AndreaBozzo/ceres-open-data-index huggingface dataset:
Chemical and refining study of some Wyoming black oils

"This paper is essentially a progress report giving the results of the thermodecomposition studies to the present time. It includes data on the yields and characteristics of products obtained by cracking Oregon Basin, Dallas-Derby, and Garland topped Crude oils to dry coke at several different pressures and temperatures.  Oregon Basin crude oil was selected for the first thermodecomposition studies because the field is one of the largest potential sources of black oil in the State; the crude oil from that field is being used in several refineries, and it yields products that are difficult to refine. Dallas-Derby crude oil, although similar to that from Oregon Basin, is produced from the first black-oil field in Wyoming and in from a different section of the State. Garland crude oil is produced from the Madison limestone formation, whereas Oregon Basin and Dallas-Derby crude oils are produced from both the Embar and Tensleep formations. These three black oils are among the more difficult to refine and should not be considered as representing average Wyoming black crude oil. Analyses of the crude oils by the Bureau of Mines Hempel method are given in the appendix.  This report also includes the results of chemical treatment of some of the naphthas and the determination of their octane numbers before and after treatment. Some of the samples were doctor-treated; others were treated with sulphuric acid at low temperatures (usually about 20 degrees F.). Acid treatment was used to reduce the sulphur content of the naphthas to 0.10 percent or less. The data resulting from the several tests show the effect of different methods of treatment on the characteristics of the different naphthas."

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Thermal decomposition of sulfur compounds. I. 2-methyl-2-propanethiol

2-Methyl-2-propanethiol was decomposed in a quartz tube under various conditions of time and temperature. The temperatures employed wee 300, 350, 400, 450 and 500 degrees, with residence times of 10 to 120 sections. These conditions resulted in decompositions ranging from 0 to 97%. The decomposition at temperatures above 500 degrees, where secondary reactions become preponderant, was not studied. Satisfactory sulfur balances were obtained, and results were found to be reproducible. Hydrogen sulfide, elemental sulfur, and residual sulfur (compounds unreactive to ordinary reagents) were found as decomposition products in addition to the gaseous hydrocarbons, isobutylene and isobutene. The amount of decomposition increased with each rise in temperature and/or time of exposure. Based on experimental evidence and supported by similar known reactions, a free radical decomposition mechanism is proposed.

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Purification and some physical properties of nitromethane

In order to make available high-purity nitromethane for thermodynamic measurements, a commercially prepared sample was purified by chemical and physical means to better than 99.9 mole per cent as determined by the freezing point method. In addition to the thermodynamic properties reported by McCullough, et al., values for freezing point, density, refractive index, viscosity and surface tension were determined on the purified nitromethane. This paper describes the purification procedures and presents values for the latter properties.

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Structure of abelsonite

Abelsonite, a C11 nickel-porphyrin of the deoxophylloerythroetioporphyrin type, is shown to have methyl groups in the 2, 3, 7, 12, and 18 positions and ethyl groups in the 8 and 17 positions by high-resolution, high-field H nuclear magnetic resonance and nuclear Overhauser effect studies. Removal of the nickel by treatment with methanesulfonic acid permitted confirmation of the structure on the fee base porphyrin and demonstrated structural integrity under the conditions required for demetallation. The structure is best accounted for geochemically by the hypothesis that abelsonite is derived from a chlorophyll.

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Some asphalts from Oregon Basin (Wyoming) crude oil. [Black oils; viscosity, API gravity, POUR point, color, distillates]

"Asphalts from Wyoming “black oils” are being studied at the Petroleum Experiment Station of the Bureau of Mines at Laramie, Wyo., in cooperation with the University of Wyoming. These black oils are characterized by their high-asphalt, high-sulphur, and low-gasoline content and are difficult to refine by present methods into high-octane motor fuels, burning oils, and lubricants. Accordingly, their principal use, at present, is for the manufacture of road oil and asphalt.  The present production of black oil could be increased to meet a greater demand. During 1937 the daily production of these crude oils in Wyoming was slightly over 13,000 barrels, while the estimated potential production from existing wells was 56,000 barrels.  To aid in the more economical use of the black crude oils, the Bureau of Mines has published Hempel analyses of samples from various fields and is studying the thermo decomposition of all or part of the crude oil and methods of treating the straight-run and cracked distillates for their manufacture into motor fuels. From these crude-oil analyses it was estimated that some of the oils contain as much as 50 percent of 100-penetration asphalt; however, no comparative data have been published concerning the properties of these asphalts. Accordingly, a related study of the yields and properties of the asphaltic fraction would be of value in finding more economical uses for this type of crude oil.  This paper is a progress report of a study of the asphaltic fraction of Wyoming black oils. It describes the apparatus and method used in reducing Oregon Basin (Wyoming) crude oil to a dsired percentage of residuum or asphalt and gives the properties of the asphalts as determined by tests commonly used by the industry. From these data the properties of the 100-penetration asphalt were estimated. The temperature susceptibilities or the changes in consistency with changes in temperature, of the asphalts were calculated according to published formulas. These values were compared with the published values for similar asphalts from other crude oils."

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Asphalts from Rocky Mountain crude oil (Tech. 21-54)

In all, 117 asphalts were prepared to obtain a series of asphalts of different consistency from each crude oil. The crude oil was distilled in the glass apparatus shown in figure 1 (slide 2) first at atmospheric pressure and then at reduced pressures of about 1 to 5 mm. mercury to the desired amount of asphaltic residuum. The yields and properties of each of the asphalt products were then determined by conventional specification tests or by other means. From these data the properties of the 100-penetration (at 77 degrees F.) asphalts from each series were calculated in order to compare products of the same consistency from the different crude oils.

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Well level monitoring investigation. Series 1, Series 2 and Supplemental Well Series final reivew

During an 18 month period, three separate well level monitoring programs were conducted on the GKI Research Site. The Series 1 Well, located around blasted, operational and spent retorts, confirmed that rubblization does improve horizontal communication and may possibly be effecting vertical communication. The Series 2 Wells, in contrast, have suggested that there is perched water above the mahogany oil shale bed, flowing in cracks and fissures, but not communicating freely either horizontally or vertically in areas not affected by retorting. The Supplemental Wells strengthened the findings of the Series 2 Wells by noting that there is very little horizontal communication of waters throughout the entire section ast he heads of many of the wells are above surface elevations of another well a short distance away. All programs confirmed that the water table does vary seasonally, but even during wet periods this variance is not statistically significant.

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Flotation behavior of digested asphalt ridge tar sands

"The hot water process for Utah tar sands differs significantly from that used for Canadian tar sands due to inherent differences in respective bitumen viscosities and the nature of bitumen-sand association. These differences have led to the identification of certain design criteria necessary to achieve satisfactory phase disengagement during digestion . Subsequent flotation of digested tar sand is a subject of current attention and is considered in this publication for the Asphalt Ridge deposit.  Although contact angle measurements of solvent extracted Asphalt Ridge bitumen indicated moderate hydrophobicity, air bubble attachment to the bitumen concentrate is not possible. This surprising result suggests that flotation separation is dependent on air bubble entrapment rather than on air bubble attachment due to surface hydrophobicity. The entrapment of air bubbles in the bitumen was apparent from examination of the bitumen concentrate, especially at lower flotation temperatures.  A factorial design of the major operating variables in flotation separation indicated that the quality of separation was significantly dependent on the flotation temperature and to a lesser extent on the degree of agitation. For a flotation temperature of 77 degrees C a recovery of 96.7 degrees was realized at a grade of 61.0 degrees bitumen. The improved separation at higher flotation temperatures was found to be due to the decrease in bitumen viscosity resulting in more effective rejection of coarse sand form the concentrate.  This research effort, which has been sustained for the past six years at the University of Utah, is being continued to provide necessary design data for the construction of a pilot plant to treat Utah tar sands."

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Multiple thermal analysis of natural materials. [Containing dawsonite and nahcolite]

"Thermal study of natural materials, particularly rock samples, is a demanding, adventurous, and highly rewarding application of thermal analysis techniques. Many natural rocks are raw materials requiring heat processing to convert them to useful products. Many more can be evaluated, identified, or characterized by thermal analysis techniques (for example, see Beck).  Anyone attempting thermal analysis of natural rock samples, however, faces special problems in addition to the complex problems inherent in all thermal analysis techniques. These additional problems arise largely from the heterogeneity of rock samples. A rock consists of a collection of individual chemical compounds (minerals) mixed together in variable proportions. Sampling rock to represent its overall composition requires a sample significantly larger than the few milligrams accommodated by much of the commercially available thermal analysis equipment."

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Structural study of asphalts by nuclear magnetic resonance

The usefulness of a nuclear magnetic resonance method for the determination of average structural formulas and formula weights of asphalts is evaluated. The average formula weights are compared to molecular weights, showing fair agreement in the majority of cases. The more polar fractions of one asphalt had molecular weights up to three times the formula weights, while the less polar fractions had molecular weights in excellent agreement with formula weights. Comparison of aromaticity values from nuclear magnetic resonance data of one asphalt and its fractions with data from other investigators who studied the same samples using different methods showed the validity of the methods used in this investigation. Elution behavior of asphalt fractions on a chromatographic column correlated with aromaticity and with the number of condensed rings per average structural unit.

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Evaluation of the use of UCG gas to produce 4000 BPD and 12,000 BPD of methanol with conversion to M-gasoline

This study, which was undertaken by the Pritchard Corporation for the Office of Oil, Gas and Oil Shale Technology of the Department of Energy, involves an examination of the technical and economic feasibility of using raw gas from an underground coal gasification facility as feedstock for methanol synthesis, and producing M-gasoline from the methanol. It differs from previous studies in considering facilities smaller than those previously studied. Addressed also is the economic and technical feasibility of using equipment from existing ammonia plants for the production of methanol.

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Identification of frozen liquid samples with x ray diffractometer

The x-ray diffractometer unit can be used to identify components of frozen liquid samples. The low-temperature apparatus consists of a special sample holder with an attached cooling chamber, a Pliofilm cover to prevent frost formation on the sample, and an air-cooling system. Identifications are made by comparing the x-ray chart obtained for the powdered frozen sample with x-ray charts of known frozen liquids. This low-temperature technique has been successfully applied to identifying and making percentage estimates of the components of the liquid shale-oil distillate fractions of high boiling point.

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Keys to the mystery of crude oil. [Critical literature review on petroleum composition and origin; 107 references]

"This paper is a study and evaluation of recent literature on the composition of crude oil to determine the extent and direction of the findings reported as they may contribute to our further understanding of the origin of crude oil. The work of American Petroleum Institute projects is particularly stressed. There is a brief review of current theories regarding the origin of petroleum to form a background against which to consider the contributions of the research on composition. Then studies are considered on the following: nitrogen compounds, porphyrins, trace elements, and sulfur compounds; hydrocarbons in the gasoline, middle distillate, and heavy-oil boiling ranges; olefins; aromatics; chromatography; and thermal diffusion. The pertinent facts from various papers in these fields are pointed out in so far as these facts may concern the origin of petroleum in one way or another.    The authors believe that researches in the nonhydrocarbon field of nitrogen and sulfur compounds, for example, have provided, and will continue to provide, many clues helpful in determining the origin of petroleum. New instruments and techniques also are making possible important contributions from studies of hydrocarbons, even in the lubricating oil range. A great many individual pieces of information which may pertain to the origin of oil are available, and it should become increasingly possible to tie these together so that eventually a theory embracing many of these data can be expected."

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Thermal decomposition of sulfur compounds. II. 1-pentanethiol

1-Pentanethiol was theremally decomposed in a quartz tube utilizing a flow method. The apparatus and techniques used in this investigation have been described in a previous publication. The conditions (300-500 degrees with exposure times of 10 to 120 seconds) employed in this study resulted in decompositions ranging from 0.2 to 87%. The predominant sulfur containing decomposition product was hydrogen sulfude. Small amounts of sulfides and residual sulfur were also produced. The decomposition, as postulated, proceeds by way of an intramolecular splitting of 1-pentanethiol to produce pentene and hydrogen sulfide.

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Crude oil characterization by the Bureau of Mines routine method

Several thousand crude oil samples have been analyzed over the past 35 years by the Bureau of Mines, using its routine method. Because these analyses have been made on a comparable basis, they form an invaluable store of information concerning the differences in petroleum produced in this country during that period. They also serve as a reference basis for comparison with newly discovered crude oils, so that the latter may be classified as to possible methods of utilization.

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Aviation gasoline and its component hydrocarbons:  wartime research (1940--1945). [Data compilation and manual of analytical procedures]

This report is a summary of research conducted by the Bureau of Mines on aviation gasoline and its components from 1940 to 1945. The work was one part of the total wartime accomplishments of the Bureau’s Petroleum and Natural Gas Branch on recovery of petroleum, petroleum chemistry and refining, and production of helium.

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Autoxidation of three 1-alkylpyrroles. [26 refs]

Self-initiated autoxidation of 1-methylpyrrol, 1-isopropylpyrrole, and 1-butylpyrrole formed peroxidic polymers and carbonyl compounds thought to arise from peroxide decomposition. Four of these carbonyl compounds were isolated form 1-methylpyrrole oxidation products and spectral examination detected their homologs in oxidation products of the other two pyrroles. It is suggested that 1-alkylpyrroles react with oxygen by a free-radical peroxy addition process typical of conjugated dienes.

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Solid-state NMR studies of the reactions of silica surfaces with polyfunctional chloromethylsilanes and ethoxymethylsilanes

The silylation of silica surfaces by dimethyldichlorosilane, methyltrichlorosilane, dimethyldiethoxysilane, and methyltriethoxysilane has been studied by solid-state Si and C NMR, by use of cross polarization (CP) and magic-angle spinning (MAS). An earlier formalism for the quantitative analysis of the NMR data has been extended for use with polyfunctional silylating agents and applied in detail to dimethyldichlorosilane reactions. Silylation with ethoxylane reagents is less amenable to quantitative interpretation but appears to parallel closely the behavior of analogous chlorosilane reagents. With ethoxysilane reagents C NMR is found to be quite useful, especially for determining the fate of ethoxy groups. In all of the cases studied, the products are characterized primarily by single silane-to-surface attachments of each silane silicon atom. The presence of adsorbed water is found to plan an important role in the course and rate of the silylation reactions, especially those employing ethoxysilane reagents. The NMR data are used to address the question of “horizontal” and “vertical” polymerization within the “silane phase” on the silica surface.

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Silicon-29 nuclear magnetic resonance study of hydroxyl sites on dehydrated silica gel surfaces, using silylation as a probe

A detailed Si NMR analysis is presented on the silylation of a series of heat-treated silica gels by hexamethyldisilizane (HMDS) with the aim of elucidating details of the surface hydroxyl population of the unsillylated samples. It is found that the complete removal of all silanol groups from silica is probably approached only at temperatures higher than those normally employed in silica treatments (i.e., higher than 1000 degrees C) and that some molecular water may remain on the surfaces of samples normally considered “dried” (e.g., evacuated at 200 degrees C). The population and reactivity patterns of surface hydroxyls are considered in terms of reasonable surface and dehydration models.

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Thermal analysis of natural fuels

The natural solid fuels – coals, oil shales, and black shales – constitute present and potential sources of fossil fuel energy. Thermal degradation of many materials in this group also generates valuable products – coke and coal tar from coal types, and shale oil from oil shales and some black shales – so that the thermal properties of natural fuels largely determine their value. Application of thermoanalytical techniques to evaluating the thermal characteristics of natural fuels, however, presents problems not solved with the usual DTA and TG equipment. During their study of oil shales the U.S. Bureau of Mines developed thermoanalytical equipment and techniques to overcome the particular problems presented by natural fuels. This apparatus is described, together with its application to a study of natural fuels, particularly oil shale from the Green River Formation.

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Properties of crude oil from the Greasewood Flat area in Colorado

"The Bureau of Mines has recently collected two samples of crude oil from wells in the Greasewood Flat area of northeastern Colorado.  Sample 31310 was taken from the Continental Oil Co.’s well Briggs No.1 which came in on September 27, 1931, with a maximum production of 940 barrels per day. Sample 31311 was taken from the Reiter-Foster Oil Co.’s well Ida Johnson No. 1 which came in on August 24, 1931 with a maximum production of approximately 1000 barrels per day.  The characteristics of these two samples, as shown by the Hempel analyses, indicate that they are almost identical. They have very low sulfur content and the residuum has a low carbon-residue content which would indicate that they are excellent crude oils for refining. Crude oils yielding a residuum which has a carbon—residue content of 4 per cent or less usually make good material for the manufacture of cylinder stocks.  The pour points of the samples and the cloud test of the fractions obtained from the vacuum distillation indicate that the Greasewood Flat oil contains considerable wax. The high wax content would cause some difficulty in transmitting this oil though a pipe line during extreme cold weather."

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Stationary phases for separation of basic and nonbasic nitrogen compounds or hydrocarbons by gas--liquid chromatography

"Retention data and bleed rates have been measured for some relatively stable liquid phases to obtain operational limits for gas-liquid chromatographic separation of polar shale-oil concentrates with boiling points above 200 degrees C. Gas chromatographic separation of polar compounds with boiling points over 400 degrees C in quantities adequate for spectral identification may be accomplished on packed columns with efficiencies near 5000 theoretical plates and with less than one percent column bleed contamination.  Relative retention values were determined for some basic and nonbasic nitrogen compounds, and some hydrocarbons on polyethylene glycol (Carbowax 20M), polyethylene glycol terminated with terephthalic acid (Carbowax 20M-TPA), octylphenoxypolyethoxy ethanol (Triton X-305), and purified Apiezon L doped with Carbowax 20M-TPA. Retention data were obtained at 180 degrees and 220 degrees C on the polar liquid phases. Triton X-305 was found to show more alkyl character than Carbowax 20M.  Column bleed rates were measured with five percent liquid phase at 220 degrees C, the maximum temperature round appropriate for extended use of the polar columns. The Carbowax 20M bleed rate was 0.10 micro grams hydrocarbon-equivalent/min with very slightly less for the Carbowax 20M-TPA, while the Apiezon L rate was 0.01 micro grams/min, all at 73 ml/min (25 degrees C, 1 atm) flow rate. An Apiezon L column doped with five percent Carbowax 20M to reduce tailing exhibited a bleed rate characteristic of Carbowax 20M.  Hydrogen flame response factors were determined for several heterocyclic nitrogen compounds. By the agreement of hydrogen flame response factors for samples put through polar and nonpolar columns it was concluded that the polar columns do not destroy the relatively unstable indole-type nitrogen compounds although they are strongly retained."

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Problems in analysis of wide boiling range materials using a gas liquid chromatography-flame ionization detector system

The bureau of Mines investigated the sources of error of a GLC-FID system in quantitative analysis of wide-boiling-range mixtures such as are encountered in simulated distillation of crude shale oil or petroleum. The sample-introduction system, column effects, and the FID itself were studied using normal alkane as a diagnostic aid. The on-column inlet technique of sample introduction is compared with the flash-vaporization inlet technique. Column-adsorption effects and the use of tail-reducing materials are discussed. Problems with the FID relating to insulator and electrode contamination, electrode emissivity, sample capacity, and burner design are illustrated and discussed. Normal alkane FID response relative to n-heptane over the C-C range is shown to be 1.00 plus or minus 0.03 for a parallel-plate FID when operating normally.

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