Release of organic nitrogen compounds from Kerogen via catalytic hydropyrolysis

Abstract

High hydrogen pressure pyrolysis (hydropyrolysis) was performed on samples of solvent extracted Kimmeridge Clay Formation source rock with a maturity equivalent to ca. 0.35% vitrinite reflectance. We describe the types and distributions of organic nitrogen compounds in the pyrolysis products (hydropyrolysates) using GC-MS. Compounds identified included alkyl-substituted indoles, carbazoles, benzocarbazoles, quinolines and benzoquinolines. The distributions of the isomers of methylcarbazoles, C2-alkylcarbazoles and benzocarbazoles in the hydropyrolysates were compared to a typical North Sea oil. The hydropyrolysates compared to the North Sea oil, showed increased contributions from alkylcarbazole isomers where the nitrogen group is "exposed" (no alkyl substituents adjacent to the nitrogen functionality) and appreciable levels of benzo[b]carbazole relative to benzo[a]- and benzo[c]carbazoles. Hydropyrolysis is found to be an ideal technique for liberating appreciable quantities of heterocyclic organic nitrogen compounds from geomacromolecules. The products released from the immature Kimmeridge Clay are thought to represent a potential source of nitrogen compounds in the bound phase (kerogen) able to contribute to the free bitumen phase during catagenesis.