Gas generation and intramolecular isotope study in laboratory pyrolysis of the Springfield coal from the Illinois Basin

Li, Xiaoqiang; Mastalerz, Maria; Horita, Juske

doi:10.1016/j.orggeochem.2022.104466

Gas generation and intramolecular isotope study in laboratory pyrolysis of the Springfield coal from the Illinois Basin

Journal Article · Sat Jul 16 00:00:00 EDT 2022 · Organic Geochemistry

DOI:https://doi.org/10.1016/j.orggeochem.2022.104466· OSTI ID:1977526

Li, Xiaoqiang ^[1]; Mastalerz, Maria ^[2]; Horita, Juske ^[3]

Texas Tech Univ., Lubbock, TX (United States); OSTI
Indiana Univ., Bloomington, IN (United States)
Texas Tech Univ., Lubbock, TX (United States)

Position-specific (PS) isotopes of propane have been proposed as a potential geochemical tool to decipher various geological processes (e.g., thermal cracking, biodegradation, H exchange) in natural reservoirs. The limited studies have been conducted on the PS isotopes of propane from the pyrolysis gases from marine shales, and natural gases sourced from lacustrine and marine kerogens, but little is known on gases produced from the humic kerogen. Here, this study investigated the PS δ¹³C of propane in the closed-system pyrolysis of the Springfield coal, Illinois Basin, Indiana, at 310 to 470 °C (Easy %Ro: 0.76 to 3.07). The C kinetic isotope effect (KIE) of CH₄ produced in both this study and previous low-temperature pyrolysis of the same coal indicates the cleavage of C—O bonds is the main generation pathway at the early kerogen cracking stage, followed by the breakdown of alkyl groups. At the wet-gas cracking stage, C₃H₈ production from thermally stable compounds has a significant influence on the bulk and position-specific C KIE in the pyrolysis of marine Woodford kerogen and Springfield coal. According to the PS δ¹³C of propane, the central site is likely more enriched in ¹³C and the δ¹³C of the terminal site is relatively heterogeneous within the propyl group attached to different functional groups of the gas-prone kerogen. Our findings based on the pyrolysis experiments and natural gas samples indicate thermal cracking and biodegradation appear to alter the δ¹³C_cen values more significantly than the δ¹³C_ter values of propane. The larger magnitude of ΔC_c-t in the kMC simulations (Peterson et al., 2018) compared with those from the marine shale and coal possibly implies the non-random distributions of ¹³C of propane precursors in the kerogens. As a new dimension of intramolecular isotopic information of propane, the PS δ¹³C values can contribute to fingerprinting the gas origins and identifying the various geological processes (e.g., kerogen cracking, wet-gas cracking, microbial activities) in sedimentary basins.

View Accepted Manuscript (DOE)

Research Organization:: Texas Tech Univ., Lubbock, TX (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: SC0016271

OSTI ID:: 1977526

Journal Information:: Organic Geochemistry, Journal Name: Organic Geochemistry Journal Issue: C Vol. 171; ISSN 0146-6380

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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