Fuel, Vol.239, 804-813, 2019
Gas generation potential and processes of Athabasca oil sand bitumen from gold tube pyrolysis experiments
Gold-tube pyrolysis experiments were conducted on two oil sand bitumens (OSBs) from the top and bottom of the McMurray Formation in the Athabasca oil sand region of Alberta, Canada. Temperatures ranging from 300 degrees C to 650 degrees C and a pressure of 50 MPa with heating rates of 2 degrees C/h were used to investigate the gas generation behavior of OSB. The extractable residual bitumen content decreased systematically with increasing heating temperatures resulting in a continuous increase in total hydrocarbon gas yields with the highest value of about 480 mg/g bitumen at 650 degrees C. Among hydrocarbon gases, the yields of methane (C-1) increased consistently with experimental temperatures, while the yields of ethane (C-2), propane (C-3), butanes (i + n-C-4) and pentanes (i + nC(5)) increased initially to a critical pyrolysis temperature and then decreased at higher temperatures. Molecular indices (C-1/C-2, C-2/C-3, C-2/i-C-4, C-3/C-4, i-C-4/n-C-4, i-C-5/n-C-5 and C-1/Sigma C1-5) obtained in this work are different from typical primary thermogenic gases generated from kerogen or secondary thermogenic gases derived from thermal cracking of oil. Three stages of OSB thermal evolution were identified over a wide range of heating temperatures. The first stage (300-425 degrees C) reflects initial decomposition of thermally unstable moieties in resins and asphaltenes. Gas generated at this stage was dominated by carbon dioxide and hydrogen sulfide with minor amounts of hydrocarbon. Hydrocarbon gases were enriched in wet gas components with increasing heating temperatures. The second stage (425-525 degrees C) corresponds to liquid oil cracking and wet gas generation. While the yields of methane and ethane still increased with heating temperatures, yield of propane reached a maximum and yields of butane and pentane started to decline. The third stage (525-650 degrees C) reflects wet gas cracking and dry gas generation as indicated by the dramatic decrease of wet gas components and increase in gas dryness. Variations of gas yields and chemical compositions from two OSBs were partially caused by different levels of biodegradation. The top OSB has experienced less biodegradation influence than the bottom one as indicated by higher saturated and aromatic hydrocarbon contents and intact alkylphenanthrene distribution. Increased biodegradation of OSB yielded a higher concentration of polar compounds and an overall lower hydrogen content, which reduced the hydrocarbon gas generation potential. Slightly higher amounts of wet gas components were generated from the top OSB because of the relatively higher content of reactive moieties (mainly alkyl groups) at a lower biodegradation level, while a higher proportion of methane was observed from the bottom, severely biodegraded OSB that was enriched in cross linked ring structures.
Keywords:Gold-tube pyrolysis;Gas generation;Gas geochemistry;Athabasca oil sand bitumen;Biodegradation