Single carbon surface reactions of 1-octadecene and 2,3,6-trimethylphenol on activated carbon: Implications for methane formation in sediments

Abstract

The reactions of a terminal alkene (1-octadecene) and a polymethyl phenol (2,3,6-trimethylphenol) on activated carbon have been investigated in closed system pyrolysis experiments in the temperature range 170-340 C. The reaction products of 1-octadecene included methane, isomeric octadecenes, methyl substituted alkanes, alkyl aromatics and an homologous series of n-alkanes with carbon numbers indicative of progressive single carbon depletion of the reactant. The reaction products of 2,3,6-trimethylphenol also contained methane, as well as C1-C4 methyl phenols produced by demethylation and methyl transfer reactions. A carbon surface reaction involving the formation of a reactive single carbon intermediate (i.e. methylene/carbene) is proposed. This reaction accounts for the products observed from the pyrolysis experiments and also is consistent with liquid hydrocarbon distributions found in petroleum basins. Methane was the dominant (ca. 85% of C1-C4) gaseous hydrocarbon product of 2,3,6-trimethylphenol but accounted for only ca. 17% of the C1-C4 hydrocarbons from 1-octadecene. These findings suggest that single carbon surface reactions may play an important role in the geochemical formation of crude oil and natural gas and that the composition of the source material and therefore the type of organic compounds undergoing such reactions, influences the hydrocarbon gas composition in sedimentary basins.