AndreaBozzo/ceres-open-data-index huggingface dataset:
COREHOLE DATA ON COLORADO GREEN RIVER OIL SHALES

The Bureau of Mines, as part of its work on synthetic liquid fuels, has undertaken to evaluate the character and extent of the oil-shale reserves in northwestern Colorado. This enormous deposit embraces an area of over 1,000 square miles and is characterized by marked variations in quality at different localities. Our work indicates that reliable assay data are insufficient to describe these shale deposits accurately. Furthermore, there is a wide difference of opinion among interested parties in both the  Bureau and in industry as to the interpretation of core hole assay information in the prediction of shale reserves.  The Bureau of Mines is planning a meeting of interested  persons on shale reserve evaluation, to be held at the Oil-Shale Mine and Engineering Experiment Station, Rifle, Colorado, on May 10, 1954. The objectives. Of this meeting are:  1. Present new core hole assay information.  2. Establish a uniform procedure for estimating  shale-oil reserves.  3. From the isopachous maps prepared by the Bureau,  discuss the additional drilling required to make more reliable reserve estimates.  Over the past several years, the Bureau of Mines has made Fischer assay analyses of cores from holes drilled by various shale landowners. Part of this information was published in 1951 in Bureau of Mines Report of Investigations 4769, entitled "Green River Oil Shale  Reserves of Northwestern Colorado, " by Carl Belser. Since  this was published, additional cores have been assayed. Results obtained from 29 new core holes will be presented at the meeting. It also is planned to distribute analyses on the 53 holes drilled to date to those attending.

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HIGH TEMPERATURE REACTIONS OF OIL SHALE MINERALS AND THEIR BENEFIT TO OIL SHALE PROCESSING IN PLACE

Limited temperatures reached by Green River Formation oil shale during surface retorting restrict accompanying mineral reactions to decompositions whose products may  have aqueous and gaseous mobility . The substantially higher temperature " reached during combustion processes in place initiate solid-state mineral reactions . Three solid- state reactions are examined: (1) gas-solid combination retaining sulfur in the shale; (2) solid- solid formation of new minerals; and (3) gas-solid  recarbonization. To evaluate the unknown solid- solid reactions the Laramie Energy Research Center conducted tests on two sample representing possible resources for in situ combustion, heating them to temperatures up to 1200oC. new minerals appearing in samples during these experiments were identified by X-ray diffraction. Evaluation  of all these solid state reactions indicate that they work to minimize possible environmental consequences of in situ oil-shale development.

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ORIGIN AND CHARACTERISTICS OF GREEN RIVER OIL SHALE

The Green River Formation of Colorado, Wyoming, and Utah consists of an organic rich shale or marlstone. This deposit consists of varying amounts of soluble organic material, insoluble organic material, and minerals. The mileral composition depended upon the amounts of soluble and insoluble minerals washed into the basin lakes and upon conditions which caused precipitation of minerals from the aqueous phase. Precursors for organic material consisted of algae which grew profusely in the saline lakes, and the plant sports and pollen grains which were wind borne into the lakes. The amount of organic material remaining in the sedimentary shale depended upon the amount of accumulation, preservation, and alteration of the original precursor organic material.

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CONSTITUTIONAL ASPECTS OF OIL-SHALE KEROGEN

"Various tests were performed on 12 domestic and foreign oil shales to ascertain differences or similarities of the structure of kerogens and the composition of the soluble organic material associated with the kerogens. The oil shales varied in geologic age, environment, source material, and elemental composition.  The kerogens were studied by oxidative degradation, pyrolytic degradation and physical property analyses. The associated bitumens were studied by bitumen compositional analyses.  The results of this study showed major differences in the structure of the kerogens and in the composition of the associated bitumens. Most of the differences appear to be related by geologic age, but in some instances, the differences are related to source material or elemental compounds."

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CONSTITUTION OF THE ORGANIC MATERIAL IN GREEN RIVER OIL SHALE

This paper presents the available data related to the constitution of kerogen. By correlating and summarizing this data, an attempt was made to obtain the best concept of the present knowledge of the structure of kerogen. Many of the methods of degradation have limitations, however, much information concerning the structure of kerogen is obtained by determining the constitution of these products. It is recognized that kerogen is not a chemical compound but a mixture of components which may vary stratigraphically and geographically in different deposits. However, this variation is not as pronounced as it is with coal. Unless indicated otherwise, the data presented was obtained from a study of the kerogen of Green River oil shale from the vicinity of Rifle, Colorado.

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MODELING OF ELECTROMAGNETIC FIELDS IN DISSIPATIVE DIELECTRICS SUCH AS OIL SHALE

The in situ heating of oil shales for recovery of oil is a problem of great significance to the United States. There have been attempts in the past to set up pilot plants to study various methods of in situ heating of oil shales with electromagnetic radiation and recovery of the oil produced from the oil shales. the purpose of this thesis is to study one particular geometry that could be of use in this process.

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MINERAL PROFILE OF OIL SHALES IN COLORADO CORE HOLE NO. 1, PICEANCE CREEK BASIN, COLORADO

Mineral profiles of oil shales in the Green River Formation in Colorado Core Hole No 1 were made by the US Bureau of Mines using x-ray diffraction data. The corrected peak heights of 8 minerals and the oil yields in gal/ton of the samples were plotted against depth. The mineral distributions are described in relation to 4 mineral zones of widely used stratigraphic divisions. Relationships between minerals and between mineral amounts and organic matter amounts were investigated statistically. Direct relations between the organic content and the amounts of silicate minerals were the most significant correlations found.

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MINERAL AND ORGANIC  RELATIONSHIPS THROUGH COLORADO'S  GREEN RIVER FORMATION ACROSS ITS SALINE DEPOSITION CENTER

Stratigraphically correlated profiles of organic matter concentration and the distribution and relative abundance of 8 major minerals in oil shales, through Colorado's Green River Formation near its saline depositional center, ere used to evaluate relationships among these components in Colorado oil shales.  Strong direct relationships between the volume of organic matter in Colorado's  Green River Formation oil shales and the relative amounts of the silicate minerals quartz, soda feldspar, and potash feldspar were demonstrated singly and collectively.  The silicate minerals were also shown to be directly related to each other.  Dawsonite, in the saline zone of the Formation, was also shown to be directly related to the volume of the organic matter and indirectly to the amount of nahcolite.  These relationships were all interpreted as resulting from CO2  arising from organic matter in the sediment.  A strong relationship, demonstrated between dawsonite and quartz, was credited to both the organic CO2mechanism and to ash-fall decomposition.  Significant noncorrelaton with organic matter or any of the other minerals was found for calcite and analcite.  Lack of significant correlation among any of the components in a particular horizon demonstrated absence of geochemical control during its deposition.  In addition to their geochemical value, these relationships provide an additional interpretive tool for the Green Rive Formation deposits.

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KEROGEN OF THE GREEN RIVER FORMATION

The decomposition of plant and animal remains in marine and non marine environments and the alteration of this debris during subsequent geologic periods by numerous reactions, produced a wide variety of carbonaceous materials. Source material and conditions of deposition were major factors influencing the types of final products formed, which range from anthracite coal to petroleum. Between these two extreme types are numerous other carbonaceous substances of different compositions and properties. Oil shales, kukersite, and torbanite represent types of carbonaceous material that contain various amounts of organic matter, commonly called kerogen, from which high yields of oil can be produced at elevated temperatures, even though the constitutions of the kerogens differ.

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PROTON AND CARBON-13 NMR STUDIES ON NAPHTHA AND LIGHT DISTILLATE HYDROCARBON FRACTIONS OBTAINED FROM IN SITU SHALE OIL

"The proton and carbon-13 NMR studies were made on the saturates, olefins, and aromatic fractions obtained from the naphtha and light distillate cuts of in situ shale oil. Carbon-13 NMR area measurements were used to compute the C/C ratio and, thus, the average paraffinic chain length for the saturate fractions. Identification and the relative concentrations of the various olefins were determined from carbon-13 NMR data. The NMR  results are compared with the mass spectroanalysis data on the same fractions. The percent of carbon types in the aromatic fractions were also determined by both NMR and mass spectral data . Qualitative agreement between the two techniques was evident. However, some definite disagreement also exists."

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PHYSICO-CHEMICAL INVESTIGATION OF EASTERN AND WESTERN SHALE OILS PRODUCED BY THE IGT HYTORT AND FISCHER ASSAY PROCESSES

"The major interest in oil shale development within the United States, thus far, has focused on the oil shales In the Green River Formation In Colorado, Utah and  Wyoming . However, a substantial portion (nearly 25 ,000 square miles) of the Eastern United States is underlain by the Devonian Black Shales, and in principle, represents a sizeable potential resource. These shales, however, yield only less than one-half as much liquids upon heating as do the Green River Formation oil shales, because of the lesser hydrogen contents of the Devonian shales. Therefore, processes to extract liquids or improve recovery ratios from the Devonian shales must necessarily deal with special retorting techniques for hydrogen deficient  materials. One such candidate process is the Institute of Gas Technology 's Hytort process, which retorts oil shale under hydrogen pressure with the result that oil yields of Devonian shales are increased 2.5 times over those obtained by the standard Fischer assay . Characterization of the Eastern and Western oils that are produced by the IGT and Fischer assay  processes would be beneficial toward: a) assessing the quality of the product oils , c) understanding the retort process and c)  providing information or optimizing the process."

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HYDROCARBON TYPE ANALYSIS OF EASTERN AND WESTERN SHALE OILS PRODUCED BY THE IGT HYTORT AND FISCHER ASSAY PROCESSES

Shale oils produced form Eastern and Western oil shales by the Fischer assay and IGT Hytort processes have been investigated by both 1H and 13C high resolution NMR techniques, as were hydro treated Eastern shale oils obtained by the IGT Hytort process.  From the NMR data of the shale oils, the average molecular structure parameters were calculated as well as mole percents of aromatics, olefins and alkanes.  Although it is recognized that the parameters have little exact meaning, the values do represent quantitatively the compositional differences observed in the NMR spectra of the shale oils resulting from the two retorting processes.  Differences in chemical composition are discussed for the Eastern and Western shale oils.  Also discussed are the solid state carbon 13 NMR spectra of Eastern and Western oil shales before and after retorting by the Fischer assay and IGT Hytort processes.

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HIGH RESOLUTION NMR SPECTROSCOPY: ITS APPLICATION TO SHALE OIL COMPONENT/TYPE ANALYSIS

"A brief review is given of the state-of-the-art in shale oil  analysis by instrumental methods with emphasis on high resolution nuclear magnetic resonance (HMR) spectroscopy. The technique was applied to the analysis of saturate, olefin and aromatic cuts from the naphtha and light distillate fractions obtained from shale oil . The  types of alkanes present in the saturate cut, as well as their percent branching and average carbon number were determined. Also described is the use of carbon-13 HHR to determine the location of the double bonds in the olefin cuts, and to determine certain average molecular  properties for the aromatic cuts ."

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EFFECT OF PALLADIUM CATALYST ON HYDROGENATION OF SHALE OIL

For the past several years new reserves of petroleum have been found at a rate about equal to consumption.  In the foreseeable future other sources of oil will be needed to keep up with the demand for gasoline and other oil products. Oil shale is one of the other sources of oil that has been investigated.  It  has not been used commercially in this country because of unfavorable  economics. The estimated recoverable shale oil reserves in the Green River Formation of Colorado, Utah and Wyoming alone are in excess of a trillion barrels of oil (1).  If an economic method could be found to liberate the organic matter now locked in the compact sedimentary rock of the Green River Formation, it could become the biggest oil field in the world.  Because of the similar physical nature of shale oil and petroleum, considerable effort has been directed toward establishing reaction conditions so that  shale oil may be processed by conventional petroleum refinery operations.  The shale oil, however, contains a high nitrogen and sulfur content, and the hydrocarbons present in it are highly unsaturated.  Nitrogen compounds have an adverse effect on most of the cracking catalysts and are partially responsible for extensive gum formation.  Sulfur compounds not only promote  corrosion, but also have objectionable odors.  Thus the upgrading of shale oil is essential prior to its processing in the usual refinery equipment.  Because of the large percentage of olefinic hydrocarbons present, which are adversely affected by severe chemical treatments, and to overcome the major refining difficulties caused by nitrogen and sulfur, hydrogenation is recommended to upgrade the shale oil.

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PRODUCTION OF BENZENE, ETHYL  ALCOHOL, AND OTHER PRODUCTS FROM OIL SHALE

Benzene is one of the most important organic chemicals both in quantity consumed and variety of products in which it plays an essential part.  While used directly as a solvent and gasoline additive, it finds its greatest use as a chemical raw material.  The major derivatives are stryrene, phenol, nylon, aniline, synthetic detergents, chlorobenzenes, and nitrobenzene. These find ultimate outlet in every phase of industry; synthetic rubber, resins, plastics, medicinal, dyes, insecticides, textiles, detergents, explosives and others.  Of comparable importance is ethyl alcohol.  It ranks as one of the top chemicals in the organic field, entering either directly or indirectly into innumerable articles of commerce.  It is indispensable in the manufacture of scores of products for national defense, such as smokeless powder, protective coatings, plastics, pharmaceuticals, and in supplementing petroleum as a source of butadiene for synthetic rubber manufacture.  It has potential use as a fuel for internal combustion engines and has been shown to have value as a blending agent for raising the octane number of shale gasoline.

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THERMAL PROCESSING AND CHEMICAL TREATING OF COLORADO SHALE OIL

For the past 5 years the Bureau of Mines at Rifle, Colorado has conducted experimental work on the thermal processing of shale oil and the chemical treating of distillate products.  This work was completed at the end of June 1954.  Although the large volume of data has not yet been assimilated and evaluated, this paper summarizes in a general way our current conclusions from the work.  Before discussing the refining work it is desirable to have in mind the physical  and chemical properties of Colorado shale oil.  Some of the properties of Colorado shale oil is in the heavy oil class, about 20 API gravity, and contains almost no material in the gasoline boiling range.  Its pour point and viscosity are high, making it difficult to handle without heating.  Actually, some treatment to reduce the pour point is required to make long distance pipeline transportation practical.

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NITROGEN TYPES IN LIGHT DISTILLATES FROM ABOVEGROUND AND IN SITU COMBUSTION PRODUCED SHALE OILS

There is some evidence that in situ retorted shale oils may have generally lower heteroatom and polar compound concentrations than aboveground retorted oils.  This could make in situ oils more attractive as an refinery feedstock or as  fuel sources than aboveground produced oils.  To help determine if differences in heterocompound composition might exist between oils produced in these different ways, light distillate fractions (400 to 600 F nominal boiling range) from two different types of internal combustion retorting processes, on aboveground and one in situ, were compared in analyses.  Both oils were produced in forward-burn type processes in which the exiting oil had the opportunity for contacting raw oil shale or included minerals. The main difference in the two retorting processes was the time-temperature history of the oils produced.  The aboveground process using crushed shale was a rapid-heat, high temperature process whereas the in situ process was apparently a slow-heat, low temperature process.  Direct gas-to- solids heat exchange occurs in both processes.  Other imponderables such as  the contact of the product oil with raw shale or air in either case, or raw or spent shale in situ could, of course, affect the character of the oil also.

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IDENTIFICATION OF ISOPRENOIDS, STERANES, AND TERPANES IN FISCHER ASSAY RETORTED SHALE OILS

Most of the geochemical studies have been made on the unpyrolyzed bitumen because of the suspicion that pyrolysis of the kerogen would destroy or alter the biological markers and thus negate the results.  However, recent studies suggest that some of these markers survive pyrolysis.  Gallegos (8) reported the presence of gammacerane and the C-27, C-28 and C-29 steranes in a pyrolysis study of so called "kerogen shale" -- shale residue after the extraction of solubles with a benzene-methanol mixture.  Takeo (9) reported the presence of C-18 and C-20 alkane isoproenoids in an N.T.U.  shale-oil distillate.  In this study, saturate fractions of Fischer assay oils from an earlier study (10) were examined in detail to see of the biological markers survive the retorting process.  A study of these biological markers in the oils produced from a core might be used as an aid in the geochemical study of sediments. Although this core is not identical to that studied by Robinson and Cook, it is from the same area so that some comparisons can be made between the bitumen and the pyrolyzed product.

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APPLICATIONS OF NUCLEAR MAGNETIC RESONANCE TO OIL SHALE EVALUATION AND PROCESSING

This paper is concerned with the application and refinement of recently introduced 13C NMR techniques for obtaining high resolution spectra of solid materials. These techniques, known as cross polarization and magic angle spinning show promise for the characterization of fossil fuels. One reason is because the CP/MAS techniques provide important information about the organic carbon distribution in intractable solids.

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REACTIVITY OF RETORTED MICHIGAN ANTRIM OIL SHALE IN O2/N2 ATMOSPHERE

The reactivity and the kinetics of oxidation of retorted Michigan Antrim oil shale were determined for the final stage of the combustion process using thermogravimetric techniques. The variations in the reactivity of the residues are discussed in terms of the amount of oxygen uptake, pseudo-ignition temperature, peak reaction temperature, and the magnitude of the maximum oxidation rates.

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KINETICS OF OXYGEN CHEMISORPTION ON MICHIGAN OIL SHALE RESIDUE

The adsorption of oxygen on Michigan oil shale residue obeys the same kinetic model as the chemisorption of gases on metallic surfaces. Both processes show that the activation energy and the pre-exponential factor depend on a pseudo-coverage, X. The methodology by which the data could be tested and the kinetic parameters evaluated are discussed in this paper.

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KINETICS GOVERNING THE PYROLYSIS OF MICHIGAN OIL SHALE

An investigation of the thermal decomposition of Michigan Antrim oil shale showed that the kinetics obeyed a second-order power-model equation over the region where the kerogen decomposes. This kinetic model holds over the range of heating rates investigated which was from 0.625 degrees C/minute to 40 degrees C/minute. The methodology by which the kinetics were determined is discussed in this paper.

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TRUE IN SITU RECOVERY OF SHALE OIL

True in situ recovery is defined as recovery in place, and means mining is not used in the recovery process. The properties of oil shale must be considered to put the problems of true in situ shale oil recovery into perspective. The negligible permeability, from one millidarcy to 10^-8 Darcy, limits fluid movement within oil shale. An elastic range up to 2% strain, and a plastic range up to 12% strain, absorb fracturing energy at high strain rates. Low thermal conductivity limits heat transfer by conduction. Thermal swelling of as much as 3 to 5% at 300 degrees C can close off many potential flow paths in a fractured oil shale formation. A pronounced loss of strength above 315 degrees C changed oil shale at retorting conditions. The high decomposition temperature of kerogen makes shale oil recovery more difficult than recovery of high viscosity petroleum by steam flooding.

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WASTEWATER VARIATIONS AND TREATMENT ALTERNATIVES FOR SELECT OIL SHALE PROCESSES (ABSTRACT ONLY)

Wide variations in constituent and parameter concentrations have been observed in wastewaters resulting from different oil shale extraction processes. Extreme difficulties in preservation, analysis, and treatment of these fluids have been noted. As the DOE's lead center for synfuel activity, LETC has been charged with developing protocols for each of these areas. This paper presents the results of several years'research conducted by LETC and its contractors and by the Department of Civil Engineering at the University of Arizona into proper procedures necessary to collect, store, analyze, and treat representative samples of oil shale process waters. Data are presented which will describe five waters collected from true and modified in situ retorts as well as surface facilities. Recommended preservation and analysis techniques are presented as are treatment methods and approaches found to be appropriate at the laboratory scale. This paper concludes with a description of ongoing and planned research at LETC.

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OHIO OIL SHALE CORE STUDY, SHAWNEE NO. 1 SCIOTO COUNTY, OHIO

While Ohio is underlain by 25,000 square miles of Devonian/Mississippian organic rich shales, only the southern unglaciated portion of the main north-south outcrop represents a readily mineable resource. This five county area has been studied by previous ODOE projects which have focused on surface field and archive data. The current study represents a transition to a more detailed effort of documentation based on subsurfaced coring, sampling, and testing. The subject core hole is l located at Shawnee State forest headquarters seven miles west of Portsmouth, Ohio on the Ohio river is Scioto County. The entire up split core was shipped to the USDOE Laramie Energy Technology Center, where it was split and tested. The second half was then returned to ODOE for further retort testing.

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