Determining quantity and quality of retained oil in mature marly chalk and marlstone of the Cretaceous Niobrara Formation by low-temperature hydrous pyrolysis

Low-temperature hydrous pyrolysis (LTHP) at 300°C (572°F) for 24 h released retained oils from 12- to 20-meshsize samples of mature Niobrara marly chalk and marlstone cores. The released oil accumulated on the water surface of the reactor, and is compositionally similar to oil produced from the same well. The quantities of oil released from the marly chalk and marlstone by LTHP are respectively 3.4 and 1.6 times greater than those determined by tight rock analyses (TRA) on aliquots of the same samples. Gas chromatograms indicated this difference is a result of TRA oils losing more volatiles and volatilizing less heavy hydrocarbons during collection than LTHP oils. Characterization of the rocks before and after LTPH by programmable open-system pyrolysis (HAWK) indicate that under LTHP conditions no significant oil is generated and only preexisting retained oil is released. Although LTHP appears to provide better predictions of quantity and quality of retained oil in a mature source rock, it is not expected to replace the more time and sample-size efficacy of TRA. However, LTHP can be applied to composited samples from key intervals or lithologies originally recognized by TRA. Additional studies on duration, temperature, and sample size used in LTHP may further optimize its utility.