Green River Oil Shale Research Articles

99/00162 Effect of the mineral matrix in the reactions of oil shales: 1. Pyrolysis reactions of Turkish Göynuk and US green river oil shales

Within the Norwegian 15th Round deep-water production Licence No. 217 on the Vøring Plateau on the Norwegian continental slope, there is an unusually rugged seafloor topography. Our study addresses new 2D-, 3D-, and bathymetric data acquired in the Vema Dome area, where evidence for active piercement shale diapirism is found. The cores of the shale diapirs consist of coccolith oozes deposited during the Paleocene and Miocene. Individual shale diapirs and diapiric escarpments rise up to 70 m above the general sea floor (at 1200 m water depth). One of the key questions in our study has been to find out why diapirism is triggered over the Vema Dome and not over the nearby Nyk High, which has similar buried deposits of coccolith oozes. On the basis of interpretations of the new data, we conclude that the triggering is caused by a combination of at least three factors: (a) a buried low-density, high-porosity layer of deformable material (the coccolith ooze) ; (b) a doming substratum which causes extension and faulting; (c) migration of light hydrocarbons through some of the faults and fault zones. A fourth factor which probably contributes to triggering is tectonic instability. The one factor that discriminates the Vema Dome area from the neighbouring Nyk High area is the dome itself. We therefore suspect that this in some way is the main factor responsible for the triggering. Furthermore, we conclude that the process of piercement shale diapirism in the Vema Dome area is probably still active, but, because the movement of the sediments is suspected to be very slow, it should be of only minor concern to future oil field development.

Applications of laser micropyrolysis–gas chromatography–mass spectrometry

An apparatus which couples a laser microprobe with a GC–MS has recently been constructed in our laboratories to facilitate analytical micropyrolysis studies. The utility and versatility of the technique is demonstrated through the analysis of micro-sized quantities of various organic fossils. Results are reported from a torbanite coal, Green River oil shale, Tasmanite oil shale, an isolated Tasmanites microfossil and oil-bearing fluid inclusions. A diverse range of aliphatic products including distributions of n-alkene/ n-alkane pairs, isoprenoids, polycyclic biomarkers and various alkylaromatics have been detected from these materials. The analytical credibility of the laser micropyrolysis GC–MS technique is confirmed by the favourable comparison of the laser derived molecular data to corresponding data obtained from more traditional methods.

Effect of the mineral matrix in the reactions of oil shales: 1. Pyrolysis reactions of Turkish Göynük and US Green River oil shales

The effect of the mineral matrix of Turkish Göynük and Green River oil shales on the conversion of kerogen into organic material in pyrolysis reactions was investigated in this study. The conversion of kerogen to volatile organic material in pyrolysis reactions increased with increased reaction temperatures for the original and demineralized products of oil shales. Increasing the heating rate also caused greater kerogen conversion. It was found that pyrolysis reactions were catalyzed by alkaline earth metal cations in carbonates and inhibited by silicates. The inhibition effect of the silicates seemed to be greater than the catalytic effect of the carbonates in the pyrolysis reactions of the original Göynük and Green River oil shales.

96/01487 Metallopetroporphyrins as process indicators: Mass spectral identification of NI(ETIO) and Ni(DPEP) homologous series in Green River shale oil

96/01487 Metallopetroporphyrins as process indicators: Mass spectral identification of NI(ETIO) and Ni(DPEP) homologous series in Green River shale oil

96/00163 Detailed structural characterization of the organic material in Rundle Ramsay Crossing and Green River oil shales

96/00163 Detailed structural characterization of the organic material in Rundle Ramsay Crossing and Green River oil shales

95/05807 Metallopetroporphyrins as process indicators: Separation of petroporphyrins in Green River oil shale pyrolysis production

95/05807 Metallopetroporphyrins as process indicators: Separation of petroporphyrins in Green River oil shale pyrolysis production

Organic Matter Accumulation in a Thick, Lacustrine, Lower Cretaceous Sedimentary Sequence in Gabon: Facies and Maturity Variations: ABSTRACT

A total of about forty core samples representing an almost two kilometer thick, lacustrine sedimentary sequence of Neocomian age in the south Gabon basin was analysed for its hydrocarbon generation potential, maturity and further organic matter characteristics. Organic carbon concentrations are variable and not particularly high (0.4-5%), but the organic matter is hydrogen-rich. This hydrogen-richness finds its expression in high hydrogen indices (about 600 to 700 mg hc/g TOC) which decrease with increasing maturation. According to pyrolysis experiments, hydrocarbon generation from the immature sediments is predicted to begin only at temperatures greater than 100{degrees}C and reaches a maximum only at temperatures greater than 150{degrees}C, because the organic material possesses a very high thermal stability. Such a high thermal stability was already established for lacustrine organic matter from some other deposits (e.g. Green River oil shales) and is certainly an important factor for the evaluation of hydrocarbon potentials in lacustrine basins. The maturity of the organic matter changes from immature to mature with increasing depth. Peak oil generation stage was almost reached by the deepest samples as indicated by a variety of optical and geochemical parameters. Generated petroleum should be wax-rich and rather poor in gas, except if oil to gasmore » cracking occurs within the source rocks. With respect to molecular geochemistry, several interesting pecularities were found. As an example, variable distributions of several unknown tetracyclic terpanes (molecular formula C{sub 24}H{sub 42}) were detected in the samples of lower maturity. Two series of terpane pseudohomologues occur in the more mature samples, one of which is assumed to consist of diahopanes, the other yet remaining unknown. These compounds seem to be widely distributed in lacustrine sediments of higher maturity, thus possibly representing maturity and/or facies indicators.« less

Oxidized oil shale for removal of nitrogen oxides in combustion gas streams

Oxidized oil shale from the combustor in the Lawrence Livermore National Laboratory (LLNL) hot recycled solids (HRS) oil shale retorting process has been found to be a catalyst for removing nitrogen oxides from laboratory gas streams, using NH 3 as a reductant. Oxidized Green River oil shale, heated at 10 °C min −1 in an Ar/O 2/NO/NH 3 mixture (~93%/6%/2000 ppm/4000 ppm) with a gas residence time of ~0.6 s, removed NO between 250 and 500 °C, with maximum removal of 70% at ~400 °C. Under isothermal conditions with the same gas mixture, the maximum NO removal was ~64%. When CO 2 was added to the gas mixture at ~8%, the NO removal dropped to ~50%. However, increasing the gas residence time to ~1.2 s, increased NO removal to 63%. Nitrogen balances of these experiments suggest selective catalytic reduction of NO is occurring using NH 3 as the reductant. These results are not based on completely optimized process conditions, but indicate that oxidized oil shale is an effective catalyst for NO removal from combustion gas streams using NH 3 as the reductant. Parameters calculated for implementing oxidized oil shale for NO x remediation on the current HRS retort, indicate an abatement device is practical to construct.

Solvent Swelling Studies of Green River Kerogen

Kerogen has been isolated from Green River oil shale by dissolving the minerals in HF and HCI and also by using aqueous ammonium sulfate. The resulting kerogen samples were swollen in 28 different solvents. The volumetric solvent swelling of the kerogen roughly follows the predictions of regular solution theory for almost all of the solvents including good hydrogen bond acceptors. The solubility parameter from the swelling studies is close to that calculated from Siskin's structure. Hydrogen bonding does not seem to be an important factor because good hydrogen bonders show swellings similar to non-hydrogen bonders of similar solubility parameter. The inorganic content of the isolated kerogen does not have a large effect on solvent swelling. Samples containing 42% inorganics generally swell somewhat more than samples containing 5% inorganics. The cross-link density of this kerogen is high.

Partial resolution of sources of n-alkanes in the saline portion of the Parachute Creek Member, Green River Formation (Piceance Creek Basin, Colorado)

Systematic variations in the 13C contents of individual extractable n-alkanes (C 16–C 29) can be modelled quantitatively and interpreted as indicating contributions from at least five distinct sources. These appear to be cyanobacterial ( C 16– C 18, δ 13 C = − 37 0 00 vs PDB ), phytoplanktonic C 16–C 23, δ = −32 0 00 ), chemoautotrophic bacterial ( C 20– C 29, δ = −38 0 00 ), phytoplanktonic or heterotrophic bacterial ( C 20– C 29, δ = −30‰ ), and vascular plants ( C 23– C 29, δ = −29‰ ). Hydrous pyrolysis of related kerogens yields large quantities of additional n-alkanes with different and much more uniform δ values. The latter materials are apparently derived from the thermolysis of aliphatic biopolymers whose presence in the Green River Oil Shale has been recognized visually.

Organic and mineralogic factors influencing Green River oil shale methane emissions

Potential influences on methane emissions from the Green River oil shale were tested. The factors investigated in this study were: 1. 1. thermal maturity, 2. 2. total organic carbon (TOC), 3. 3. organic matter composition, and 4. 4. mineral matter composition. Analyses conducted include maceral reflectance ( R 0), qualitative and quantitative fluorescence petrography, TOC testing, modified Fisher assay, Rock-Eval pyrolysis and quantitative X-ray diffraction (XRD). Yellow lamalginite content was directly related to methane content. Methane content was more highly correlated to yellow lamalginite than any other factor. TOC did not influence the methane contents of the samples. Thermal maturation did not control methane emissions because no thermal variation was measured in the sample suite. The altered maceral group (AMG) played no significant role in methane production from the samples. Stepwise linear multivariate regressions were performed to combine and equate variables to methane content.

Methane in Green River Oil Shale: ABSTRACT

Methane in Green River Oil Shale: ABSTRACT

Simulations of the Origin of Fluid Pressure, Fracture Generation, and the Movement of Fluids in the Uinta Basin, Utah

The Altamont oil field in the deep Uinta basin is known to have reservoir fluid pressures that approach lithostatic. One explanation for this high pore-fluid pressure is the generation of oil from kerogen in the Green River oil shale at depth. A three-dimensional simulation of flow in the basin was done to test this hypothesis. In the flow simulation, oil generation is included as a fluid source. The kinetics of oil generation from oil shale is a function of temperature. The temperature is controlled by (1) the depth of sediment burial and (2) the geothermal gradient. Using this conceptual model, the pressure buildup results from the trade-off between the rate of oil generation and the flow away from the source volume. The pressure increase depends primarily on (1) the rate of the oil-generation reaction and (2) the permeability of the reservoir rocks. A sensitivity analysis was performed in which both of these parameters were systematically varied. The reservoir permeability must be lower than most of the observed data for the pressure to build up to near lithostatic. The results of the simulations indicated that once oil generation was initiated, the pore pressure built up rapidly to near lithostatic. We simulated hydrofractures in that part of the system in which the pressures approach lithostatic by increasing both the horizontal and the vertical permeability by an order of magnitude. Because the simulated hydrofractures were produced by the high pore pressure, they were restricted to the Altamont field. A new flow system was established in the vicinity of the reservoir; the maximum pore pressure was limited by the least principal stress. Fluids moved vertically up and down and laterally outward away from the source of oil generation. The analysis indicated that, assuming that one is willing to accept the low values of permeability, oil generati n can account for the observed high pressures at Altamont field.

An isotopic biogeochemical study of the Green River oil shale

Thirty-five different samples from three different sulfur cycles were examined in this stratigraphically oriented study of the Shell 22x-1 well (U.S.G.S. C177 core) in the Piceance Basin, Colorado. Carbon isotopic compositions of constituents of Green River bitumens indicate mixing of three main components: products of primary photoautotrophs and their immediate consumers ( σ ∼ −30‰ vs PDB ), products of methanotrophic bacteria ( σ ∼ −85‰), and products of unknown bacteria ( σ ∼ −40‰). For individual compounds synthesized by primary producers, σ-values ranged from −28 to −32‰. 13C contents of individual primary products (β-carotene, steranes, acyclic isoprenoids, tricyclic triterpenoids) were not closely correlated, suggesting diverse origins for these materials. 13C contents of numerous hopanoids were inversely related to sulfur abundance, indicating that they derived both from methanotrophs and from other bacteria, with abundances of methanotrophs depressed when sulfur was plentiful in the paleoenvironment. γ-Cerane coeluted with 3β(CH 3),17α(H),21β(H)-hopane, but α-values could be determined after deconvolution. γ-Cerane ( σ ≈ −25‰) probably derives from a eukaryotic heterotroph grazing on primary materials, the latter compound ( σ ≈ −90‰) must derive from methanotrophic organisms. 13C contents of n-alkanes in bitumen differed markedly from those of paraffins generated pyrolytically. Isotopic and quantitative relationships suggest that alkanes released by pyrolysis derived from a resistant biopolymer of eukaryotic origin and that this was a dominant constituent of total organic carbon.

The pyrolysis reactions and jet fuel potential of a Green River shale oil

Oil shale deposits constitute a possible large reserve of oil stocks. The immense Green River shale deposits can potentially be used as a source of middle distillate fuels, such as jet fuel. A major requirement for the jet fuel distillation cut is a high (37%) n-alkane content. Quantities of n-alkanes in the Green River shale oil are insufficient to explain the observed amounts of n-alkanes in jet fuels made from this oil. To study the thermal chemistry of the Green River shale oil, it was separated into three fractions; a saturate, an aromatic, and a polar fraction by distillation and silica-gel desorption. The fractions were pyrolyzed for 15–120 min reaction time periods at temperature and pressure conditions similar to the refining process known as delayed coking. Each fraction was assayed by combined capillary column GC/MS for n-alkane and 1-alkene content. All fractions attained similar n-alkane + 1-alkene yields, with the saturate fraction giving the highest yield of aliphatic compounds.

Distribution of pentacyclic triterpenoids in Green River oil shale kerogen

Pentacyclic triterpenoids released from Green River kerogen by a low temperature, mild, stepwise oxidative degradation using sodium dichromate in glacial acetic acid have been investigated by high resolution gas chromatography and computerized gas chromatography-mass spectrometry. Three series of stereoisomeric hopanoic acids (C30–C33) were found based on their αβ, ββ, and βα configurations. In addition, the following compounds were tentatively identified: 29,30-bisnorhopanoic acid, 30-norhop-22-one, 22,29,30-trinorhopan-21-one, 3-hopanone, and 3-gammacerone. The distribution of isomeric hopanoic acids supports previous suggestions of an extremely mild thermal history of Green River kerogen. Bonding of these triterpenoids to kerogen is likely to occur through the terminal positions (e.g. positions 3, 21, 22, 30, 31, etc.). The results also provide further evidence in favor of the microbiological origin of at least part of the organic matter in Green River oil shale kerogen.

Nature of porphyrins in kerogen. Evidence of entrapped etioporphyrin species

Computerized capillary gas chromatography-mass spectrometry (GC-MS) was employed to investigate maleimides (1H-pyrrole-2,5-diones) produced from a controlled stepwise oxidation of bitumen-free kerogen samples isolated from Green River and Monterey oil shales. On the basis of the evidence obtained from the analysis of all fractions, it is suggested that etioporphyrin species are most likely entrapped in the molecular sieve type network of kerogen

Quantitative mineral distributions in Green River and Rundle oil shales

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTQuantitative mineral distributions in Green River and Rundle oil shalesG. Brons, M. Siskin, R. I. Botto, and N. GuvenCite this: Energy Fuels 1989, 3, 1, 85–88Publication Date (Print):January 1, 1989Publication History Published online1 May 2002Published inissue 1 January 1989https://doi.org/10.1021/ef00013a015RIGHTS & PERMISSIONSArticle Views182Altmetric-Citations8LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (553 KB) Get e-Alerts Get e-Alerts

CHARACTERISTICS OF PYROBITUMEN AND OIL OBTAINED FROM GREEN RIVER OIL SHALE PYROLYSIS

ABSTRACT Pyrobitumens and oils generated from the isothermal pyrolysis of Green River oil shale at 400° 425°, and 440° C for different times were characterized. Elemental contents, average molecular weights, and hydrocarbon contents were determined for the pyrobitumens and oils. The pyrobitumens, a major initial pyrolysis product, had an average molecular weight exceeding 1200 and contained about 85% polars. The atomic hydrogen-to-carbon ratio, nitrogen content, and average molecular weight of the pyrobitumens changed with pyrolysis temperatures and times. The variable composition of the pyrobitumens suggests that pyrobitumen should not be considered as a single intermediate for kerogen decomposition. In contrast, oils contained 60% hydrocarbons and had a constant atomic hydrogen-to-carbon ratio and average molecular weight of about 250. However, the nitrogen content of the oils increased with increasing reaction time. The ratios of normal heptadecane/ pristane and normal octadecane/phytane, and odd-even predominance of oils were sensitive to pyrolysis temperatures and times. The rate constants, frequency factors, and activation center, for funding this work under cooperative Agreement Number DE-FE21-86MC11076.

Particle size reduction studies on Green River oil shale

Essais de reduction de la dimension des particules de schiste bitumineux de Green River par traitement a 60°C dans differents solvants aqueux de facon a ramollir et a creer une porosite dans le schiste avant la recuperation de l'huile