Hydrous pyrolysis of New Albany and Phosphoria Shales: production kinetics of carboxylic acids and light hydrocarbons and interactions between the inorganic and organic chemical systems

Hydrous pyrolysis in flexible gold-bag autoclaves was used to study the production of carboxylic acids and light hydrocarbons from two marine type IIb source rocks (New Albany and Phosphoria Shales). Kerogen pyrolysis produced significant amounts of the monocarboxylic acids (acetic>propionic>butyric). The gases were dominated by CO2 and methane, in that order, and progressively smaller amounts of the alkanes (ethane>propane>butane>pentane). Kinetic analyses of production rates for the New Albany Shale suggest mean activation energies (E) of 51–54 kcal/mol for both the light hydrocarbons and acids. Pressure had little effect on measured production rates for either shale over the pressure range investigated. Chemical thermodynamic speciation modeling suggests that in these experiments metal–organic acid anion complexation had little impact on aluminum speciation/solubility, but was important with respect to the alkaline earths.