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By R. A. Stauffer

THE chief ore of lithium is spodumene, a lithium-aluminum silicate containing up to 3 pct lithium. The preparation of lithium salts from spodumene is costly because of the low concentration of the metal and the difficulty of separating it from the other alkali metals present. Dr. Kroll's and Dr. Schlecten's recent paper' has reviewed various methods proposed for preparation of lithium. It will be seen from this paper that the methods proposed to date have required one or another of the lithium salts as a raw material. The high cost of these salts has been the chief item of expense in the lithium metal produced. This situation has made it interesting to investigate the possibility of producing the metal directly from spodumene. When spodumene is calcined at 1000°C in the presence of lime, lithium oxide is replaced in the ore as is evidenced by the fact that it may be leached from the reaction mixture with water.2 Free energy calculations suggested that lithium oxide might be reduced with aluminum or silicon and the lithium produced distilled from the reaction mixture by heating to about 1000°C in a vacuum. These facts taken together suggested that it might be possible to prepare lithium metal directly from spodumene by heating a mixture of the ore, lime, and a suitable reducing agent in vacuum and distilling off the lithium metal as formed. THE REPLACEMENT OF Li20 IN SPODUMENE A series of experiments were undertaken to determine the ratio of lime to spodumene necessary to free substantially all the lithium oxide present in the ore. The spodumene used in these experiments was supplied by Foote Mineral Co. in the form of powder of about 200 mesh. Analysis of the spodumene was as follows: [ ] Lime (cp -200 mesh) was added in various ratios to spodumene and thoroughly mixed in a ball mill. Two hundred gram samples of spodumene-lime mixtures were charged loosely in fireclay crucibles and held at 1000°C in a gas-fired furnace for 5 hrs. The product in each case was ground to pass 140 mesh and then placed in a thimble in a soxhlet extractor. Extraction with water was carried on for 6 hrs. After this period the extract was reduced in volume by evaporation in order to precipitate dissolved lime and was then filtered and titrated with 1/4 normal hydrochloric acid. After correcting for residual calcium oxide in solution, the alkali present was calculated as lithium oxide. The results of these experiments are shown in Table I and Fig I. At lime-spodumene ratios less than 1.5, the products were invariably fused. At the ratio of 1.5 and above, the product was loosely sintered with little evidence of fusion. When the ratio of lime to spodumene was three, replacement of alkali oxides in the

Jan 1, 1947

By G. S. Jenkins

The statistics set forth by Professor Mitchell in a proceding paper very carefully brought out the points that indicate that a marked amount of consideration must be given to" the haulage problem to adapt it to local conditions as encountered. Professor Mitchell's paper showed a spread of from 10 tons per man to 50 tons per man on the production crews, which spread can be recognized as entirely too large when one considers that the product is being sold at a price within very close limits. While a portion of this spread may be explained by different methods in cost accounting as to what employees are applicable to the production crew, it cannot all be blamed on an accounting method. A good portion must be explained by the improper application of equipment to the needs incurred by the local conditions. It is in an endeavor to go into this phase that this paper is given. It will be necessary to qualify the points covered in order to keep the subject from becoming too wide in scope. Along this line, conditions will be only those involved in bituminous coal mine practices and only the haulage of coal that is loaded with mobile loading machines in seams 4 ft thick and better. Haulage Methods Employed The Consolidated Coal Co. (Illinois) has been operating on a modernized basis for about 20 yr. By modernized we mean the loading of coal with mobile loading equipment. In review of haulage methods, it must be remembered that the main line electric haulage locomotive has been in service for some 40 or jo years. To augment this main line haulage, the mule did a quite satisfactory job during hand-loading days, but was later replaced by the gathering locomotive, either battery or cable-reel operated. This type of haulage was the method in common use at the time the mechanical loading of coal became of major importance and the success or failure of loading machine installations may be largely accredited to haulage facilities in the early days; that is, in the period around 1930. The Consolidated Coal Co. had its struggle with this problem beginning in about 1927 or 1928. We were somewhat fortunate in that we were already using gathering locomotives powered by storage batteries at the time we introduced mechanical loading. This meant that we did not have to spend as much time training motormen and trip riders as many mines did that utilized only mules for their secondary haulage. This was all advantage, and our efforts could be focused on ways and means of providing adequate car service to the loading machine. Like most operations, we endeavored to gear the car service to the capacity of the machine, with a large crew endeavoring to load the maximum tonnage that the machine would handle. Toward that end our first move was to install switches

Jan 1, 1949

By Stanley J. LeFond, Neal Davis

Drilling an oil well or most other types of drilling or coring is no longer a simple and uncomplicated operation. Drilling today at depths which exceed 9144 m (30,000 ft) is hazardous and requires personnel with long and varied experience in drilling. It also requires extensive experience and knowledge in the use of materials which are added to the drilling fluid or "mud," more often than not materials utilizing an industrial mineral. The drilling fluid can vary from a simple mixture of water and "mud" to a very sophisticated, scientifically compounded drilling fluid. Industrial Minerals Used in Drilling Fluids Industrial minerals which are commonly used in oilwell drilling and completion are listed in Table 1. The most important minerals, determined by sales, are bentonite and barite. The other minerals listed are either used to achieve a specific purpose or are used regularly but in limited quantities. The main suppliers of drilling fluids internationally are Magcobar Div., Dresser Industries, Inc.; Baroid Div., National Lead Co.; IMC Drilling Mud Co., (a subsidiary of international Minerals and Chemicals Corp. and Halliburton Co.); and Milchem, a division of Baker Industries. Most of the industrial minerals are found in North America, with barite mines and processing plants located in Nevada, Arkansas, Missouri, and Arizona, and bentonite mines near Graybull, WY. Other mines, such as those in Nova Scotia, are capable of shipping to South America and to the European and Middle East countries. Most of the materials processed by any of the suppliers must conform to specifications set by the American Petroleum Institute (API) or the Oil Companies Material Organization (OCMA). These specifications provide for uniform physical and chemical properties of the materials to be sold on the open market. Function of Drilling Fluids In the early days of rotary drilling, the primary function of drilling fluids was to bring the cuttings from the bottom of the hole to the surface. Today it is recognized the drilling fluid has at least ten important functions: 1) To remove the cuttings from the bottom of the hole and carry them to the surface. 2) To cool and lubricate the drill string and drill bit. 3) To build an impermeable cake on the wall of the hole. 4) To control subsurface pressures. 5) To hold cuttings and weight material in suspension when circulation is interrupted. 6) To release sand and cuttings at the surface. 7) To support part of the weight of drill pipe and casing. 8) To reduce to a minimum any adverse effects upon the formation adjacent to the hole. 9) To insure maximum information about the formation penetrated. 10) To transmit hydraulic horsepower to the bit. In order to accomplish some or all of these functions while penetrating formations of various characteristics, several types of drilling fluids systems have been designed. Types of Drilling Muds There are two basic drilling fluid systems-water-base muds and oil-base muds. There is a wide variety of groups within these two main

Jan 1, 1983

By N. V. Peterson, R. S. Mason

Pumice, pumicite, and cinders are all products of explosive volcanic eruptions. Pumice and pumicite are produced by the violent expansion of dissolved gases in a viscous silicic lava such as rhyolite or dacite. Pumice is a light-colored, cellular, almost frothy rock made up of glass-walled bubble casts. It may occur as coherent, massive blocks composed of highly vesicular glassy lava in either a flow or vent filling, or it may be more or less fragmented by violent eruption. Pumicite has the same origin, chemical composition, and glassy structure as pumice differing only in particle size. Particles less than 4 mm in diam are designated pumicite. Pumice is usually found relatively close to the vent from which it was erupted while pumicite may be carried by winds for great distances before settling as an accumulation of fine-grained ash or tuffaceous sediment. Volcanic cinders are the reddish to black vesicular fragments that pile up during explosive eruptions of volcanoes of basaltic composition. Most deposits of cinders occur as cones or mounds of stratified fragments that range in size from a fraction of an inch to several inches in diameter. Individual cones or mounds of cinders may be several hundreds of feet in diameter and as much as 500 ft high. Properties The properties that make pumice and pumicite useful in industrial applications include: low-bulk density, good heat and sound insulating properties, and excellent abrasive capability. Cinders, even though less cellular and somewhat heavier, also have a variety of industrial uses. Uses The main use of pumice and cinders continues to be in the construction industry as road-surfacing material, railroad ballast, building block aggregate, in lightweight structural concrete, and as plaster aggregate. Both pumice and pumicite continue to be used as abrasives for polishing glass, metal, leather, stone, and wood. Some scouring powders and soaps also contain pumicite. Minor uses include fillers, absorbents, carriers for insecticides, catalyst carriers, filters, and soil conditioners. Pumicite is also used in sizable quantities as a pozzolanic additive in monolithic concrete where it increases the workability, strength, and durability of the concrete and reduces the heat of hydration. Volcanic cinders are generally denser and more coarsely cellular than most pumice. Markets for cinders include aggregate for road construction and surfacing and in lightweight concretes, particularly blocks. Some producers having access to both pumice and cinders offer a variety of blends of the two materials to block manufacturers. Most pumice deposits are unconsolidated and usually have a minimum of overburden. Mining is by open pit and can be easily carried out with conventional loading equipment. Sometimes air-drying precedes hauling to a crushing and screening plant which yields the size product desired. Multiple bins at railroad hauling facilities permit blending if desired. Pumice for abrasive use may require more sophisticated processing by fine grinding and air classification before being bagged for market. Block pumice in economic quantity and quality is limited to a few geologically young

Jan 1, 1975

By P. B. Crawford, W. L. Huskey

A study has been made to determine the effects of random vertical fractures existing in a reservoir matrix on the effective matrix properties and producing characteristics of a well. The study indicated that short vertical fractures may distort the isopotentials by 1 percent in the vicinity of the fracture. A correlation was developed which showed the effect of fracture density on the producing capacity of a well. The correlation indicated that fracture shape had little effect on producing capacity, but that total fracture length was closely correlated with the producing capacity. Effective values of reservoir permeability were found to correlate closely with fracture density when measured parallel to the direction of flow. INTRODUCTION In reviewing the petroleum literature, it is found that in most analytical solutions of hydrocarbon reservoir behavior the assumption is made that the rock is uniform throughout although core analysis and well logging surveys indicate that substantially all reservoirs are heterogeneous and some are fractured. Only in recent years have investigators studied the effects of reservoir hetrogeneity. Russell1 discussed the effect of fractures in reservoirs. The literature indicates that fractures greatly affect the exploitation of man reservoirs. This is described by Elkins and Skov2 and Little-field et al. 3 Several types of reservoir heterogeneity have been studied by unsteady-state methods. In 1959, Landrum et al. 4 showed that transient phenomena in hydrocarbon reservoirs could be studied by thermal models. pickering5 studied the flow of heat in stratified linear reservoirs consisting of plates of different metals separated by sheets of rubber which were suddenly exposed to a low-temperature source at one end. Cotman6 studied both laterally and vertically heterogeneous thermal model reservoirs with special reference to cross flow. Another type of reservoir heterogeneity involves the presence of highly permeable, circular lenses around or near the wellbore which was studied by Miesch7 using a thermal and a steady-state model. Many studies have been made of the effects of induced hydraulic fractures on well performance. 8-10 Work regarding vertical fractures that exist initially in the reservoir was reported by Givens, et al.11 Since there appears to be little published work on the importance and influence on reservoir performance of fractures that exist out in the rock matrix, this study was conducted to determine the effects of vertical fractures on pressure distribution, producing capacity and the effective permeability of the reservoir rock. The analogy between the flow of electrical current through a conducting body and the flow of fluid in a porous medium provides a convenient method of studying various aspects of petroleum reservoirs. For electrical radial steady-state flow,12 For steady-state fluid flow, With the above analogy, it is only necessary to establish the ratio of the values of the electrical units in terms of the corresponding flow units to make the analogy quantitative. The ratios are shown below.

By Maurice Rey, H. Brevers

THROUGH circumstances connected with the war, the senior author lost his records therefore it has been impossible to include numerical data in this paper. The arsenical quicksilver ore investigated had been roasted, with poor metallurgical results. The vapor-tension temperature curves of mercury and arsenious trioxide are similar, and the arsenical compound hampers the coalescence of mercury drops in the condenser and is the cause of large stack losses. The ore was a gray limestone carrying small amounts of carbon and mineralized with cinnabar and two arsenic minerals, realgar (As2S2) and arsenopyrite (FeAsS). The proportion of realgar often exceeded that of cinnabar; the proportion of arsenopyrite was smaller. The grade of the ore varied between 0.8 and 4 per cent Hg. The problem was to make a high-grade mercury concentrate, as free from arsenic as possible. The water used throughout the testing was hard, having a pH- of about 8. FLOTATION OF REALGAR Realgar showed a very strong tendency to float. It formed a film at the surface of the pulp and floated in abundance with only pine oil. Therefore an attempt was made to float the realgar before the cinnabar, but this was not very successful; the percentage of mercury in the realgar concentrate could never be brought below 2 or 3 per cent. Cinnabar slimed easily and floated with pine oil, so that some of it always accompanied the realgar. There was also the question of the cinnabar-arsenopyrite separation. On further investigation it was found that realgar can be floated not only with pine oil but even better with a combination of hydrocarbons and pine oil. Washing the ore with ether revealed that it contained hydrocarbons, which helped to float the realgar. In this connection it belongs to the same class as carbon, sulphur and talc. It can be floated also with a xanthate, when activated by a heavy-metal salt. The conditions favoring the two types of flotation are opposed, as activation by a copper salt facilitates xanthate flotation (in fact, is even necessary to it), whereas it hinders pine oil and petroleum flotation. One type of flotation can be termed nonpolar and the other polar, a distinction that has been stressed in a previous paper. DEPRESSION OF REALGAR AND FLOTATION OF CINNABAR Many chemicals were tested in an attempt to float the cinnabar and depress the realgar. Finally starch rendered soluble with caustic soda was tried, also several grades of commercial soluble starch, and dextrin was found to be the best and the most convenient reagent. Several of these starch preparations have a strong flocculating effect on the pulp, which is a distinct disadvantage. Dextrin, with its low flocculating power, is excellent. It is noteworthy that starch preparations are also depressants for carbon and talc, so that the fact apparently has a general

Jan 1, 1941

By Maurice Rey, H. Beavers

THROUGH circumstances connected with the war, the senior author lost his records, therefore it has been impossible to include numerical data in this paper. The arsenical quicksilver ore investigated had been roasted, with poor metallurgical results. The vapor-tension temperature curves of mercury and arsenious trioxide are similar, and the arsenical compound hampers the coalescence of mercury drops in the condenser and is the cause of large stack losses. The ore was a gray limestone carrying small amounts of carbon and mineralized with cinnabar and two arsenic minerals, realgar (As2S2) and arsenopyrite (FeAsS). The proportion of realgar often exceeded that of cinnabar; the proportion of arsenopyrite was smaller. The grade of the ore varied between 0.8 and 4 per cent Hg. The problem was to make a high-grade mercury concentrate, as free from arsenic as possible. The water used throughout the testing was hard, having a pH of about 8. FLOTATION OF REALGAR Realgar showed a very strong tendency to float. It formed a film at the surface of the pulp and floated in abundance with only pine oil. Therefore an attempt was made to float the realgar before the cinnabar, but this was not very successful; the percentage of mercury in the realgar concentrate could never be brought below 2 or 3 per cent. Cinnabar slimed easily and floated with pine oil, so that some of it always accompanied the realgar. There was also the question of the cinnabar-arsenopyrite separation. On further investigation it was found that realgar can be floated not only with pine oil but even better with a combination of hydrocarbons and pine oil. Washing the ore with ether revealed that it contained hydrocarbons, which helped to float the realgar. In this connection it belongs to the same class as carbon, sulphur and talc. It can be floated also with a xanthate, when activated by a heavy-metal salt. The conditions favoring the two types of flotation are opposed, as activation by a copper salt facilitates xanthate flotation (in fact, is even necessary to it), whereas it hinders pine oil and petroleum flotation. One type of flotation can be termed nonpolar and the other polar, a distinction that has been stressed in a previous paper.1 DEPRESSION OF REALGAR AND FLOTATION OF CINNABAR 'Many chemicals were tested in an attempt to float the cinnabar and depress the realgar. Finally starch rendered soluble with caustic soda was tried, also several grades of commercial soluble starch, and dextrin was found to be the best and the most convenient reagent. Several of these starch preparations have a strong flocculating effect on the pulp, which is a distinct disadvantage. Dextrin, with its low flocculating power, is excellent. It is noteworthy that starch preparations are also depressants for carbon and talc, so that the fact apparently has a general

Jan 1, 1941

By John T. Galey

An intensified search for gas, because of the shortage in the area, led to the completion of 482 wells in southwestern Pennsylvania during 1944. This number was 27 more than the number in 1943, but 118 of the wells were nonproductive. Shallow Development Oil The initial production of the 25 producers completed was slightly less than was obtained from four wells above last yearJs total. The largest well, 20 bbl., was found in the Big Injun (Miss.) sand in Morris township, Washington County, at a depth of 2085 ft. It is currently producing about 3 bbl. per day. Outside the main producing area, a well drilled in Nicholson township, Fayette County, obtained 15 bbl. per day from 1864 to 1866 ft. in the Gantz (U. Dev.) sand. The Federal subsidy of 75¢ per barrel, effective , 1, 1944, which increased to $3.40 the current pipe-line price in this area, seems to have been insufficient stimulus to materially increase drilling for oil, although more repressuring operations are contemplated. Gas The volume of initial open flow of gas developed is off slightly over 10 million cu. ft. from 36 more wells than were completed a year ago, and the average rock pressure of this new gas is more than 100 lb. less than that obtained a year ago. Apparently the best find of this year was reported in Patton township, Allegheny County, where an initial volume of over 4 million cu. ft, was encountered in the Speechley (U. Dev.) sand at a depth of from 3293 to 3303 ft. The rock pressure there, 1190 lb. per sq. in., is nearly virgin. However, this area is fairly well delimited by dry holes and docs not seem nearly so promising from the standpoint of reserves as the Armbrust area, which was discovered several Years ago. In the patton township locality another fair well with 1303 M cu. ft. open flow and 400 lb. Per 59. in. rock pressure completed in the Hundred-Foot (U. Dev.) sand at a a depth of 2125 feet. Armstrong County, as usual, leads in number of producing wells completed with lowest percentage of failures but ranks only fou th in volume of production developed. Only two wells here had more than one million cubic feet capacity, but the rock pessure was under 200 Ib. Per sq. inch. In Fayette County, where the largest portion of new gas was found, activity appears to be shifting eastward. In Luzerne township, four producers having a total combined initial open flow in excess of 10 million cu, ft, were found in the Big Injun (Miss.) sand. The best well was found also in the same area in the Speechley sand (U. Dev.) at a depth of 3460 ft. This was a 2500-M CU. ft. well in Georges township. Several wells of more than a million cubic feet capacity were found in Jackson, Washington, Wayne and Whitley townships, Greene County. None of these, however, was in a new pool.

Jan 1, 1945

By Louis Ware

At the beginning of the present war, the United States faced the need to multiply its production of magnesium metal almost roo times within the shortest possible period. Urgently needed for construction of military aircraft, incendiary bombs, and other war uses, magnesium was at the top of the list of critical war materials. Up to that time only one Producer, employing Only One process and using One raw material in a single plant, represented this country's entire Production capacity. It was immediately desirable to plan a numher of plants located strategically over the Count'Y and to expand an industry more rapidly and to a greater extent than ever before had been attempted in so short a time. In '939 this American producer, the Dow Chemical .9 was making about 7 million Pounds of magnesium metal. It utilized as a raw material brine containing magnesium chloride, which was pumped from wells in Michigan. The logical ap-preach to certain increased production was to employ the same process on the same raw material in other sections of the United States. In Europe and other countries, different processes had been used and different raw materials were being utilized, but all of the skill and knowledge for production in this country was that of using the Dow type of cell and magnesium chloride as a raw material. The Government was testing other processes, but none then had been proved commercially feasible. Development OF New Process The International Minerals and Chemical Corporation had available a large quantity of magnesium ,chloride at Carls-bad, New Mexico, contained in the end liquor produced from its potash plant sillce the buildng of the plant in 1941 It was the only company mining commercially a magnesium ore and having anything like this quantity of magnesium chloride liquor. The magnesium ore, langbeinite, was being mined from the 800-ft. level for its content of potassium sulphate. This ore, a potassium magnesium sulphate, was reacted in a base exchange plant with potassium chloride to produce potassium sulphate, the discharge liquor having a high content of magnesium chloride. Three potash-producing companies are in the Carlsbad area, but only International has developed and is commercially producing the potash-magnesium ores. The lower, or No. 4, veil, in that area is potassium chloride ore, and is continuous through all the properties. The langbeinite, or No. 2, vein is minable at the International property, but occurs sparsely, if - at in other areas being mined in that vicinity. It is understood that most of the mag. nesium produced] by Germany comes from magnesium and magnesium-potassium ores obtained from potash mines. It was logical for International to pro-pose to make available this magnesium material and to offer its technical staff to design, construct and manage a magnesium plant for the account of the Government. The plan that finally was adopted by the

Jan 1, 1944

By J. H. Frye, J. W. Caum

ONE of the most important methods of increasing the hardness of metals is alloying. In spite of the widespread use of alloys, the fundamental mechanism of alloy hardening is little understood. This is true even of the simplest form of alloy, the primary substitutional solid solution in which solute atoms substitute for solvent atoms at random in the crystal lattice of the latter. A fundamental understanding of the mechanism of solid-solution hardening would be important, both because of the widespread use of alloys of this type and because of the light that might be thrown on the mechanism of hardening in more complicated alloys. The present investigation covers the hardness of primary substitutional solid solutions of zinc, gallium,, germanium; and arsenic in copper. All of these are B subgroup elements from the third period of the periodic table. Cu, Zn, Ga, Ge, and As are in groups I, II, III, IV, and V, respectively and lie just to the right of the transition elements. Because of their cost, it is unlikely that Ga-Cu and Ge-Cu solutions will ever be of commercial importance, but the intent of this study has been to discover some of the fundamentals of solid-solution hardening and it has been demonstrated that such a study is far more likely to be fruitful if alloys are made up on the basis of position of the constituent elements in the periodic table than if commercially important alloys are used. Many investigations have. been made of the hardness of substitutional solid solutions, but lack of attention to purity of the metals, infrequent grain-size control, and the use of varying testing techniques have virtually invalidated any comparisons. The purpose of most investigations has been to solve immediate problems and not to solve the primary problem: Why do solid solutions usually have a greater hardness than pure metals? PREVIOUS WORK Theories have been advanced to account for the hardness of solid solutions,, but relatively little experimental work has been done. Perhaps the first experimental work of merit was that of Norbury1 on copper alloys. He showed that for several alloys there was a correspondence between the hardness of one atomic per cent solutions and atomic volume of the solutions. More recently Brick, Martin, and Angier2 have investigated the effect of various solute elements on the hardness of copper. They concluded that the hardening effect of these solutes depended "primarily on the difference in atomic volume of solute and solvent or, relatedly, upon the parameter, change of the solvent or the extent of solid solubility." They also observed the effect of these elements on hardness and texture developed by rolling and by annealing of rolled material. Austin3 examined the hardness and response to heat-treatment of various iron solid solutions. Frye and Hume-Rothery4 measured the hardness of a number of silver solid solutions containing approximately

Jan 1, 1943

By Stuart E. Buckley, C. R. Hocott

The viscosity of the oil in the reservoir is one of the properties that influence its movement through the sand to producing wells. Measurements of viscosity, therefore, are pertinent to problems associated with well behavior and with the estimation of recoveries, and afford an indirect means for partial evaluation of various methods of controlling reservoir behavior. The effect of dissolved gases on the viscosity of crude oil has been determined,ls2 but no data have been published on the viscosity of representative samples of reservoir oils. This paper describes a simple instrument that has been used to determine the viscosities of a number of subsurface oil samples at the temperatures and pressures existing in the reservoirs, and presents the results of the determinations for typical fields. Construction oF the Apparatus The principal requirements of any instrument used for the examination of subsurface samples are that it be strong and simple both in design and in method of operation. Accuracy beyond that of the degree of reproducibility of subsurface Sam-~les from various wells in a reservoir or exceeding that of the common measure-merits of reservoir temperatures and Pressures is not required. Because of the expense of procuring subsurface samples, it is necessary also that the instrument operate on a relatively small fraction of a sample, leaving the remainder for other tests, and that there be few or no failures of the equipment to cause undue delay or loss of a sample. After preliminary experiments with a falling bullet, the results of which were not satisfactory, a simple viscosimeter was built of the rolling ball type first proposed by Flowers3 and later used by several investiga-tor. 5.8 The apparatus consists essentially of a removable, accurately bored cylindrical barrel of 1/4-in. nominal internal diameter, 8 in. long, in which a closely fitting steel ball rolls through the oil with the barrel inclined at a definite angle. The ball makes contact at one end of the barrel with ail insulated electrode, closing an electrical circuit, which actuates a buzzer. The meas-urements consist essentially in determining the time required for the ball to travel the length of the barrel. The details of the construction are shown in Fig. I. The barrel in which the ball rolls was made from a section of 25-caliber blank rifle barrel, specially bored to an exact uniform diameter and polished. The barrel slides snugly into a hole bored in a solid stainless-steel cylinder, an upper external shoulder of the barrel compressing a small spring, and is held in place by a hollow nut. The spring prevents the barrel from seating against the bottom of the bored hole in the cylinder, while narrow external longitudinal slots in the barrel permit fluid to flow around it and through the bottom. The upper part of the recess in the steel cylinder is enlarged to form a tapered chamber, which acts as a reservoir for the oil and affords space for agitation to ensure

Jan 1, 1941

By C. R. Hocott, Stuart E. Buckley

The viscosity of the oil in the reservoir is one of the properties that influence its movement through the sand to producing wells. Measurements of viscosity, therefore, are pertinent to problems associated with well behavior and with the estimation of recoveries, and afford an indirect means for partial evaluation of various methods of controlling reservoir behavior. The effect of dissolved gases on the viscosity of crude oil has been determined,ls2 but no data have been published on the viscosity of representative samples of reservoir oils. This paper describes a simple instrument that has been used to determine the viscosities of a number of subsurface oil samples at the temperatures and pressures existing in the reservoirs, and presents the results of the determinations for typical fields. Construction oF the Apparatus The principal requirements of any instrument used for the examination of subsurface samples are that it be strong and simple both in design and in method of operation. Accuracy beyond that of the degree of reproducibility of subsurface Sam-~les from various wells in a reservoir or exceeding that of the common measure-merits of reservoir temperatures and Pressures is not required. Because of the expense of procuring subsurface samples, it is necessary also that the instrument operate on a relatively small fraction of a sample, leaving the remainder for other tests, and that there be few or no failures of the equipment to cause undue delay or loss of a sample. After preliminary experiments with a falling bullet, the results of which were not satisfactory, a simple viscosimeter was built of the rolling ball type first proposed by Flowers3 and later used by several investiga-tor. 5.8 The apparatus consists essentially of a removable, accurately bored cylindrical barrel of 1/4-in. nominal internal diameter, 8 in. long, in which a closely fitting steel ball rolls through the oil with the barrel inclined at a definite angle. The ball makes contact at one end of the barrel with ail insulated electrode, closing an electrical circuit, which actuates a buzzer. The meas-urements consist essentially in determining the time required for the ball to travel the length of the barrel. The details of the construction are shown in Fig. I. The barrel in which the ball rolls was made from a section of 25-caliber blank rifle barrel, specially bored to an exact uniform diameter and polished. The barrel slides snugly into a hole bored in a solid stainless-steel cylinder, an upper external shoulder of the barrel compressing a small spring, and is held in place by a hollow nut. The spring prevents the barrel from seating against the bottom of the bored hole in the cylinder, while narrow external longitudinal slots in the barrel permit fluid to flow around it and through the bottom. The upper part of the recess in the steel cylinder is enlarged to form a tapered chamber, which acts as a reservoir for the oil and affords space for agitation to ensure

Jan 1, 1941

By H. Brevers, Maurice Rey

Through circumstances connected with the war, the senior author lost his records, therefore it has been impossible to include numerical data in this paper. The arsenical quicksilver ore investigated had been roasted, with poor metallurgical results. The vapor-tension temperature curves of mercury and arsenious trioxide are similar, and the arsenical compound hampers the coalescence of mercury drops in the condenser and is the cause of large stack losses. The ore was a gray limestone carrying small amounts of carbon and mineralized with cinnabar and two arsenic minerals, realgar (As2S2) and arsenopyrite (FeAsS). The proportion of realgar often exceeded that of cinnabar; the proportion of arsenopyrite was smaller. The grade of the ore varied between 0.8 and 4 per cent Hg. The problem was to make a high-grade mercury concentrate, as free from arsenic as possible. The water used throughout the testing was hard, having a pH of about 8. Flotation of Realgar Realgar showed a very strong tendency to float. It formed a film at the surface of the pulp and floated in abundance with only pine oil. Therefore an attempt was made to float the realgar before the cinnabar, but this was not very successful; the percentage of mercury in the realgar concentrate could never be brought below 2 or 3 per cent. Cinnabar slimed easily and floated with pine oil, so that some of it always accompanied the realgar. There was also the question of the cinnabar-arseno-pyrite separation. On further investigation it was found that realgar can be floated not only with pine oil but even better with a combination of hydrocarbons and pine oil. Washing the ore with ether revealed that it contained hydrocarbons, which helped to float the realgar. In this connection it belongs to the same class as carbon, sulphur and talc. It can be floated also with a xanthate, when activated by a heavy-metal salt. The conditions favoring the two types of flotation are opposed, as activation by a copper salt facilitates xanthate flotation (in fact, is even necessary to it), whereas it hinders pine oil and petroleum flotation. One type of flotation can be termed non-polar and the other polar, a distinction that has been stressed in a previous paper.' Depression of Realgar and Flotation of Cinnabar Many chemicals were tested in an attempt to float the cinnabar and depress the realgar. Finally starch rendered soluble with caustic soda was tried, also several grades of commercial soluble starch, and dextrin was found to be the best and the most convenient reagent. Several of these starch preparations have a strong flocculating effect on the pulp, which is a distinct disadvantage. Dextrin, with its low flocculating power, is excellent. It is noteworthy that starch preparations are also depressants for carbon and talc, so that the fact apparently has a general

Jan 1, 1943

By Maurice Rey, H. Brevers

Through circumstances connected with the war, the senior author lost his records, therefore it has been impossible to include numerical data in this paper. The arsenical quicksilver ore investigated had been roasted, with poor metallurgical results. The vapor-tension temperature curves of mercury and arsenious trioxide are similar, and the arsenical compound hampers the coalescence of mercury drops in the condenser and is the cause of large stack losses. The ore was a gray limestone carrying small amounts of carbon and mineralized with cinnabar and two arsenic minerals, realgar (As2S2) and arsenopyrite (FeAsS). The proportion of realgar often exceeded that of cinnabar; the proportion of arsenopyrite was smaller. The grade of the ore varied between 0.8 and 4 per cent Hg. The problem was to make a high-grade mercury concentrate, as free from arsenic as possible. The water used throughout the testing was hard, having a pH of about 8. Flotation of Realgar Realgar showed a very strong tendency to float. It formed a film at the surface of the pulp and floated in abundance with only pine oil. Therefore an attempt was made to float the realgar before the cinnabar, but this was not very successful; the percentage of mercury in the realgar concentrate could never be brought below 2 or 3 per cent. Cinnabar slimed easily and floated with pine oil, so that some of it always accompanied the realgar. There was also the question of the cinnabar-arseno-pyrite separation. On further investigation it was found that realgar can be floated not only with pine oil but even better with a combination of hydrocarbons and pine oil. Washing the ore with ether revealed that it contained hydrocarbons, which helped to float the realgar. In this connection it belongs to the same class as carbon, sulphur and talc. It can be floated also with a xanthate, when activated by a heavy-metal salt. The conditions favoring the two types of flotation are opposed, as activation by a copper salt facilitates xanthate flotation (in fact, is even necessary to it), whereas it hinders pine oil and petroleum flotation. One type of flotation can be termed non-polar and the other polar, a distinction that has been stressed in a previous paper.' Depression of Realgar and Flotation of Cinnabar Many chemicals were tested in an attempt to float the cinnabar and depress the realgar. Finally starch rendered soluble with caustic soda was tried, also several grades of commercial soluble starch, and dextrin was found to be the best and the most convenient reagent. Several of these starch preparations have a strong flocculating effect on the pulp, which is a distinct disadvantage. Dextrin, with its low flocculating power, is excellent. It is noteworthy that starch preparations are also depressants for carbon and talc, so that the fact apparently has a general

Jan 1, 1943

By J. H. Frye, J. W. Caum

One of the most important methods of increasing the hardness of metals is alloying. In spite of the widespread use of alloys, the fundamental mechanism of alloy hardening is little understood. This is true even of the simplest form of alloy, the primary substitutional solid solution in which solute atoms substitute for solvent atoms at random in the crystal lattice of the latter. A fundamental understanding of the mechanism of solid-solution hardening would be important, both because of the widespread use of alloys of this type and because of the light that might be thrown on the mechanism of hardening in more complicated alloys. The present investigation covers the hardness of primary substitutional solid solutions of zinc, gallium, germanium, and arsenic in copper. All of these are B subgroup elements from the third period of the periodic table. Cu, Zn, Ga, Ge, and As are in groups I, 11, 111, IV, and V, respectively, and lie just to the right of the transition elements. Because of their cost, it is unlikely that Ga-Cu and Ge-Cu solutions will ever be of commercial importance, but the intent of this study has been to discover some of the fundamentals of solid-sdstion hardening and it has been demonstrated that such a study is far more likely to be fruitful if alloys are made up on the basis of position of the constituent elements in the periodic table than if commercially important alloys are used. Many investigations have been made of the hardness of substitutional solid solutions, but lack of attention to purity of the metals, infrequent grain-size control, and the use of varying testing techniques have virtually invalidated any comparisons. The purpose of most investigations has been to solve immediate problems and not to solve the primary problem: Why do solid solutions usually have a greater hardness than pure metals? Previous Work Theories have been advanced to account for the hardness of solid solutions, but relatively little experimental work has been done. Perhaps the first experimental work of merit was that of Norbury1 on copper alloys. He showed that for several alloys there was a correspondence between the hardness of one atomic per cent solutions and atomic volume of the solutions. More recently Brick, Martin, and Anger2 have investigated the effect of various solute elements on the hardness of copper. They concluded that the hardening effect of these solutes depended "primarily on the difference in atomic volume of solute and solvent or, relatedly, upon the parameter change of the solvent or the extent of solid solubility." They also observed the effect of these elements on hardness and texture developed by rolling and by annealing of rolled material. Austin3 examined the hardness and response to heat-treatment of various iron solid solutions. Frye and Hume-Rothery4 measured the hardness of a number of silver solid solutions containing approximately 1 References are at the end of the paper.

Jan 1, 1943

By J. H. Frye, J. W. Caum

One of the most important methods of increasing the hardness of metals is alloying. In spite of the widespread use of alloys, the fundamental mechanism of alloy hardening is little understood. This is true even of the simplest form of alloy, the primary substitutional solid solution in which solute atoms substitute for solvent atoms at random in the crystal lattice of the latter. A fundamental understanding of the mechanism of solid-solution hardening would be important, both because of the widespread use of alloys of this type and because of the light that might be thrown on the mechanism of hardening in more complicated alloys. The present investigation covers the hardness of primary substitutional solid solutions of zinc, gallium, germanium, and arsenic in copper. All of these are B subgroup elements from the third period of the periodic table. Cu, Zn, Ga, Ge, and As are in groups I, 11, 111, IV, and V, respectively, and lie just to the right of the transition elements. Because of their cost, it is unlikely that Ga-Cu and Ge-Cu solutions will ever be of commercial importance, but the intent of this study has been to discover some of the fundamentals of solid-sdstion hardening and it has been demonstrated that such a study is far more likely to be fruitful if alloys are made up on the basis of position of the constituent elements in the periodic table than if commercially important alloys are used. Many investigations have been made of the hardness of substitutional solid solutions, but lack of attention to purity of the metals, infrequent grain-size control, and the use of varying testing techniques have virtually invalidated any comparisons. The purpose of most investigations has been to solve immediate problems and not to solve the primary problem: Why do solid solutions usually have a greater hardness than pure metals? Previous Work Theories have been advanced to account for the hardness of solid solutions, but relatively little experimental work has been done. Perhaps the first experimental work of merit was that of Norbury1 on copper alloys. He showed that for several alloys there was a correspondence between the hardness of one atomic per cent solutions and atomic volume of the solutions. More recently Brick, Martin, and Anger2 have investigated the effect of various solute elements on the hardness of copper. They concluded that the hardening effect of these solutes depended "primarily on the difference in atomic volume of solute and solvent or, relatedly, upon the parameter change of the solvent or the extent of solid solubility." They also observed the effect of these elements on hardness and texture developed by rolling and by annealing of rolled material. Austin3 examined the hardness and response to heat-treatment of various iron solid solutions. Frye and Hume-Rothery4 measured the hardness of a number of silver solid solutions containing approximately 1 References are at the end of the paper.

Jan 1, 1943

By J. Lemish

Considerable research has been conducted in Iowa in recent years on carbonate aggregate reactions in concrete. Groups outside the state have become active in the past few years after recognizing that certain carbonate aggregates are reactive in concrete. The paper reviews the nature and extent of the problem and a summary is given of research by the author and his associates. In recent years considerable research has been conducted in Iowa on carbonate aggregate reactions in concrete. The research is part of a general study on the behavior of carbonate rocks as concrete aggregates sponsored by the Iowa State Highway Commission. Research on carbonate aggregates has not been extensive in the past. Laughlin1 published one of the first papers on carbonate aggregates in 1928 and was followed by others, notably H. S. sweet,' B. Mather et al.,3 and K. Mather4 who emphasized the petrographic and physical aspects of carbonate aggregates. The recognition that certain carbonate aggregates are reactive in concrete has led to increased participation in research in the past few years by groups outside of Iowa. Significant contributions have been made by Swenson and Gillot,5 Hadley,6 and Chaiken and Halstead7 in work which emphasizes the expansion of carbonate rocks in alkaline environments and the reaction of carbonate minerals or dedolomitization with alkalies. It is the purpose of this paper to review briefly the nature and extent of the problem and present a summary of the research by the author and his associates. EXTENT AND NATURE OF THE PROBLEM The problem is the deleterious behavior of certain carbonate aggregates in concrete. It was first recognized in Iowa over 20 years ago when poor service records of certain highways were correlated with aggregates produced from the Glory and LeGrand quarries. Deleterious behavior of carbonate aggregates have been reported in Canada and, more recently, in New York and Virginia. As more knowledge is gained concerning the problem, distress in concrete related to carbonate aggregates may be recognized over a widespread area. The problem may potentially exist in the Midwest, the Northeast, and other parts of the country underlain by thick sections of carbonate rocks readily available for utilization as aggregates. The nature of distress in Iowa highways is a general weakening and deterioration of concrete characterized by progressive cracking and spalling away from joints and edges (Fig. 1). The distress generally occurs after 15 years of service and becomes progressively worse. Specimens of such concrete lack the toughness of sound concrete and break easily under the hammer in the manner of a soft brick. The matrix is generally highly carbonated and dark borders, or reaction shells or rims outline the argillaceous carbonate aggregate fragments (Fig. 2). Cracks observed in cores cut across the aggregates and concrete matrix. Although localized volume change (expansion) is associated with spalling, there is no definite field evidence in Iowa that excessive growth of concrete slabs has occurred. The experience with carbonate aggregates in Iowa indicates that the concrete deterioration is not the same as that induced by the alkali-aggregate reaction associated with siliceous aggregates. The principal difference is that in Iowa the distressed concrete is weakened throughout the slab. In concrete affected by the alkali aggregate reaction, the

Jan 1, 1961

By H. S. Price, D. A. T. Donohue

The system of equations describing displacement of a hydrocarbon liquid by a hydrocarbon vapor in a porous medium where mass transfer takes place between the phases is solved numerically for a variety of gas injection processes. Even though the method of solution is quite general, only systems with three hydrocarbon components are considered. Computer simulations of displacement processes wherein mass transfer between phases is both considered and neglected are compared, and it is shown that neglecting mass transfer can give pessimistic displacement efficiencies. INTRODUCTION The role of the gas displacement process in the recovery of petroleum has been subjected to a series of detailed analyses; as a result, a number of predictive models have been published in the literature. However, because of major simplifying assumptions, most of these models do not completely represent the physical system. As a result, the effect of making the simplifying assumptions is unknown. Therefore, a complete representation of this process — one without major simplifying assumptions —should lead to a fuller understanding of the process, and perhaps to methods of improving it. The general method of developing a model for two-phase fluid flow in a porous medium is to solve simultaneously the continuity equation, the energy equations and the equation-of-state for each phase under the prescribed initial and boundary conditions. For an isothermal system, the energy equations reduce to the momentum equation. Darcy's law. However, since natural gas is the vapor state of the reservoir liquid, interphase mass transfer may take place with concomitant changes in both the intensive and extensive thermodynamic properties of each phase. It is this phenomenon that has often been omitted in previous mathematical models. An additional relation, then, which accounts for mass transfer between the phases, must be included with the other equations to specify a complete model. Completely formulating the equations to be solved is not a difficult task1 but obtaining their solution has been intractable up to now. Availability of large-memory, high-speed digital computers now makes an attack on this formidable problem possible. This paper presents a preliminary study of the problem. Since this investigation is intended to be exploratory, it is restricted to the linear, horizontal, isothermal, two-phase viscous flow of oil and gas in an oil reservoir. In the early development of predictive models of this process, the reservoir system was considered as a unit and various forms of the material balance equation were proposed.2-4 Pressure and saturation gradients were then added in the Buckley-Leverett model.5 The Buckley-Leverett formulation considered the fluids to be incompressible; thus, the mathematical model reduces to a steady-state system. In the 1950's, studies incorporating numerical techniques were being published.6-9 These mathematical models differed in the efficiency of finite difference techniques, the inclusion or exclusion of capillarity or the number of space dimensions considered. To solve these nonlinear, partial differential equations, each phase was considered to be homogeneous with time; therefore, mass transfer between phases was neglected. The effect of mass transfer on the gas displacement process was first reported by Attra. 10 He simulated the one-dimension flow system by a series of cells in each of which the fluids were equilibrated during a time step. In addition, the pressure throughout the system during each time step was predetermined and constant-phase velocities were calculated according to the Buckley-Leverett incompressible fluid flow model. Welge et al.11 developed a model for the displacement of oil by an enriched gas where composition is considered to be a dependent variable. Fluid

By F. C. Schora, H. P. Meissner

Both a graphical and an analytical technique are presented for calculating stream compositions and temperatures in adiabatic staged systems in which solids travel countercurrently to a gas stream. Such a system might be a tower containing several plates, on each of which the descending solid is fluidized by the rising gas stream. Examples are presented in which chemical reactions occur, including the oxidation of SO, by a solid catalyst and the gaseous reduction of iron oxides. COUNTERCURRENT staged processes involving reactions between solid and gas streams are becoming more common. These operations are generally carried out in a series of beds of fluidized solids, with each bed or "plate" acting as a stage. Fig. 1 is a schematic diagram of such a series of stages located in a column, down through which a solids stream moves from stage to stage counter to a rising gas stream. Typical reactions carried out in such systems are the dehydration of aluminum trihydrate, the calcining of limestone, and the gaseous reduction of iron oxides. Calculation of the performance of these counter-current systems rapidly becomes more complex with increases in the number of stages and in the number of chemical reactions occurring. Calcula-tional procedures for isothermal operations of such systems have been described.4 Actual tower operations, however, are generally adiabatic, and in consequence far from isothermal. The object here is to present both graphical and analytical techniques applicable to such adiabatic towers operating continuously and in steady state. In this introductory discussion, the graphical techniques presented are of the McCabe-Thiele type, rather than of the Pon-chon type. In all the examples presented, it will be assumed that both thermal and chemical equilibrium are attained in each bed. The assumption that the gas and solid streams leaving each bed are at the same temperature as the bed is in accordance with the familiar behavior of actual fluidized solid systems. Chemical equilibrium, on the other hand, is not necessarily attained in any given stage between these two streams, even with deep beds, since reaction rates may be slow. In the last section of this paper, discussion is presented of methods suitable for use when chemical equilibrium is not attained. The adiabatic tower in Fig. 1 has "n" stages numbered from 1 to n, starting with the bottom stage as number 1. In analyzing this tower's performance, it is important to express gas flow rates in terms of a key component or element which remains completely within the gas stream throughout the tower. Similarly, solid flow is best expressed in terms of a key compound or element which remains within the solid phase throughout the tower. Thus, in burning limestone with a hot flue gas, the gas flow might be expressed as G, the pound mols of nitrogen flowing through the tower per unit time, while solid flow might be expressed as S, the pound atoms of calcium in all forms in the solid stream per unit of time. Defined in this way, both G and S are constant throughout the tower. The enthalpy of the gas and solid streams are now best expressed in terms of these key components. That is, the gas stream enthalpy H is expressed as Btu in the total gas per mol of the key component in the gas. Similarly, the solids stream enthalpy h is expressed as Btu in the total solid stream per pound mol (or pound atom) of the key component in this stream.

Jan 1, 1962

By Tell Ertl

The term oil shale is defined. Foreign oil-shale developments are outlined briefly. The richest and most extensive oil-shale deposits in the United States lie in western Colorado. The Bureau of Mines is opening two adjacent areas for underground mining. in western Colorado. From the first area the oil shale is mined selectively as required by the retorting plant. The second area is being developed as a unit of a full scale oil-shale mine to ascertain the most practical methods of mining oil shale and to determine costs. In both of these mining areas, research will be carried on to develop new and improved practices for mining oil shale. Introduction Oil shale is a sedimentary rock containing a solid mineraloid of indefinite composition known as kerogen. On heating oil shale, the kerogen undergoes thermal decomposition and some of the vapor products of the decomposition can be condensed as shale oil. Oil from shale can be a major source of liquid fuels since extensive deposits of oil shale are known to exist throughout the world. The United States considers the establishment of an oil-shale industry only when doubt exists of the adequacy of the domestic supply of crude petroleum. On the other hand, oil shale is not strange to foreign oil men. The industry is an old one in other parts of the world. The French industry has been in existence since 1838, the Scottish since 1859, the Australian since 1860, the Estonian and Swedish The since World War 1, and the Manchurian industry since 1929. The most highly exploited oil-shale deposits are the Carboniferous shales of Scotland. About 20 seams ranging from 4 to I2 ft in thickness are worked. The yield during recent years in scotland has been 18 to 25 gal of shale oil per ton, from 3&"30'000 tons per year' The French and Swedish oil-shale deposits are of lower grade than the Scottish. The Estonian oil-shale deposits are 7 ft thick, and the oil yield averages 50 gal per ton. Over 1,000,-ooo tons are mined each year, half of which is used directly as fuel to substitute for coal and the other half is used for the production of oil. Immense deposits of oil shale that will yield 10 to 15 gal per ton exist in Germany. Because of the impending loss of the Rumanian and Polish oil fields and the bombing of synthetic liquid fuel plants, the Nazis in 1943 started a large-scale oil-shale program in Germany. By V-E Day, it is said, oil-shale production had reached the rate of 2500 tons per day and rapid expansion of the industry was imminent. Australian oil shale, known as torbanite, occurs in beds 2 to 6 ft thick. It is of a very high grade and on retorting yields 80 to 160 gal per ton. The oil-shale industry of Manchuria was the largest in the world during the past decade. The well-known Fushun coal deposit in Manchuria has an overburden of 500 million tons of oil shale about 450 ft thick that will yield 10 to 15 gal of shale oil per ton. The oil shale is

Jan 1, 1949