Incorporation of wet gases to kerogen in petroleum formation and evolution

Abstract

The formation mechanism for thermogenic gas remains unresolved. Disputes are focused on: (1) stability barrier for decomposition of oil to gas and wet gas to methane, and (2) inconsistence in dryness ratio (C1/ΣC1–5) between gases produced in pyrolysis experiments and in natural reservoirs. Here, we demonstrate the variation trend of dryness ratio (C1/ΣC1–5) with temperatures and thermal stress levels, and the correlation of dryness ratios with the yields of liquid components (ΣC8+) in confined pyrolysis experiments (gold capsules) of twenty coals. At both heating rates of 2 and 20 °C/h, dryness ratios of gaseous hydrocarbons at first decrease, and then increase with increasing temperatures and thermal stress levels. Dryness ratios of produced gases can be very high in the range of 66.3–95.7 wt% at initial temperature about 334 °C and heating rate of 20 °C/h, corresponding to EASY%Ro 0.56. We suggest that these gases are not the original products released from kerogen, but have been altered via wet gas incorporation to kerogen. Larger oil molecules (C8+) are more competitive in incorporating to kerogen compared with wet gases, and therefore, prohibit wet gas incorporation, leading to the observed trend of gas dryness ratios with increasing temperature and maturity and the negative correlation between dryness ratios and the yields of liquid components (ΣC8+). The conflicting results between the yields and carbon isotopes of wet gases produced in the isothermal confined pyrolysis experiments for coal plus oil can be well interpreted using the reaction mechanism that wet gases incorporate to kerogen while oil components retard this incorporation. Once free oil and wet gas molecules are reincorporated to kerogen, the bound molecules can easily decompose to smaller molecules due to substantial reduction of activation energy for carbon-carbon bond rupture. Petroleum formation from kerogen can be a recycling process: kerogen first releases oil compounds, and then free molecules reincorporate to kerogen and further decompose to smaller molecules, and finally to methane.