Composition, peat-forming vegetation and kerogen paraffinicity of Cenozoic coals: Relationship to variations in the petroleum generation potential (Hydrogen Index)

Abstract

Coals with similar thermal maturity and from the same deposit normally show a considerable range in petroleum generation potential as measured by the Hydrogen Index (HI). This variation may partly be related to variations in plant input to the precursor mires and organic matter preservation. It is widely accepted that some Cenozoic coals and coaly sediments have the potential to generate oil, which is related to the coal's paraffinicity. Coal paraffinicity is not readily reflected in the bulk HI. In this paper, the relationships between measured HI and coal composition, coal kerogen paraffinicity and floral input have been investigated in detail for three sets of coals from Colombia/Venezuela, Indonesia, and Vietnam. The samples in each coal set are largely of iso-rank. The petroleum generation potential was determined by Rock–Eval pyrolysis. Reflected light microscopy was used to analyse the organic matter (maceral) composition and the thermal maturity was determined by vitrinite reflectance (VR) measurements. The botanical affinity of pollen and spores was analysed by palynology. Coal kerogen paraffinicity was determined by ruthenium tetroxide-catalysed oxidation (RTCO) followed by chain length analysis and quantification (mg/g TOC) of the liberated aliphatic chains. The coals are dominated by huminite, in particular detrohuminite. Only the Vietnamese coals are rich in microscopically visible liptinite. The pollen and spores suggest that the coals were derived principally fromcomplex angiospermmire vegetations, with subordinate proportions of ferns that generally grew in a subtropical to tropical climate.Measured HI values vary considerably, but for the majority of the coals the values lie between approximately 200 mg HC/g TOC and 300 mg HC/g TOC. Aliphatics yielding monocarboxylic acids dominate in the coal kerogen, whereas aliphatics yielding dicarboxylic acids are secondary. However, the dicarboxylic acids show that crosslinking long-chain aliphatics are present in the kerogen structure. All studied coals are paraffinicwith C19–35 aliphatic chains in the kerogen, and the aliphatics in the range C25–35 show that the coals may have the potential to generate waxy crude oil. The Indonesian coals are richest in long-chain aliphatics and are thus potentially most oil-prone. Multivariate statistical analysis shows that for the present three sample sets variations in HI are positively correlated to different combinations of the C10+ aliphatic chains in the kerogen and the amount of detrohuminite + liptodetrinite and liptinite. Furthermore, part of the HI can be attributed to hydrogen in compounds with less than 10 carbon atoms, which is the lowest alkyl detected by RTCO analysis, thus representing a potential for generation of gas and light liquid hydrocarbons. The measured HI is therefore not always a good indicator for humic coal's potential to source waxy oil. Vegetational influence (palynology) on the variation of HI cannot be shown within the investigated span of variance and for the present coals. However, it is likely that some of the range in measured HI values is caused by floral vairiations not revealed by the palynological analysis and to variations in the preservation of the organic matter. (Less)