Effects of smectite on the oil-expulsion efficiency of the Kreyenhagen Shale, San Joaquin Basin, California, based on hydrous-pyrolysis experiments

Abstract

The amount of oil that maturing source rocks expel is expressed as their expulsion efficiency, which is usually stated in milligrams of expelled oil per gram of original total organic carbon (TOC O ). Oil-expulsion efficiency can be determined by heating thermally immature source rocks in the presence of liquid water (i.e., hydrous pyrolysis) at temperatures between 350°C and 365°C for 72 hr. This pyrolysis method generates oil that is compositionally similar to natural crude oil and expels it by processes operative in the subsurface. Consequently, hydrous pyrolysis provides a means to determine oil-expulsion efficiencies and the rock properties that influence them. Smectite in source rocks has previously been considered to promote oil generation and expulsion and is the focus of this hydrous-pyrolysis study involving a representative sample of smectite-rich source rock from the Eocene Kreyenhagen Shale in the San Joaquin Basin of California. Smectite is the major clay mineral (31 wt. %) in this thermally immature sample, which contains 9.4 wt. % total organic carbon (TOC) comprised of type II kerogen. Compared to other immature source rocks that lack smectite as their major clay mineral, the expulsion efficiency of the Kreyenhagen Shale was significantly lower. The expulsion efficiency of the Kreyenhagen whole rock was reduced 88% compared to that of its isolated kerogen. This significant reduction is attributed to bitumen impregnating the smectite interlayers in addition to the rock matrix. Within the interlayers, much of the bitumen is converted to pyrobitumen through crosslinking instead of oil through thermal cracking. As a result, smectite does not promote oil generation but inhibits it. Bitumen impregnation of the rock matrix and smectite interlayers results in the rock pore system changing from water wet to bitumen wet. This change prevents potassium ion (K + ) transfer and dissolution and precipitation reactions needed for the conversion of smectite to illite. As a result, illitization only reaches 35% to 40% at 310°C for 72 hr and remains unchanged to 365°C for 72 hr. Bitumen generation before or during early illitization in these experiments emphasizes the importance of knowing when and to what degree illitization occurs in natural maturation of a smectite-rich source rock to determine its expulsion efficiency. Complete illitization prior to bitumen generation is common for Paleozoic source rocks (e.g., Woodford Shale and Retort Phosphatic Shale Member of the Phosphoria Formation), and expulsion efficiencies can be determined on immature samples by hydrous pyrolysis. Conversely, smectite is more common in Cenozoic source rocks like the Kreyenhagen Shale, and expulsion efficiencies determined by hydrous pyrolysis need to be made on samples that reflect the level of illitization at or near bitumen generation in the subsurface.