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By Sam S. Taylor, H. M. Smith

"INTRODUCTION In most oil fields, natural gas is the major source of energy causing flow of oil to the well. The amount of gas Produced with the oil generally exceeds actual energy requirements, so that in time the gas reserve of the field becomes seriously depleted and the oil production must be stimulated by some auxiliary means. One of these is to repressure the oil formation with natural gas; or, where a gas supply is not available, often air is used.Although P.ir is a Cheap and convenient repressuring medium, its use sometimes is attended with several disadvantages. First, the return air-gas mixture decreases rapidly in fuel value, often until it can be used no longer as a source of power. At the same time, explosive mixtures may result if recycling is used, causing hazards to life and equipment. Second, some fields experience considerable trouble with the formation of emulsions which become increasingly difficult to treat. Although there is no definite proof that air repressuring always causes these emulsions, many operators are convinced that this is the case. The Petroleum Experiment Station of the United States Bureau of Mines at Bartlesville, Okla., has been interested in problems connected with air-repressuring for a number of years. Some time was spent in studying the so-called ""bad gas""--return,mixture of low fuel value. However, it appeared impossible to attack the problem successfully from this angle, and an approach was made through a laboratory--scale study of direct oxidation of crude oil."

May 1, 1934

By Jack L. Henry, Davis E. Traut, L. R. Penner

The Bureau of Mines conducted solvent extraction batch tests to evaluate the usefulness of neodecanoic acid ( NDA) for extracting Co 3+ from ammoniacal leach liquors high in ammonium sulfate . This work is an outgrowth of previous Bureau research in which technology was devised for the recovery of cobalt , nickel , and byproduct copper from domestic laterites . The previously devised technology uses an oxidative ammoniacal sulfate leach to treat the laterite , and nickel and copper are then recovered from the leach solution by solvent extraction and electrowinning . This report deals with the subsequent solvent extraction of cobalt from the nickel - copper raffinate solution . The results showed that about 70 pct of the contained Co 3+ can be extracted batchwise at pH 8 using NDA ( a 10 - carbon - chain highly branched carboxylic acid ) . However , NDA had a solubility of approximately 0.6 to 0.8 g / L in aqueous raffinate following extraction , and this high solubility makes it impractical for use with alkaline solutions that are low in cobalt . In addition , the extracted cobalt species ( predominately cobaltic hexammine ) is not amenable to the electrolytic recovery of cobalt metal because of its extreme stability . This fundamental prob-

Jan 1, 1965

By J. A. McAllister

In the course of a study of domestic Manganese resources, 2-ton representative samples of ore were taken by Bureau of Mines' engineers from the Payday claim, Weber County, and the Newcomb-claims, Rich County, Utah. The Payday No. 1 deposit is situated 13 miles northeast of Huntsville, Weber County, Utah. The manganese ore is a. replacement deposit in limestone and consists of manganese oxides imbedded 'in clay and also as the cementing agent consolidating small pebbles and pieces of quartz and limestone.

Jan 1, 1949

By J. L. Shultz

The Bureau of Mines extended its investigation of methanation catalysts. The noble metals (platinum, palladium, ruthenium, rhodium, osmium) and rhenium), molybdenum, and tungsten were tested in hydrogenations of carbon monoxide and carbon dioxide at 21 atmospheres in a temperature range between 200° and 600° C. From the 8 metals studied) 25 catalysts represent 5 catalyst types were prepared and tested. The impregnated 0.5-percent-ruthenium catalyst proved to be the most active and versatile of all the catalysts produced. Tungsten and the noble metals other than ruthenium were low in activity and usually required temperatures above 500° C for appreciable production of hydrocarbons. Molybdenum was moderate in activity, but further improvement in molybdenum catalysts seems possible.

Jan 1, 1967

By H. M. Thorne

Oil shale, a potential source of products presently obtained from petroleum, is found in many countries. The most extensive known deposits from the standpoint of potential shale oil in place are those in Brazil and the United States of America. Mining methods used for oil shale range from open-pit operations for shallow deposits to room-and-pillar and longwall techniques for deposits with thick overburdens. Oil shales from different sources vary greatly in the amounts and types of organic and inorganic constituents. By retorting, the organic material is converted to oil, gas, and coke. The largest percentages of oil are obtained from materials having the highest hydrogen content. Over 2,000 retorting systems have been patented, but only a few have been used industrially, and no single process seems best for all types of shales or economic conditions. Shale oils have different characteristics, depending on the source rock and method of retorting. They contain large quantities of olefinic hydrocarbons and more oxygen, nitrogen, and sulfur derivatives of hydrocarbons than most petroleums. Consequently, petroleum refining methods usually must be modified for shale oil. This is particularly true in catalytic processing. Hydrogenation, even under mild conditions, improves shale-oil refinability. Several byproducts may be obtained from both the retorting and refining steps,

Jan 1, 1964

By Oren C. Baptist, Carlon S. Land, Eliot J. White

The water sensitivity of the oil - gas - producing sandstones in three fields in the Patrick Draw area of southwestern Wyoming was estimated by laboratory testing . The tests used to estimate sensitivity , which is a measure of the loss of well productivity if the producing formation is invaded by fresh water , are : Porosity ; permeability to gas , water , and brines ; saturation characteristics with air displacing water from the samples and by mercury injection ; and identification of clay minerals by X - ray diffraction . Laboratory results indicate that the degree of water sensitivity of the sands in the Patrick Draw, Table Rock , and Desert Springs fields vary , in that order , from moderately sensitive to highly sensitive . The main cause of the sensitivity appears to be the movement of fine particles in the pores , but the swelling of a small amount of an expandible clay mineral may also contribute to the permeability reduction observed in the samples . Laboratory results further indicate that the permeability of the sands to fresh water is seriously reduced if they are first flushed with sodium chloride brine ; calcium chloride brine is less harmful to the sands than sodium chloride brine . The low original permeability of the oil sand in the Patrick Draw field , together with its moderate sensitivity , indicate that the rate of water injection for the secondary recovery of oil will be low . Limited field experience in two pilot - injection wells confirms this prediction .

Jan 1, 1964

By W. W. Adams

[S,1.1.8'"' of explordves -permissible explosivos,21 other high explosives, and black blasting povrder -in the Uni ted States during the caJ.endar yenr 1937 reached a ~ombined total that slightly exceeded the quantity sold in 1936. A larger output was re orted. for permisAiblA and other hig! explosives but asmal-ler for black po~~er. Production of the three classes of explosives totaled 404, 744,294 pounds, more than 3 pel'CGnt over 1336. The total qrumti ty produced included 49,579,441 pounds of perminsibles, 2~8,924,253 pounds of other high ex-plosives, 36,403,950 pounds of black powder in pellet form, and 29,836,65q pounds of bla~k powder in granular form.]

Jan 1, 1938

By R. O. Dannenberg

The Bureau of Mines investigations described in this report were undertaken to devise a process to economically recover precious metals and copper from low-grade, complex electronic scrap generated in large quantities by military and civilian electronic operations. Leaching with various media is applicable to certain selected items of electronic scrap but cannot be practically applied to complex mixtures of scrap. A process comprising incineration, caustic leaching to remove aluminum, smelting with a siliceous slag, and electrolysis recovered 99.9-percent-pure copper metal and anode slimes assaying more than 7,000 ounces per ton of combined precious metals. Silver, gold, and copper recoveries were 93, 95, and 87 percent, respectively. Cost analysis indicated that an alternative process using direct smelting of the scrap to make assayable products for sale to a custom smelter would provide better overall financial returns.

Jan 1, 1972

By F. W. Wessel

Manganiferous carbonate slates of the Cuyuna range, which are part of the unoxidized thin-budded iron formation, represent a large potential source of manganese. This report details recent bench-scale research by the Federal Bureau of Mines in applying mineral-dressing techniques to these materials in order to investigate their potential uses. Work outlined in the report was directed toward the production of concentrates usable as iron-blast furnace feed, but an equally important objective might have been to furnish an enriched feed for extractive processes for recovering manganese. Flotation concentrates were prepared that contained 11.1 percent manganese, 27.8 percent iron, and 12.2 percent silica, with recoveries of 73 percent of the manganese and 48 percent of the iron. Calculated analysis for a simulated sinter suggests a product containing 16.0 percent manganese, 40.2 percent iron, and 17.6 percent silica, with 31 percent recovery of the dry weight of the ore. The silica in the flotation concentrates was due to quartz and iron silicates. Substantial quantities of the iron silicates (stilpnomelane and smaller amounts of minnesotaite) were present in the slate, and the need to reject these minerals limited the recovery of iron. The sintered flotation concentrate would be usable as ferruginous manganese ore for iron blast-furnace feed because of its favorable manganese silica ratio. The unsintered flotation concentrates, representing 45 percent of the feed weight and containing manganese enriched in the ratio of 1.6 : 1, also could be used as feed to processes for extracting manganese.

Jan 1, 1961

By Effie T. Kurt, Jack Wright, J. W. Watkins, Cynthia Pearson

"The analysis of water produced with crude petroleum has interested oil producers since inception of the industry. Records of the first analysis of mineralized water produced from an oil-productive formation are obscure, and references to the first use of brine analyses to assist in solving problems of petroleum production are not available in the technical literature. However, many early reports of the Federal Bureau of Mines 5-8/ and. Federal Geological Survey, 9-11/ as well as articles in engineering and geological placed special emphasis on journals ,12-l4/ the importance, interpretation, and application of water analyses.One of the earliest applications of water analyses, and still a major one today, is for identification of intrusive waters in oil wells. This may be done by comparing the chemical constituents of a sample of water indigenous to the oil-productive formation with those of samples from upper, water-bearing formations within the same general area. Some earlier investigators recognized the need for analyzing samples of all waters encountered in drilling operations. Ambrose15/ stated, in part, ""In wells being drilled, the engineer should grasp every opportunity to get a true sample of water from each sand. . .,"" and, ""The waters of each oil field are chemically different from those of another field."" The validity of the latter observation and the importance of the former one have been borne out by comparing the results of analyses of many samples and noting the differences in relative concentrations of like constituents of waters from the same geological formation in different localities or oil pools."

Apr 1, 1957

By Raymond W. Hiteshue, Sam Friedman, Martin D. Schlesinger

The Bureau of Mines in cooperation with the El Paso Natural Gas Co. investigated the effect of high temperature and pressure at short residence times on the hydrogenation of a New Mexico coal to gaseous and liquid hydrocarbons . The study was made in a bench - scale semicontinuous unit at pressures of 500 to 6,000 psig , 480 ° to 1,000 ° C , and residence times of less than 1 minute to 15 minutes . Ammonium heptamolybdate was impregnated on the coal to furnish 1 percent molybdenum based on maf coal . Coal could be rapidly hydrogenated at elevated temperatures and pressures to yield large quantities of gaseous hydrocarbons and small quantities of lowboiling oils , high in single - ring aromatics . At 800 ° C and 6,000 psig and a residence time of 1 minute , the yield of hydrocarbon gas was 43 percent and of liquid hydrocarbons 9 percent , based on maf coal . With a 15 - minute residence time , the yield of gaseous hydrocarbons increased to 68 percent with a decrease in yield of oil to 6 percent . At higher hydrogen velocities , the yields of oil were much greater but contained large quantities of asphaltene . Low concentrations of molybdenum (0.01 and 0.1 percent ) or a high concentration of iron ( 1 percent ) were ineffective at 800 ° C , 6,000 psig , and short residence time .

Jan 1, 1964

By L. R. Fisher

The purpose of this investigation was twofold: (1) To devise a rapid method for determining quantitatively the porphyrin-carboxylic acid content of a particular crude-oil porphyrin aggregate, and (2) to isolate porphyrins in the crystalline state from crude-oil porphyrin aggregates. The first purpose was accomplished by applying adsorption chromatography. In fulfillment of the second aim three different crystalline porphyries were isolated by methods which involved both adsorption chromatography and fractionation of benzene solutions with hydrochloric acid of varying strength. The three porphyrins had etio, rhodo-, and phyllo-type absorption spectra, respectively. INTRODUCTION Many samples of petroleum have, as interesting minor constituents, chemical compounds known as metalloporphyrins. Their presence in crude oil and other bituminous materials was first discovered by Treibs a quarter century ago. Much experimental work has been done on metalloporphyrins because of their importance to the petroleum industry. They have a deleterious effect on refining catalysts. The ash resulting from the burning of heavy fuel oil is very reactive, We to the presence of metallic constituents, particularly vanadium. In oil-fired gas turbines, the ash may build up on the blades, causing imbalance of the rotors and, in addition, severe corrosion. In industrial boilers, the ash residue is responsible for severe damage to boiler tubes and to the refractory brickwork (15).4 Through study of the chemical constitution of the various metalloporphyrins found in petroleum, much can be learned concerning the origin, migration, and history of crude oils.

Jan 1, 1961

By E. B. Kester

A study of the composition of the corresponding fractions of a primary and a high- temperature tar was undertaken to throw light on the net results of the pyrolysis of the primary products of coal decomposition in high-temperature coking practice, with reference both to total quantities of the chemically similar constituents and to their distribution throughout the boiling range. No exactly parallel investigations are on record. The distribution of substances in high-temperature tars, however, is fairly well understood. Such tars are more or less similar, for they consist of the more stable phenols, aromatic and olefinic compounds resulting from the pyrolytic decomposition of a wide variety of primary tar constituents. For example, from a typical distillation curve for high-temperature tar phenols4 it may be seen that the greatest portion of the phenols distills between 180° and 220° C., a fairly narrow range.

Jan 1, 1932

By H. H. Schrenk

One phase of Bureau of Mines work in health and safety is promotion of the use of safe, satisfactory, and reliable respiratory protective devices. To insure that such devices will be. available, the Bureau has established schedules of minimum requirements for oxygen breathing apparatus,3/ gas masks,/ supplied-air respirators (hose masks, air-line, respirators, and abrasive blasting helmets, hoods, or masks),5/ and dispersoid (dust, fume, and mist)

Jan 1, 1943

By R. V. Higgins, A. J. Leighton

A computer program has been devised to calculate the reservoir performance of water floods of complicated well - spacing patterns . The method and program have been tested by calculating the waterflood performance of fivespot patterns using oils of different viscosities and the performance calculations agreed closely with laboratory results . The program on a high - speed digital computer will process the performance prediction in about 1 minute , which is very rapid for a prediction using so much fluid mechanics and nonlinear geometry . The program has been presented in such a way that one may use it as given and save the time required to write and " debug " one of his own . gram processes a complex reservoir analysis , many of the complicated steps are explained in detail , both for the fluid mechanics and the directions for the computer . The subtle features that originally delayed the application of the program to unusual combinations of permeability and viscosity relationships are incorporated and explained

Jan 1, 1963

By J. H. Field

Synthesis of hydrocarbons by the Fischer-Tropsch reaction in a hot-gas- recycle system was demonstrated to be technically feasible. This project was undertaken, by the Bureau of Mines, to determine if the system was operable and to ascertain the optimum conditions for the production of gasoline. Carbon steel turnings packed with a void volume from 88 to 90 pct. were satisfactory catalysts, but steel catalysts with greater void volume, either turnings or steel wool, were not as active. Good temperature control with a pressure drop of less than 0.5 pounds per square inch (p.s,i,) per foot of catalyst bed of turnings was obtained by operating with a recycle to fresh feed ratio of 20 and by splitting the total gas flaw and injecting portions into the reactor at different entry ports.

Jan 1, 1961

By Bernard Porter, E. A. Brown

Electrical conductivities and densities of the LiF- UF , LiF- ThF4 , NaF - C1F4 , and NaF - ThF systems were measured as functions of composition and temperature . The specific conductance and density varied linearly with temperature . Molar and equivalent volumes , as well as heats of activation for conductance , were calculated from the experimental data . At 1,000 ° C , the molar volumes ranged from 16 to 40 cubic centimeters per mole and the specific conductance ranged from 9.8 to 2.5 per ohm- centimeter as the actinide metal fluoride concentration changed from 0 to 60 mole - percent . Heats of activation for conductance were 3 to 7 kcal per mole . The data are interpreted on the basis of a semilattice model for the melts .

Jan 1, 1964

By Donald E. Redmon

This Bureau of Mines report examines the injury experience in the quarrying industry for the years 1964-65. Twenty-eight tables for each year are presented in which disabling work injuries are summarized by department, source of injury, extent of disability, part of body injured, and nature of injury. Correlative information on employment, worktime, and operating activity is also presented.

Jan 1, 1973

By W. C. Holliman

This report is one of a series of reports on the characteristics of commercial aviation gasolines, It presents compilations of inspection test data on their products furnished by 16 manufacturers of commercial grades of aviation and special date obtained in Bureau of Mines laboratories on 66 samples of these gasolines, Data are presented for 19 samples of grade SO, 17 of grade 91/98, 22 of grade 100/130, and 8 of grade 115/145 aviation fuels. These gasolines are designated July 1948 production, although some of the samples may have been produced a month earlier or later.

Jan 1, 1948

By O. C. Blade

This report on the properties of aviation gasolines and aviation jet fuels produced in the United States during 1954 was made under a co-operative agreement between the American Petroleum Institute and the Bureau of Mines of the United States Department of the Interior. Analytical data are presented for 101 samples of aviation gasoline. Data also are given for 30 samples of aviation jet fuel. The analyses were made on samples typical of the manufacturers I 1954 production in their laboratories and the results submitted to the Bureau of Mines for compilation. The products of 19 manufacturers of aviation gasolines and of 15 producers of aviation jet fuels are represented.

Jan 1, 1955