth, and the rougher froth product was returned to the cell and cleaned. The results are presented in Table 1. The cleaner concentrate at this point analyzed 45.3% Fe. The cleaner concentrate coated with fatty acid was transferred to a 2-L (0.53-gal) beaker. While the pulp was agitated with a glass T-stirrer, ozone was bubbled into the agitated pulp for 15 minutes at a rate of 10 mg/min (0.00035 oz per min) ozone (250 g/t or 0.5 lb per st 03 feed). It was observed that the pulp ceased to froth after about 10 minutes. The amine flotation of siliceous gangue from the ozonated pulp was carried out first by conditioning with a dextrin, a commonly used starch depressant for iron oxides. This was followed by flotation with a stage addition of an ether amine at increments of 100 g/t (0.2 lb per st). Three stages were required to float the siliceous gangue to near completion. The three froth products were combined and cleaned twice. When the cationic flotation Rougher, Cleaner 1 and Cleaner 2 cell products were combined, an iron concentrate analyzing 64.5% iron was obtained at an overall iron recovery of 72.8%. Pelletizing Fatty acid flotation concentrates have been pelletized successfully in northern Michigan mills. But at other locations, fatty acid coatings on iron flotation concentrates proved so undesirable in agglomeration that other methods of concentration had to be sought. For example, a sinter mix containing iron ore concentrates upgraded by fatty acid flotation resulted in decreased productivity. This occurred because the micropellets of particles with the hydrophobic coating are less tolerant of moisture. Thus, the bed permeability is lost (Beebe, 1965). The agglomeration of concentrates obtained by the fatty acid flotation alone, and the hydrophobic coatings destroyed by ozonation or by the duplex flotation process, is not expected to cause any difficulty since the surfaces of the concentrates would be hydrophilic. Removal of the fatty acid coating with activated carbon, indicated by the loss of floatability, was shown to restore the decrepitation temperature of wet balls during drying cycle (Iwasaki et al., 1967). Disposal of Cationic Silica Flotation Froths Recent demands of iron blast furnaces place the silica content of the magnetic taconite pellets at about 5%. Conventional process for magnetic taconite involving fine grinding and magnetic separation often produces magnetic concentrates analyzing in excess of 5% silica. This is due to the presence of the middling grains of siliceous gangue and magnetite. Cationic silica flotation of magnetic taconite concentrates (DeVaney, 1949) may be used to reduce the silica content. But the amine coating on siliceous gangue becomes of environmental concern when the flotation tailings are discarded in tailing ponds.

Jan 1, 1986

By Michael Tenenbaum, T. L. Joseph

Recent researches on the reduction of iron ores have stimulated interest in the effect of increased pressures within the iron blast furnace. From a physicochemical viewpoint, it seems logical to suppose that the increased pressure would increase the rate of reduction of the iron ore within the furnace. This increased reaction velocity would in turn be reflected in an increase in the output of the blast furnace. Any substantial effect of elevated blast-furnace pressures should accordingly be of both technical and economic interest to the operator. It is doubtful whether it is possible to increase the pressure in the stack of the blast furnace beyond two or three atmospheres without incurring severe mechanical difficulties. The benefits to be procured by elevations in pressure must therefore be restricted to pressures below two, or at the most, three atmospheres. Within this range it would seem both economically and mechanically feasible to modify the present design of the upper portion of the blast furnace to accommodate these more stringent operating conditions. This investigation was undertaken to study the effect of moderate pressures on the rate of reduction of iron ore with hydrogen. The use of carbon monoxide is contemplated for later work. Although any results that are obtained in the laboratory cannot be interpreted directly in terms of large-scale commercial operations, it is possible, through such an investigation, to ascertain the order of magnitude of the effects of higher pressure. A more quantitative conception of the effects that would result from the use of increased pressures in the modern blast furnace is needed. In some recent work, Diepschlagl found that, all other factors remaining constant, the degree of reduction of iron ores was much greater when carried out under pressure. Pressures as high as seven atmospheres were used. The degree of reduction was determined from the ferrous and ferric iron in the sponge iron. Results were obtained using both carbon monoxide and hydrogen at temperatures of 400°, 600° and

Jan 1, 1939

By Michael Tenenbaum, T. L. Joseph

Recent researches on the reduction of iron ores have stimulated interest in the effect of increased pressures within the iron blast furnace. From a physicochemical viewpoint, it seems logical to suppose that the increased pressure would increase the rate of reduction of the iron ore within the furnace. This increased reaction velocity would in turn be reflected in an increase in the output of the blast furnace. Any substantial effect of elevated blast-furnace pressures should accordingly be of both technical and economic interest to the operator. It is doubtful whether it is possible to increase the pressure in the stack of the blast furnace beyond two or three atmospheres without incurring severe mechanical difficulties. The benefits to be procured by elevations in pressure must therefore be restricted to pressures below two, or at the most, three atmospheres. Within this range it would seem both economically and mechanically feasible to modify the present design of the upper portion of the blast furnace to accommodate these more stringent operating conditions. This investigation was undertaken to study the effect of moderate pressures on the rate of reduction of iron ore with hydrogen. The use of carbon monoxide is contemplated for later work. Although any results that are obtained in the laboratory cannot be interpreted directly in terms of large-scale commercial operations, it is possible, through such an investigation, to ascertain the order of magnitude of the effects of higher pressure. A more quantitative conception of the effects that would result from the use of increased pressures in the modern blast furnace is needed. In some recent work, Diepschlagl found that, all other factors remaining constant, the degree of reduction of iron ores was much greater when carried out under pressure. Pressures as high as seven atmospheres were used. The degree of reduction was determined from the ferrous and ferric iron in the sponge iron. Results were obtained using both carbon monoxide and hydrogen at temperatures of 400°, 600° and

Jan 1, 1939

By V. H. Gottschalk

THE solubility of gases in metals has been of interest since Graham's time in 1866, but, although the subject was actively studied by iron and steel metallurgists during the eighties, the era of painstaking laboratory investigation begins in 1907 with the publication of Sieverts'1 thesis on the occlusion and diffusion of gases in metals. Since then, Sieverts has worked almost continuously in this field, and his views on the subject are the prevailing ones at the present time.2 Probably the most important result obtained by Sieverts, and frequently verified since by other observers, is the discovery that at a constant temperature the solubility of almost all gases in both the liquid and solid state of most of the metals is proportional to the square root of the pressure (for pressure above 100 mm.). The obvious explanation of this fact is that the gas dissolves as atoms and not as molecules, although it has been pointed out a number of times, first by Donnan and Shawl in connection with their work on the solubility of oxygen in silver at 1075° C., that the formation and solution of a compound of the metal and gas would also be indicated by a variation of the solubility with the square or higher root of the pressure. Sieverts4 himself raised the question whether the usual explanation (i. e., that the gas dissolves as atoms) may not be wrong, when he found that the square root law held also for the solubility of sulfur dioxide in molten copper; in which case dissociation into simpler molecules or atoms does not take place. Stubbs5 subsequently showed that Sieverts and Krumbhaar's "constant" for sulfur

Jan 1, 1932

By Frederick N. Rhines, Robert F. Mehl

IT has been shown elsewhere1 that the data on the rates of diffusion in solid metals are fragmentary and in many cases unacceptable. As a result, relatively little is known concerning the factors determining rates of diffusion and the variations in these rates with temperature. The first form of Fick's law (equation 1 below), ‡ in which the diffusion coefficient D is assumed invariant with composition, has been recognized for many years as only an approximation. The differential equation representing the second form of Fick's law (equation 4 below) has only recently been integrated by Matano,2 and unfortunately only in cases where a full diffusion-penetration curve (concentration-distance curve) has been obtained can the Matano solution be applied. The proper analysis of diffusion data is thus confined to the data of Grube and Zedele and of Zedele.§ These data are essentially for one temperature alone and do not furnish any information on the variation of the activation heat of diffusion, Q, with concentration: no information exists on the variation of Q with concentration within a singles olid solution field. 11 Much of the argument concerning the properties of metals that determine D and Q has been drawn from data in which variations of the quantities with concentration are unknown, for these data have been taken from experiments that could not furnish this information. Speculation concerning the properties of metals that may be effective in determining D and Q on the basis of data in which the chosen D and Q values are averages over wide concentration ranges of values at particular concentrations, ranges often of 100 per cent, is likely not to be fruitful.

Jan 1, 1938

By N. Brown, R. Kossowsky

Plain carbon steels with 0.48 and 0.95 pct C were quenched and tempered at 705°C to produce carbide dispersions with spacings on the order of 1 p. The morphology of the structure consisted of a carbide-dislocation network. The strengthening due to the dispersion was found to vary linearly with M-½ where M is the mean free-ferrite path determined by the entire network. No preyield microstrain preceded the upper yield point. After prestraining, the lowest stress at which dislocation movement could be detected was 104 psi; this frictional stress was independent of the dispersion and prestrains up to 6.5 pct. The Cottrell-Petch equation for grain-size strengthening was used to discuss the dispersion strengthening in this investigation. The results support an impurity mechanism for the upper yield point rather than one based on the Johns ton- Gilman theory. IT was pointed out by Gensamerl that the mean free path in the matrix is the important variable which controls the degree of dispersion strengthening. Gensamer's data on steels showed a linear relationship between the yield point and the logarithm of the mean free-ferrite path. The first theory was by Orowan,2 who suggested the mechanism of dislocations bowing between particles, with the resulting relationship that where a is the yield point, P is the distance between particles, and G is the shear modulus. The Orowan equation applies to that range of dispersion where P is large compared to the particle size and the particles are not coherent, so that the matrix is essentially free of internal stresses. As was pointed out by Orowan, there are different degrees of dispersion which, in turn, will influence the strength-controlling mechanism. However, in this investigation, we wish to confine ourselves to the region of coarse dispersion, where the Orowan mechanism should, intuitively, be applicable. It was soon evident that the data, which existed at about the time that the Orowan theory was proposed, did not agree with the Orowan equation in that the actual strengthening was always greater than the theoretical predictions. Thus, Fisher, Hart, and pry3 modified the Orowan theory by suggesting that the Orowan process took place in the microstrain region preceding macroscopic yielding and the subsequent, rapid work hardening in the form of residual dislocation loops around the particles largely determined the observed macroscopic yield point. The F-H-P theory stated that the increment of strengthening due to the work-hardening mechanism was proportional to f3/2 where f is the volume fraction of the precipitate. F-H-P used data by Shaw, Shepard, Starr, and Dorn4 on A1 3-5 pct Cu to support their theory. Roberts, Carruthers, and Averbach5 were the first to make a microstrain study of dispersion strengthening, and they found that for steel the Gensamer relationship was obeyed. Hayman and Nutting6 suggested that in the case of tempered steel 1) the ferrite grain boundary was the primary obstacle and 2) the carbide particles simply formed part of the grain boundary obstacles. They found that the strength varied as G"" where G is the ferrite grain size. Turkalo and LOW' determined the structure of quenched and tempered plain carbon steel using a replica technique; they concluded that the carbide particles did not necessarily lie in the ferrite grain boundaries. When they defined the mean free-ferrite path as being determined by both particles and the ferrite path boundaries, their data obeyed the Gensamer relationship. Meiklejohn and skoda8 showed that the strengthening from iron particles in mercury was a function of the particle size and the distance between particles. Dew-Hughes9 explained the Meiklejohn and Skoda results by the following theory: 1) grown-in dislocations which surrounded the particles were produced by the thermal stresses during the time the material was cooled to the testing temperature, and 2) the observed strengthening was associated with the cutting of the grown-in dislocations by the glide dislocations. Ansell and Lenel10 proposed a theory in which the glide dislocations pile-up or surround the particle until the number of dislocations in the pile-up is sufficient to yield or fracture the particle. The resulting theory says that the yield point varies as p-1/2, where P is the distance between particles. The Ansell-Lenel theory is almost identical to the

Jan 1, 1965

By E. B. Hunt

Paraffin deposition has been studied in the laboratory under conditions simulating deposition in well tubing. A theoretical analysis has been made of the cooling of the oil and the precipitation of paraffin from the oil as it flows up the well tubing and through surface flowlines. It is proposed that paraffin deposits are initiated by the precipitation of paraffin directly on or adjacent to the pipe wall and grow by diffusion of paraffin from solution to the deposit. This mechanism is consistent with laboratory and field observations, and has proved useful in the design and interpretation of laboratory paraffin-deposition tests. Tests have been made of the effect of plastic pipe coatings and chemical additives on paraffin deposition. INTRODUCTION Paraffin deposits which form in well tubing and surface flowlines interfere with production and must be removed. Over the years much progress has been made in developing and improving methods of removing these deposits after they form. Much less progress has been made in developing methods of preventing or inhibiting the formation of paraffin deposits. This is due, it is believed, to the lack of knowledge of the mechanism of paraffin deposition, the absence of satisfactory laboratory testing methods and the difficulties in evaluating the results of field tests of preventive treatments. The present investigation was undertaken to elucidate the mechanism of paraffin deposition and to develop suitable laboratory tests for studying the inhibition of paraffin deposition in well tubing and surface flowlines. Current theories on the mechanism of paraffin deposition have been evolved from field observations, from laboratory studies of various factors which might be involved in paraffin deposition, and from laboratory paraffin-deposition tests.1-9 Paraffin deposits have been formed in the laboratory by immersing a cold finger into a hot wax-oil solution and by flowing hot wax-oil solutions through cooled pipe or over cooled plates. These laboratory conditions differ in important features from field conditions, and the observed deposition behavior is not entirely field-like." Thus, there is reason to question the field applicability of the results of these tests. The present investigation was undertaken to determine how to perform and interpret laboratory paraffin-deposition tests to obtain information on the inhibition of deposition in the field. The paraffin problem in the broadest sense encompasses the formation of any predominantly organic deposit in well tubing, surface flowlines and other equipment in contact with crude oil or gas. The present investigation was limited to paraffin deposition involving the precipitation of paraffin wax from solution by cooling and its concentration in a deposit on a cooled surface. This probably excludes its applicability to those problems arising from asphaltic-base crudes, but not those arising from paraffin-or mixed-base crudes. This also excludes its applicability to emulsion and congealing oil problems which are often included as part of the paraffin problem. The phenomenon of cooling appears to be the controlling factor in paraffin deposition involving the precipitation of paraffin wax and its concentration in the deposit. Deposits of this type are usually found in the field only where cooling occurs. Early in this laboratory investigation, it was not found possible to form deposits under constant temperature conditions from a wax-oil slurry, either by steady flow through pipe or by gas-lift up a pipe. Thus, the investigation was limited to situations involving cooling. THEORY The relationships involved in establishing the temperature profiles in an oil stream as it flows up well tubing with a linear (geothermal) pipe-wall temperature distribution or through surface flowlines with essentially constant pipe-wall temperature are presented in the Appendix. The relationship between radial distance in the pipe and the rate of cooling of the oil is then combined with a relationship between cloud point and rate of cooling to develop the pattern of formation of a wax cloud in the oil. The following discussion of paraffin deposition under various laboratory and field conditions is based upon this development which is presented in the Appendix. PARAFFIN DEPOSITION IN SURFACE FLOWLINES The average temperature of the oil coming out of a well is somewhat higher than the ground temperature. Thus, the oil continues to cool on its trip through the surface flowline, and wax deposition can occur. The temperature distributions calculated from Eq. A-4 are given in Fig. 1. As can be seen, almost all the cooling occurs in the first 500 ft from the wellhead. In addition, the radial temperature gradient near the wall decreases rapidly with distance and becomes very small after a few hundred feet. Thus, growth of a paraffin deposit would be expected to decrease rapidly with distance from the wellhead and become negligible after a few hundred feet, since growth is dependent on concentration gradient. Wax precipitation and diffusion of wax to the already

By J. G. Richardson, K. H. Coats

During the initial growth of a gas bubble in an aquifer storage reservoir the injected gas tends to override the water. The resulting low displacement efficiency and high rate of gas travel down-structure make it difficult to maintain water-free production. This paper illustrates the use of two-dimensional, two-phase calculations to simulate this gas-water displacement. Calculations were performed for a stratified aquifer and for several homogeneous sands differing in permeability, porosity and thickness. Results are discussed and compared with performance predictions obtained from the simpler Buckley-Leuerett and Dietz formulas. This comparison indicates the necessity for the two-dimensional calculations in realistically simulating the gravity override of the water by injected gas. INTRODUCTION In recent years natural gas has been stored near markets in aquifers where insufficient storage capacity is available in depleted fields. Operators of these aquifer storage reservoirs have encountered technical problems relating to the gas-water displacement accompanying initial growth of the gas bubble. Injected gas tends to override the water, with a resultant low displacement efficiency and high rate of gas travel down-structure toward spill points. Low displacement efficiency makes if difficult to sustain water-free gas production. Sometimes the fingering of gas down-structure may be so pronounced that the injection rate must be severely curtailed, which excessively lengthens the time required for bubble growth. This paper is concerned with estimating — for given aquifer characteristics and fluid properties — the displacement efficiency, rate of gas movement down-structure and rate of gravity drainage of water behind the gas front. Several published articles relate to simulative capability necessary to handle this problem. The Dietz formula1 and Buckley-Leverett2 method have some applicability to the problem; Woods and comer3 reported one-dimensional, radial calculations which accounted for the two-phase flow of gas and water. Most recent research directed toward understanding aquifer behavior in relation to gas storage has concentrated on single-phase flow in aquifer.4 Douglas, Peaceman and Rachford5 presented a method for calculating multidimensional two-phase flow in reservoirs; their method has been applied in work reported by Nielsen and Tek,6 Blair and peaceman7 and Goddin.8 Refs. 5 and 7 show comparisons between experimental data and calculations similar to those employed here. One purpose of this paper is to illustrate the use of two-dimensional, two-phase flow calculations in simulating the difficult problem of water displacement by gas in a vertical cross-section. The pronounced fluid density and viscosity differences combine with the disparity in horizontal and vertical dimensions of the cross-section to pose one of the more difficult problems in reservoir simulation. The calculations described account for capillary and gravity forces, relative permeability and reservoir heterogeneity. An example reservoir is described and calculated results are presented for a variety of injection rates and values of permeability, reservoir thickness and dip angle. A second purpose is to compare the two-dimensional calculations with results obtained from the Buckley-Leverett and Dietz formulas. For this reason most calculations were performed for a simplified example reservoir to which the latter techniques might reasonably be applied. However, the computer program employed applies equally well to cases involving arbitrary spatial variations of permeability, porosity, reservoir thickness and dip angle.

By W. F. Mullen, C. W. Stickler

WITH few exceptions, unit operations in the Pennsylvania slate industry in 1950 did not differ appreciably from production methods described by Behrel and Bowles2-4 several decades ago. Many traditionally picturesque but relatively inefficient hand operations continued to contribute to high operating costs in an industry in which the margin of profit, for various reasons, was admittedly low. As part of a general program in which the Pennsylvania State College has been assisting the slate industry to solve some of its problems, time and method studies were used in an effort to determine the bottlenecks of production flow. The results are as applicable to other stone industries as they are to slate. A study of the basic elements in the production of roofing slate, structural slate, and slate blackboards among selected slate producers revealed comparatively few refinements. Any marked difference in operating method was characterized largely by the available equipment, a noticeable difference in the working properties of the rock quarried by a particular company, and by either the habit thinking or ingenuity of the individual operators. With the hope that significant economies in manufacture might result, all the unit operations were broken down into elements for study and analysis. The greater part of the study encompassed those operations from the quarry rim to the finished product; however, to obtain a reasonable synthesis of time allotments per operation, several analyses of quarrying from the finish of the wire saw cut are included for reference. The complete study of quarrying made by Bowles several years ago resulted in the introduction of the wire saw into the operation; there appears to be a need for as fundamental a change in the processing of finished slate as the wire saw was in the quarrying process. Fig. 1 illustrates the flowsheet of quarried rock from the parent bed to the quarry rim with the basic elements which contribute to the difficulty of removing slate from the ground. In Pennsylvania roofing slate is produced by one of three procedures, many operations of which are quite similar. In the traditional or classical method the quarried rock is reduced by sculping and auxiliary manual treatment to workable size and then is split and dressed (trimmed to size) in the conventional shanty. Archaic as this method might appear, there are several elements that result in substantial savings over more mechanized operations. In a modified version of this method, the block is reduced by sawing and gouging preparatory to splitting and dressing in indoor stations. This method is particularly adaptable to rock which fractures unevenly by conventional sculping methods. In the third and more modern method, reduced block received from the block maker is diamond-sawed to length and finished on a production line. Fig. 2 illustrates the flow pattern in each case. In the modified and more modern plans, dressing is done on mechanically-operated trimming machines, which appreciably reduce the fatigue factor of the operator. However, it should be noted that it is advantageous for the operator to be able to control the speed of the knife to prevent breakage of certain classes of stock. In the classical plan the splitter and dresser normally act as blockmakers also and carry their eighter slabs (equivalent in thickness to eight shingles) into the shanties themselves, all of which adds to fatigue and reduced efficiency. The extremely low investment and operating expense of the classical method has undoubtedly been of paramount importance in its continuation. Production of Mill Stock The production of mill stock is accomplished by less picturesque methods than enter into the production of roofing slate but it is, in the main, relatively more efficient because of the increased use of machinery for handling and for finishing. Mill stock can be classified into two categories as far as difference in production method is concerned: structural slate and blackboards. The significant difference in operation is caused largely by the nature of the rock used for each product with the best and easiest cleaved rock being reserved for blackboards to permit the splitting of large slabs to as little as 1/2 in. in thickness. Structural stock, on the other hand, is split into panels no thinner than 11/2 in. and

Jan 1, 1952

By B. H. Bergstrom, J. J. Gilvarry

Previously the authors showed that the Gilvarry equation correctly describes the distribution of fragment size in single fracture, provided the exoclastic particles showing original surface of the specimen are removed from the distribution. In the present work this conclusion has been strengthened in two respects. First, it has been shown that the existence of two peaks in the differential distribution for the endoclastic particles, corresponding to the effect of surface and volume flaws in the interior of the specimen, can be demonstrated from the average of data for a large number of specimens. Second, it has been shown by means of a Coulter counter that data obtained from specimens fractured in gelatin display the behavior at fragment sizes approaching 1 p which is demanded by the limiting form of the Gilvarry equation in this case. In previous work, a rigorous derivation of the proper distribution function for fragment size in single fracture of a brittle solid has been given by Gilvarry,' based on a closely defined physical model and deduced strictly by the laws of probability. Experimental work has been reported by Gilvarry and Berg-str~m,~ confirming the theory in its broad outlines. Subsequently, Gilvarry and Bergstrom extended the theoretical discussion to include comminution and presented experimental data bearing on this point. They have described further experimental results for the case of single fracture recently. The experimental evidence regarding single fracture was rather convincing. However, it was based on only five specimens for which fragment sizes were determined by sieve analyses and three for which measurements in the finer sizes were made on a Coulter counter. The purpose of the present paper is to extend the experimental results as obtained by means of both sieve analyses and the Coulter technique. In the former case, sufficient specimens are included so that the average data should vield ac- curately the detailed behavior of the distribution function for the coarser fragment sizes. In the latter case, measurements for the finer sizes are reported which correspond to single fracture more closely than prior results and fill a lacuna left in the experimental verification. In addition, an extension of the theory given recently bGilvarry for the case of fracture of a two-dimensional solid will be outlined, and experimental results obtained by him will be discussed.6 THREE-DIMENSIONAL CASE Gilvarry' has shown that the Schuhmann size modulus is a measure, in a sense specified later, of the number of activated edge flaws in a specimen undergoing single fracture. Single fracture is defined as that resulting from a single instantaneous application of energy, such as the blow of a hammer whose motion is halted when fracture begins. Plural fracture consists of a short sequence of single fractures, as in a jaw or gyratory crusher; multiple fracture obtains when many applications of energy are made, as in a ball mill. The Griffith flaws associated with fracture of a specimen are flaws occurring within the volume of the body, on the new surfaces created within its interior and on the new edges (intersections of two surfaces) within the body. Fracture proceeds by activation of flaws in the volume of the specimen, in the fracture surfaces throughout its interior, and in the edges produced by intersection of fracture surfaces. If all the flaws and all groups of flaws are distributed at random, independently of other flaws or groups thereof, it has been shown by Gilvarry that the distribution function for fragment size has the form of a Poisson distribution. The fraction y, by weight or volume, passing a sieve of mesh size x is given by where k is an average spacing of activated edge flaws, j2 is an average amount of surface containing one activated surface flaw and i3 is an average volume corresponding to an activated volume flaw. The averages in question are referred to the mean dimension x of a fragment. On the basis of the theoretical

Jan 1, 1962

By P. R. Kalischer

IN the production of alloys by powder metallurgical processes it is often necessary or desirable to include one or more components that tend to form very stable oxides Included in this group of metals are aluminum, manganese, magnesium, silicon, and a few others In many cases it is not necessary for the sintered compact to have full density and the other physical characteristics of a cast alloy and in that event no undue precautions need be taken If, however, it s required that the sintered part be entirely homogeneous, and have maximum density and physical properties, some method must be found to reduce the surface films of oxide, which are always present on the metals, and for the metals mentioned above this is always extremely difficult, if not impossible Since the production of high-density alloys is of particular interest to powder metallurgists, some experiments were undertaken to devise methods of reducing the refractory oxides For this work, alloys of iron, nickel, and aluminum were chosen because aluminum oxide is one of the most stable oxides and because these alloys in the right compositions form excellent permanent magnets All of the pertinent properties of the magnets could be accurately and delicately measured by density measurements and magnetic tests of sufficient scope to give a complete demagnetization curve From such a curve the maximum coercive force, residual magnetism, and energy products could be obtained and compared with the same properties for a cast material Any lack of homogeneity, density, or solid diffusion would be immediately apparent as a decrease in the magnetic properties NATURE AND REMOVAL OF SURFACE BARRIERS The early work of the present investigation was based upon published processes In the published information it was claimed that by intimately mixing iron, nickel, and iron-aluminum alloy (50 per cent Fe, 50 per cent Al) powders, compressing such a mixture into the desired shape and size, and then sintering (heating to a temperature below the melting point of the component metals) in hydrogen at 1200ºC or higher, a sound, homogeneous article could be made having the desired physical size, shape, and strength, and good magnetic characteristics However, this early work showed clearly that something in the powder compress was inhibiting diffusion and the process was almost entirely unworkable In the initial phase of the investigation samples of iron powder, nickel powder, and iron-aluminum alloy powder were pressed into separate bars and sintered in hydrogen Both the iron and nickel powders sintered

Jan 1, 1941

By W. R. Johnson

In the spring of 1935 the writers undertook to compare the geomagnetic and direct-current earth-resistivity methods of tracing a concealed dike along its strike. As far as they are aware no such direct test has been attempted.# The area surveyed lies along United States Highway number 15 about one and one-half miles east of Chapel Hill, North Carolina, and northeast of Bolin Creek (Fig, 1). To the south of the highway is the flood plain of Bolin Crook, and to the north is a hill that rises almost to the elevation of Chapel Hill. A diabase dike, which strikes slightly west of north, out-crops in a. gully just south of the highway. Southward it has been covered by alluvium but northward outcrops again on the southeastern slope of the hill north of the highway. South of the highway the country rock is Triassic shale and sandstone, the northern limit of which is slightly north of the road. On the Geological Map of the United States I the pre-Triassic formations are shown as lower Glenarm and assigned a pre-Cambrian age. Since the ago of the Glenarm has been called into question in Pennsylvania 2, the writers prefer not to commit themselves as to the ago of these rocks further than to say that they are definitely pre-Triassic.

Jan 1, 1937

By Francis L. Vinton

THE eccentric theodolite I exhibit is one constructed by the Stack-poles of New York, from drawings, considerably modified, of Combes's theodolite. The telescope is on one side of the horizontal limb, and the vertical circle is opposite to the telescope; thus they nearly balance each other, making already the construction lighter than in the instrument of Combes, where the telescope and vertical circle are together on the same side, and are both balanced by a considerable weight. The instrument stands upon three levelling screws or feet, an improvement upon the old or general style of mounting a transit on four feet-for indeed the instrument is easier levelled, and, more-over, stands more stable on three than on four points of support. The general advantage of an eccentric theodolite is evident, namely, that it can measure any and all vertical angles, from 0 to 360, without being interfered with by the horizontal limb as is the transit; besides this advantage, it needs no preparatory adjustment or correction for eccentricity ; on the other hand, however, that correction

Jan 1, 1873

By Francis L. Vinton

THE eccentric theodolite I exhibit is one constructed by the Stack poles of New York, from drawings, considerably modified, of Combes's theodolite. The telescope is on one side of the horizontal limb, and the vertical circle is opposite to the telescope ; thus they nearly balance each other, making already the construction lighter than in the instrument of Combes, where the telescope and vertical circle are together on the same side, and are both balanced by a considerable weight. The instrument stands upon three levelling screws or feet, an improvement upon the old or general style of mounting a transit on four feet for indeed the instrument is easier levelled, and, moreover, stands more stable on three than on four points of support. The general advantage of an eccentric theodolite is evident, namely, that it can measure Any and all vertical angles, from 0 to 360, without being interfered with by the horizontal limb as is the transit; besides this advantage, it needs no preparatory adjustment or correction for eccentricity; on the other hand, however, that correction

By R. E. Boni, G. Derge

Application of surface tension measurements has been made to molten silicates in order to determine the effect of sulphur upon the surface tensions of synthetic blast furnace slags. In melts with the same molar ratios of AI2O3 + SiO2 to the basic oxides BaO, CaO, and MgO, the surface tensions increase in the order of oxides listed. Sulphur lowers the surface tensions of the basic BaO, basic CaO, acid BaO, acid CaO, and acid MgO slags in that order; and the concentration of excess sulphur at the slag surface increases in this same order of slags. The rate and amount of desulphurization of iron by these slags is favored by a low excess surface sulphur in the slag. IN a previous paper,1 the authors discussed the applications of surface tension measurements of molten silicates to problems of metallurgical interest. Of major importance is the aid that such studies lend to forming a working concept of slag structure. Since the ability of a slag to desulphurize metal depends strongly upon its composition,2"4 fundamental information about the structural differences between various slags which contain sulphur should aid the development of better desulphurizing media. For that reason, the present investigation concerns the effect of sulphur upon the surface tensions of synthetic blast furnace slags. Experimental Procedure , The maximum bubble-pressure method was used to measure the surface tensions of synthetic blast furnace slags in the temperature range 1300° to 1600°C. The method is based upon the equation which was developed by Schrödinger5 from a consideration of the forces of hydrostatic pressure and surface tension of a liquid which oppose bubble formation when a gas is forced through a tube immersed in the liquid. where y is the surface tension between argon and slag in dynes per centimeter; g is the gravitational constant, centimeters per second2; H is the manometer reading in centimeters; s2 is the density of manometer fluid in grams per cubic centimeter; S1 is the density of the medium in grams per cubic

Jan 1, 1957

By Courtenay de Kalb

REVISION of the United States mining law is needed. chiefly because of the following reasons: 1. The conceptions as to the characteristics of orebodies that were held at the time the statute of 1872 was enacted have since proved to be in many respects erroneous. 2. The operation of the existing law has been found to work unnecessary hardship upon many claimants to mineral land. 3. The existing statute fails in large degree to encourage development of mineral resources. 4. The existing law often produces conflict between placer and lode-claim rights, working unnecessary injustice to placer claimants. 5. The methods of establishing the rights of locators on United States mineral land are defective, and are not uniform throughout the States within which such lands exist. LAW OF THE APEX The objections to the so-called "law of the apex" are so well known as to require no detailed statement. It is sufficient to point out that the apex rule was based upon the notion that ore deposits consisted of well-formed veins included between definite walls, like the slice of ham in a sandwich. The fact is that veins conforming to that simple type are rare. Irregularity is the rule, and the chief metal production of the United States comes from masses which bear no resemblance to the tabular form of vein. Manifestly the law of the apex fails completely in such cases. Moreover, the tendency is constantly toward the exploitation of ores of lower grade than could formerly be worked, and such deposits exist mainly in the form of large irregular impregnated zones and masses, so that the future. development of our mineral resources would be continuously embarrassed by shadowy claims to extra-lateral rights by the locators of so-called apexes

Jan 2, 1915