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Original Article | Open Access

Establishing credible reaction-kinetics distributions to fit and explain multi-heating rate S2 pyrolysis peaks of kerogens and shales

DWA Energy Limited, Lincoln, United Kingdom
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Abstract

Extracting reaction-kinetic distributions, in terms of activation energies ( E) and pre-exponential factors ( A), from the S2 peak data generated by pyrolysis tests conducted at three or more distinct heating ramps, is a well-established technique. These reaction-kinetics distributions are of paramount importance in establishing the timing and degree of petroleum generation from shales undergoing a range of burial and thermal histories. A commonly adopted approach is to determine and define reaction kinetics using a derivative of the Arrhenius equation configured in terms of a fixed/constant A value. Although the fixed- A approach can obtain good fits to multi-rate pyrolysis data, here it is shown that a formulation of the Arrhenius equation that involves reactions with a range of E and A values provides equally good fits to the multi-rate pyrolysis data. Moreover, the kinetic distributions with variable E- A provide more credible reaction kinetics consistent with those established for a range of kerogen types known for decades.

To establish accurate fits to multi-rate pyrolysis S2 peak data at 1 ℃ intervals from 250 to 700 ℃ an optimizer is applied to the preferred Arrhenius equation formulation to derive reaction increments and transformation fractions to a range of reaction kinetics ( E- A pairs). The methodology applied involves two steps: Step 1 finds the single E- A pair that best matches the S2 peak temperatures (three or more for multi-rate pyrolysis data); step 2 uses the E- A pair from step 1 as its modal focus and fits the full S2 peak shape using a distribution of 11 distinct reaction. This approach can replicate the fixed- A approach but is best applied using reactions with variable E- A values. The results of applying this method to multi-rate pyrolysis data for ten published kerogens and shales show credible kinetic distributions spread along the established E- A trend for kerogen/shales.

Keywords

Kerogen-kinetics distributionspyrolysis S2-peak shape analysismixing kerogen kineticsmulti-versus single-heating rate kineticscase for varying A pre-exponential factorapplying optimizers to derive kineticdistributions

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Advances in Geo-Energy Research
Volume 3 Issue 1,
March 2019
Pages 1-28
DOI: 10.26804/ager.2019.01.01
Cite this article:
Wood DA. Establishing credible reaction-kinetics distributions to fit and explain multi-heating rate S2 pyrolysis peaks of kerogens and shales. Advances in Geo-Energy Research, 2019, 3(1): 1-28. https://doi.org/10.26804/ager.2019.01.01

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Received: 18 July 2018
Revised: 23 August 2018
Accepted: 24 August 2018
Published: 01 September 2018
© The Author(s) 2019

This article is distributed under the terms and conditions of the Creative Commons Attribution (CC BY-NC-ND) license, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
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