Green River Oil Shale Research Articles

Hydrocarbons from non-marine source rocks

Non-marine source rocks make a significant contribution to the world's oil reserves. They are particularly important as source rocks in China, Australia, New Zealand and Indonesia. Non-marine, mainly lacustrine oil shales from deposits in a number of locations were collected for study. Samples from Thailand (Mae Sot and Mae Moh), Yugoslavia (Aleksinac), U.K. (Lothians, Caithness Bituminous Flagstone, Brora, Skye) and France (Autun) were analysed. In addition, coals from the Mahakam Delta in Indonesia and from Australia and some Boghead coals from a number of deposits were also analysed along with Green River and Messel shale samples for comparison. Hydrocarbon characterisation was performed mainly by thermal extraction and pyrolysis-gas chromatography. Gas chromatography of oils produced by hydrous pyrolysis was also performed. Estimation of maturity was based mainly on vitrinite reflectance and spore fluorescence. There are considerable differences in hydrocarbons produced by pyrolysis of the samples from the different deposits. Paraffinic hydrocarbons are generated in abundance by all samples. In the boghead coals hydrocarbons are mostly paraffinic. In the “humic” coals aromatics are as prominent as paraffinic hydrocarbons. In the lacustrine shales and carbonates paraffinic and isoprenoid hydrocarbons vary in abundance and isoprenoids are very abundant in some of the carbonates. The thermal extracts indicate that in most cases hydrocarbon generation has not started. The presence of a number of homologous series in some of the immature lacustrine samples is interpreted to be related to the abundance of alginite. The early generation of acyclic isoprenoid hydrocarbons as well as aromatics relative to straight chain hydrocarbons is indicated by the hydrous pyrolysis results. In the case of the Green River oil shales it may be an additional reason for the lack of n-alkanes in early migrated bitumens found in the Green River Basin area along with biodegradation.

Novel identification of 17.beta.(H)-hopanoids in Green River oil shale kerogen

Novel identification of 17.beta.(H)-hopanoids in Green River oil shale kerogen

Isolation and identification of carboxylic acid salts as major components of Green River oil shale

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTIsolation and identification of carboxylic acid salts as major components of Green River oil shaleJ. F. McKay and M. S. BlancheCite this: Energy Fuels 1987, 1, 6, 525–529Publication Date (Print):November 1, 1987Publication History Published online1 May 2002Published inissue 1 November 1987https://doi.org/10.1021/ef00006a012RIGHTS & PERMISSIONSArticle Views146Altmetric-Citations3LEARN 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 (651 KB) Get e-Alerts Get e-Alerts

Simulated weathering of oil shales from Rundle, Julia Creek and Green River: Effects on oil yields and kerogen composition

An attempt has been made over 60 weeks to simulate experimentally the weathering of Rundle, Julia Creek and Green River oil shales. Finely-ground shales were subjected to three types of ‘weathering’: 1. (1) 22 °C in air without water or sunlight (‘internal’ conditions) 2. (2) 10–35 °C under water with sunlight (‘external’ conditions) 3. (3) 100 °C in air without water or sunlight (‘extreme’ conditions). All shales exhibited decreases in oil yields by Fischer assay, the highest loss being 90 wt % for Julia Creek shale under extreme conditions for 60 weeks. Solid-state 13C n.m.r. spectra of kerogens before and after weathering under extreme conditions for 60 weeks confirm increased aromaticity and greater concentrations of oxygenated functional groups. Elemental analyses show that, for these kerogens, H/C ratios decreased by ≈ 30% and O/C ratios increased by ≈ 300%. The results are important when considering natural geological weathering of shale seams, oxidation of stockpiled shale and prolonged drying of shale at elevated temperatures.

INTERACTION OF SUPERCRITICAL METHANOL AND WATER WITH ORGANIC MATERIAL IN GREEN RIVER OIL SHALE

ABSTRACT A series of experiments to study the interaction of supercritical methanol and water with Green River oil shale was performed. The volume percentage of methanol (CH30H) in water was varied. The temperature was held constant at 400°C. The products were fractionated and characterized with infrared spectroscopy and elemental analyses. A 13CH30H experiment was carried out and 13C nuclear magnetic resonance (NMR) analysis was used to prove the incorporation of methanol into the products. The methyl esters resulting from the incorporation were isolated and characterized by high resolution mass spectrometry. The experiments on a model compound and gas chromatographic/mass spectral (GC/MS) analysis of the product showed that methanol can react with carboxylic acids found in Green River oil shale to form methyl esters. However, this incorporation of methanol into the product oil from supercritical fluid extraction was found to be not sufficient to account for the increased oil yields, The role of methanol...

The effects of pyrolysis conditions on Israeli oil shale properties

This paper reports on a study which was undetaken to identify the influence of pyrolysis parameters on the qaulity and quantity of oil from the EF'E oil shale deposit in Israel. Pyrolysis experiments were performed in three reactors which allowed variations in heating rate, bed geometry, pressure, temperature, and residence time of the pyrolysis products. These parameters were varied in a series of pyrolysis tests to identify the controlling mechanisms. The pyrolysis results indicate that high oil yields can be achieved with proper process conditions. Secondary reactions of the oil (cracking and coking) are both minimized when temperature and residence time for oil in the reaction zone are kept to a minimum. When the oil remains in the hot zone, such as in the Fischer Assay, cracking lowers the oil yield and increases light hydrocarbon gases. In addition secondary reactions increase the aromaticity, decrease the nitrogen and increase the sulphur content of the oil. All evidence suggests that the Israeli shale oil is more prone to cracking than a Colorado Green River shale oil on which similar tests were performed. The average molecular weight of the Israeli oil is lower, the rate of evolution is higher and the Fischer Assay oil yield is lower.

Structure of Green River oil shale kerogen: Determination using solid state 13C n.m.r. spectroscopy

A sample of kerogen isolated from a Green River oil shale has been examined using high resolution solid state 13C n.m.r. spectroscopy. The relative concentrations of carbon types have been determined using a novel peak-synthesis technique applied to the 13C spectra. This technique has been successfully applied in determining the amount and type of individual carbon atoms in a sample of Green River oil shale kerogen, with sufficient resolution to enable an average structure to be proposed. The kerogen is highly aliphatic and appears to contain substantial quantities of both saturated polycondensed ring structures, and long chain n-alkanes or n-alkyl substituents.

Identification of arsenic-bearing minerals in a sample of Green River oil shale

The distribution of arsenic among the various components of a sample of Green River oil shale was investigated. Scanning electron microscopy with X-ray microanalysis, powder X-ray diffraction and inductively coupled plasma atomic emission spectrometry were used for identification. Approximately 65% of the total arsenic was found to be present as skutterudite, (Co,Fe,Ni)As 3, and safflorite, (Co,Fe)As 2. The presence of these minerals in oil shales has not been previously reported.

High temperature simulation of petroleum formation—IV. Stable carbon isotope studies of gaseous hydrocarbons

Laboratory simulations of petroleum formation were examined by stable carbon isotope studies of five cryogenic distillation fractions of the gases produced by thermal treatment of organic substrates. Simple heat treatment (pyrolysis) of substrates was contrasted with heat treatment in the presence of nickel and vanadium sulfides, ammonia, and water (catalysis). The effect of substrate/catalyst ratio on the isotopic composition of gases was also examined. All reactions were carried out at 440°C, and ambient pressure. Plots of stable carbon isotope ratio versus distillation temperature, for substrates representing marine and terrestrial organic matter, were compared to literature values for natural petroleum accumulations, and to the pyrolysis of Green River oil shale.

Trace elements in oil shales, their source and organic association with particular reference to Australian deposits

Transmission electron microscopy (TEM) of organic concentrate, trace-element analysis and C-isotope analysis have been used in an attempt to determine the source of particular trace elements. It has been shown that Cu was occasionally concentrated in bacterial cell walls in the Toolebuc oil shales whereas V was mostly associated with the inorganic fraction. High concentrations of Mo may have their origin in N-fixing cyanobacteria which are probably major contributors to the organic matter in these oil shales. High concentrations of Ti in the Rundle-Condor oil shales are associated with the humic acid fraction. The latter are shown to be of a terrigenous-allochthonous source. High Ti-Cr concentrations in the Green River oil shale are also associated with the humic acids. Ti in higher than average concentrations is found in oil shales of lacustrine environment whereas high V content is typical of marine-deposited oil shales.

Application of dielectric spectroscopy to chemical characterization of oil shales

Simple models to predict the variation of dielectric parameters for Green River oil shale with selected variables, are presented. The relative dielectric constant, ε′, was chosen as a representative parameter for these computations. A composite ε′ value was derived for the shale matrix while simultaneously varying shale organic content, moisture content, porosity and mineral composition. Both linear and logarithmic averaging methods were utilized to arrive at these composite ε′ values. In addition, the influence of organic pyrolysis and thermal alterations in the mineral matrix on the composite ε′ value for the shale matrix, were considered. Comparison with experimental results are presented where possible. The utility of these model predictions for assay and diagnostic applications in oil shale technology is described.

The Domino Theory of steam gasification of spent shale

This Paper reports a study of the chemistry which occurs during the steam gasification of spent (i.e. retorted) Green River oil shale. The results suggest that in the presence of steam there is an unusual and strong coupling between the decomposition of the inorganic carbonates, the gasification of organic carbon by steam, and the removal of nitrogen from the shale.

A comparison of the dissolution of model compounds and the kerogen of Green River oil shale by oxidation with perchloric acid — A model for the kerogen of Green River oil shale

A stepwise degradation of a kerogen concentrate of Green River oil shale was effected by oxidation with perchloric acid of varying boiling point and concentration. Dissolution of the kerogen concentrate occurred between 160 and 170°C. Several model compounds were also oxidized with perchloric acid. The model compounds were polyethylene, graphite, nylon, and polyethylene oxide. The results indicated that the kerogen was similar to polyethylene oxide. The results of this study and previous work were used to present a model for the structure of the kerogen of Green River oil shale.

The oxidation of green river oil shale with perchloric acid Part I — The reaction of green river oil shale with perchloric of varying concentration and boiling point

A kerogen concentrate of Green River oil shale was prepared. The kerogen concentrate and the raw oil shale from which the kerogen concentrate was prepared were oxidized with perchloric acid of varying boiling point, concentration and oxidizing ability. The reaction was studied with reference to the percentage carbon converted to carbon dioxide, the color of the aqueous phase, and the amount of undissolved material. The results indicated that the presence of the silicate mineral structure had no effect on the oxidation of the organic material. A stepwise oxidation of the kerogen of Green River oil shale was effected by varying the reduction potential of the oxidizing agent, perchloric acid. Soluble oxidation products, suitable for subsequent analysis, were produced.

The oxidation of green river oil shale with perchloric acid part II — The analysis of oxidation products

A stepwise oxidation of a kerogen concentrate of Green River oil shale was effected by varying the potential of the oxidizing agent, perchloric acid. Perchloric acid-free oxidation products were isolated and analyzed. The oxidation products were analyzed by titration with standard base, infrared spectrophotometry, mass spectroscopy, X-ray excited optical luminesence, and gas chromatography. The major oxidation product was a mixture of brown, high molecular weight, carboxylic acids. Analysis indicated these acids consisted primarily of aliphatic materials containing both saturated carbon chains and cyclic compounds. Ether groups were indicated. Aromatic material and long-chain fatty acids were also isolated in low relative concentration. A comparison was made between the results of this study and the results of previous workers.

ANALYSIS OF ORGANIC MATERIAL DIFFICULT TO RECOVER FROM OIL SHALE

Green River oil shale was supercritically treated with methanol and water and then extracted with benzene and methanol to recover approximately 85% of the organic matter in the shale. The spent shale was then extracted with pyridine to recover an additional 2-3% of the organic matter that remained on the shale. The liquid organic material extracted with pyridine contained some of the compound types most difficult to recover from shale. These materials were characterized. High-molecular nitrogen compounds of the pyridine type were found to be a predominant compound class in the pyridine extract. The pyridine-extracted material contained a higher percentage of nitrogen than a Fischer assay oil and a lower percentage of hydrogen than a Fischer assay oil indicating that more aromatic nitrogen compounds were present in the pyridine extract than in Fischer assay oil. Bonding mechanisms between organic and inorganic components of the shale were studied as were spectroscopic data showing the nature of the organic material remaining on spent shale after extraction with pyridine. 22 references, 5 figures, 3 tables.

Trace and minor elements in Green River oil shale (Colorado, U.S.A.), concentrated by differential density centrifugation

A combination of separatory and analytical techniques was used to investigate the chemistry of 3 major elements and 9 trace elements in fine-grained Colorado oil shale. The separatory procedure involved low-temperature ashing, followed by high-speed centrifugation in a liquid density-gradient column. The density gradient ranged from 2.0 to 2.9 g cm −3. Application of this combination of techniques to four samples of oil shale demonstrates the feasibility of separating micrometer-size mineral grains held tightly by carbonates and organic matter. We have defined the “maximum enrichment factor” as being the ratio of the maximum observed concentration of an element in a given density fraction of ashed sample to the concentration of the same element in the bulk ashed sample. Resulting values of the maximum enrichment factors range from 1.2 to 12 for various elements. Hierarchial cluster dendrograms reveal different mineralogical residences for the elemental groupings of: Ca-Fe-Mn; Cu-Pb-Ni; As-Zn; and Mo-F-K-Fe. Fluorine is concentrated in the 2.4- and 2.5-g-cm −3 fractions, in association with illite.

Acid dissolution of mineral matrix in Green River oil shale

The mineral matrix in Green River oil shale was partially removed by treatment with dilute HCl. The major ionic species in the solution from acid treatment (AT) were identified as Na +, Al 3+, Fe 2+, Mg 2+, and Ca 2+. The ion yields expected from reaction stochiometry, gravimetric analyses and comparison of calculated CO 2 yields with measured levels were consistent with the fact that Na + and Al 3+ originated primarily from analcite: Fe 2+ and Mg 2+ from dolomitic ankerite and Ca 2+ from both dolomitic ankerite and calcite. Temperature and shale particle size were important parameters in the efficacy of AT. An increase in temperature and a decrease in particle size increased the rate of mineral dissolution. Fe 2+ showed an anomalous trend in that the rate initially declined with increasing temperature after which it showed the usual increase with temperature. The kinetics of ion build-up in the solution from AT were analysed in detail for the case of Al 3+. The Arrhenius expression was found to be valid only for finer particle sizes (e.g., −35, +45 US mesh shale). A simple model is finally presented to account for the combined effect of temperature and shale particle size on mineral dissolution rates.

Acid dissolution of mineral matrix in Green River oil shale.: 2. Effect of ultrasonic field

An ultrasonic field was found to enhance the rate of mineral dissolution from Green River oil shale matrix when treated with dilute HCl. This effect was most pronounced forcoarse particles and minimal for finely pulverized shale. Data comparing the behaviour in an ultrasonic field with control specimens are presented in terms of gas evolution profiles, ion concentrations and gravimetric analyses.

A method for the isolation of kerogen from Green River oil shale

Presentation d'une methode combinant plusieurs techniques physiques et chimiques pour l'isolement du kerogene des schistes bitumineux. Analyse elementaire du kerogene isole par cette methode a partir d'un schiste bitumineux de la Formation Green River