A chemical and thermodynamic model of oil generation in hydrocarbon source rocks

Thermodynamic calculations and Gibbs free energy minimization computer experiments strongly support the hypothesis that kerogen maturation and oil generation are inevitable consequences of oxidation/reduction disproportionation reactions caused by prograde metamorphism of hydrocarbon source rocks with increasing depth of burial.These experiments indicate that oxygen and hydrogen are conserved in the process.Accordingly, if water is stable and present in the source rock at temperatures ≳25 but ≲100 °C along a typical US Gulf Coast geotherm, immature (reduced) kerogen with a given atomic hydrogen to carbon ratio (H/C) melts incongruently with increasing temperature and depth of burial to produce a metastable equilibrium phase assemblage consisting of naphthenic/biomarker-rich crude oil, a type-II/III kerogen with an atomic hydrogen/carbon ratio (H/C) of ∼1, and water. Hence, this incongruent melting process promotes diagenetic reaction of detritus in the source rock to form authigenic mineral assemblages.However, in the water-absent region of the system CHO (which is extensive), any water initially present or subsequently entering the source rock is consumed by reaction with the most mature kerogen with the lowest H/C it encounters to form CO2 gas and a new kerogen with higher H/C and O/C, both of which are in metastable equilibrium with one another.This hydrolytic disproportionation process progressively increases both the concentration of the solute in the aqueous phase, and the oil generation potential of the source rock; i.e., the new kerogen can then produce more crude oil.Petroleum is generated with increasing temperature and depth of burial of hydrocarbon source rocks in which water is not stable in the system CHO by a series of irreversible disproportionation reactions in which kerogens with higher (H/C)s melt incongruently to produce metastable equilibrium assemblages consisting of crude oil, CO2 gas, and a more mature (oxidized) kerogen with a lower H/C which in turn melts incongruently with further burial to produce more crude oil, CO2 gas, and a kerogen with a lower H/C and so forth.The petroleum generated in the process progresses from heavy naphthenic crude oils at low temperatures to mature petroleum at ∼150 °C. For example, the results of Computer Experiment 27 (see below) indicate that the overall incongruent melting reaction in the water-absent region of the system C–H–O at 150 °C and a depth of ∼4.3 km of an immature type-II/III kerogen with a bulk composition represented by C292H288O12(c) to produce a mature (oxidized) kerogen represented by C128H68O7(c), together with a typical crude oil with an average metastable equilibrium composition corresponding to C8.8H16.9 (C8.8H16.9(l)) and CO2 gas (CO2(g)) can be described by writing equation(A) C292H288O12(c)(kerogen,H/C=0.99O/C=0.041)→1.527C128H68O7(c)(kerogen,H/C=0.53O/C=0.055)+10.896C8.8H16.9(l)(crude oil,H/C=1.92)+0.656CO2(g) which corresponds to a disproportionation reaction in the source rock representing the sum of a series of oxidation/reduction conservation reactions. Consideration of the stoichiometries of incongruent melting reactions analogous to Reaction (A) for reactant kerogens with different (H/C)s and/or atomic oxygen to carbon ratios (O/C)s, together with crude oil compositions corresponding to Gibbs free energy minima at specified temperatures and pressures permits calculation of the volume of oil (mole of reactant organic carbon (ROC))−1 that can be generated in, as well as the volume of oil (mol ROC)−1 which exceeds the volume of kerogen pore space produced that must be expelled from hydrocarbon source rocks as a function of temperature, pressure, and the H/C and O/C of the reactant kerogen. These volumes and the reaction coefficients (mol ROC)−1 of the product kerogen, crude oil, and CO2 gas in the incongruent melting reaction are linear functions of the H/C and O/C of the reactant kerogen at a given temperature and pressure. The slopes of the isopleths can be computed from power functions of temperature along a typical US Gulf Coast geotherm. All of these reactions and relations are consistent with the well-known observations that (1) the relative abundance of mature kerogen increases, and that of immature kerogen decreases with increasing burial of hydrocarbon source rocks and (2) that the volume of oil generated in a given source rock increases with increasing weight percent total organic carbon (TOC) and the H/C and (to a lesser extent) the O/C of the immature kerogen. They are also compatible with preservation of biomarkers and other polymerized hydrocarbons during the incongruent melting process. It can be deduced from Reaction (A) that nearly 11 mol of crude oil are produced from one mole of the reactant kerogen (rk), which increases to ∼39.5 mol (mol rk)−1 as the carbon content and H/C of the reactant kerogen increase to that in the hydrogen-rich type-I kerogen represented by C415H698O22(c). The secondary porosities created in source rocks by Reaction (A) and others like it are of the order of 75–80 vol % of the oil generated, which requires expulsion of the remainder, together with the CO2 gas produced by the reaction. The expulsion of the CO2 gas and excess crude oil from the hydrocarbon source rock is facilitated by their buoyancy and the fact that the pressure in the source rocks is ⩾ the fluid pressure in the adjoining formations during progressive generation of the volume of crude oil that exceeds the kerogen pore volume produced by the incongruent melting process. The expelled CO2 gas lowers the pH of the surrounding formation waters, which promotes the development of secondary porosity and diagenetic reaction of detrital silicates to form authigenic mineral assemblages. Hence, the expulsion process facilitates initial upward migration of the oil, which is further enhanced by expansion of the oil and its reaction with H2O at the oil–water interface to generate methane gas. Mass transfer calculations indicate that the minimal volume of crude oil expelled into these formations is comparable to, or exceeds the volume of oil produced and in proven reserves in major oil fields such as the North Sea, the Paris and Los Angeles Basins, and those in Kuwait, Saudi Arabia, and elsewhere in the Middle East. For example, taking account of the average weight percent (W%) organic carbon in the immature kerogen (3.4 wt%) with an average H/C of ∼1.04 in the hydrocarbon source rocks in Saudi Arabia, which have an average thickness of ∼43 m, it can be shown (see below) that all of the oil (and oil equivalent of natural gas) produced and in proven reserves in Saudi Arabia (374 billion barrels of oil or ∼1.9 million barrels of oil km−2) can be accounted for by minimal expulsion from the source rocks of oil generated at ∼125 °C solely by the incongruent melting process. Computer experiments indicate that this process can also account for all the petroleum that can be, and has been generated in the world’s hydrocarbon source rocks. Of the latter, as much as 75–80% may still remain in these rocks.