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<p>Pyrolysis curves representing product quantities generated from shale and coal samples subjected to stepped heating ramps can be simulated by combinations of first-order Arrhenius reactions. The simulated curves closely match those of shales when using Arrhenius-equation integrals of activation energies (<i>E</i>) and frequency factors (<i>A</i>) allowed to vary along the trend <i>E</i> = 5.479<i>lnA</i>-119.283. 1928 simulations are evaluated for 6 distinctive heating ramps. The reaction distributions in those simulations are centred at <i>E</i> values between 105 and 345&#xa0;kJ/mol with the peak <i>E</i> values varying by 1&#xa0;kJ/mol for the simulated pyrolysis responses (referred to as simulated pyrograms) and cumulate transformation-factor (<i>∑TF</i>) curves, are compared to reaction-kinetic distributions fitted to the multiple-heating-rate recorded pyrolysis responses (referred to as recorded pyrograms) of real shale samples. The differences between the S2-peak temperatures generated by two different heating ramps and the peak <i>E</i> values of the kinetic distributions show good agreement between the simulated and real shale reaction-kinetic <i>A-E</i> values. However, the temperature differences between different <i>∑TF</i> fractions are substantially greater for real shales compared to the simulated reaction-kinetic distributions, making them less useful for <i>E-A</i> prediction purposes. The involvement of bitumen and kerogen reaction residues in real shales as well as unreacted kerogen of multiple compositions is the most likely explanation for such differences. The <i>E</i> and <i>A</i> weighted-mean and weighted-standard-deviation values of the reaction distributions fitted to recorded shale pyrograms are useful metrics to characterize and distinguish shale samples. These values identify appropriate shale samples to derive reaction kinetics for basin modelling to establish the temperature and timing intervals of petroleum generation. They also assist in identifying shale zones likely to be associated with high resource capacities and micropore developments suitable for gas (CH<sub>4</sub>, CO<sub>2</sub>, H<sub>2</sub>) storage.</p>

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Simulating reaction-kinetic distributions across a range of activation energies and frequency factors with relevance to shale exploitation

  • 期刊论文

  • 发表日期：

    2026年3月1日

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  • David A. Wood

摘要

Pyrolysis curves representing product quantities generated from shale and coal samples subjected to stepped heating ramps can be simulated by combinations of first-order Arrhenius reactions. The simulated curves closely match those of shales when using Arrhenius-equation integrals of activation energies (E) and frequency factors (A) allowed to vary along the trend E = 5.479lnA-119.283. 1928 simulations are evaluated for 6 distinctive heating ramps. The reaction distributions in those simulations are centred at E values between 105 and 345 kJ/mol with the peak E values varying by 1 kJ/mol for the simulated pyrolysis responses (referred to as simulated pyrograms) and cumulate transformation-factor (∑TF) curves, are compared to reaction-kinetic distributions fitted to the multiple-heating-rate recorded pyrolysis responses (referred to as recorded pyrograms) of real shale samples. The differences between the S2-peak temperatures generated by two different heating ramps and the peak E values of the kinetic distributions show good agreement between the simulated and real shale reaction-kinetic A-E values. However, the temperature differences between different ∑TF fractions are substantially greater for real shales compared to the simulated reaction-kinetic distributions, making them less useful for E-A prediction purposes. The involvement of bitumen and kerogen reaction residues in real shales as well as unreacted kerogen of multiple compositions is the most likely explanation for such differences. The E and A weighted-mean and weighted-standard-deviation values of the reaction distributions fitted to recorded shale pyrograms are useful metrics to characterize and distinguish shale samples. These values identify appropriate shale samples to derive reaction kinetics for basin modelling to establish the temperature and timing intervals of petroleum generation. They also assist in identifying shale zones likely to be associated with high resource capacities and micropore developments suitable for gas (CH4, CO2, H2) storage.