Effects of thermal maturation on steroid hydrocarbons as determined by hydrous pyrolysis of Phosphoria Retort Shale |
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| Affiliation: | 1. Amoco Production Company Research Center P.O. Box 3385, Tulsa, OK 74102, U.S.A.;2. Continental Shelf Institute, Trondheim, Norway;1. State Key Laboratory of Petroleum Resources and Prospecting, China University of Petroleum (Beijing), Beijing 102249, PR China;2. College of Geoscience, China University of Petroleum (Beijing), Beijing 102249, PR China;3. The Institute for Geoscience Research (TIGeR), Department of Applied Geology, Curtin University, GPO Box U1987, Perth, Western Australia 6845, Australia;4. The School of Earth Science and Resources, Chang’an University, Xi’an 710054, China;1. State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Institutions of Earth Science, Chinese Academy of Sciences, Guangzhou 510640 China;2. CAS Center for Excellence in Deep Earth Science, Guangzhou 510640, China;3. University of Chinese Academy of Sciences, Beijing 100049 China;4. Petro Bio Oil Consulting, Tallahassee, FL 32312, United State;5. Department of Chemical and Biomedical Engineering, Florida A & M University/Florida State University, Tallahassee, FL 32310, United States;6. State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing 102249, China;1. Geological Survey of Canada, 3303 33rd Street, NW, Calgary, Alberta, Canada;2. Research Institute of Petroleum Exploration and Development, PetroChina, Beijing, China |
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| Abstract: | Hydrous pyrolysis experiments on the Phosphoria Retort Shale generate bitumen extracts and expelled oils that have steroid hydrocarbons with m/z 217-, 231-, and 253-mass Chromatographic distributions that are similar to those of bitumens and crude oils in the natural system. These experiments agree with the natural observations that diasteroid hydrocarbons increase relative to their regular counterparts with increasing thermal stress, while their C27 through C29 proportionality shows a slight enrichment in C27. Relative concentrations of 20S to 20R configurations of 24-ethyl-14α,17α-cholestane show the expected increase with increasing thermal stress into the early part of the primary oil generation stage, but thereafter decrease with increasing thermal stress. If this reversal is found in high maturity sections of the natural system, the utility of this transformation as a maturity index will be limited. Triaromatic- to monoaromatic-steroid hydrocarbon concentrations increase with increasing thermal stress as observed in the natural system. Preferred migration of monoaromatic steroid hydrocarbons from bitumen extracts to expelled oils places considerable doubt on currently employed kinetic models for this aromatization reaction. As in the natural system, the experiments show relative concentrations of low-molecular weight- to high-molecular weight-triaromatic steroid hydrocarbons to increase with increasing thermal stress. Assuming a first-order reaction rate, the apparent activation energy and pre-exponential factor for this apparent side-chain cleavage reaction are 175.59 kJ mol−1 and 2.82 × 1013 hr−1, respectively. These kinetic parameters are geologically reasonable and are similar to those for the overall generation of expelled oil. |
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