Modelling isotope fractionation during primary cracking of natural gas: a reaction

kinetic approach

‫سيف عبد الحق‬

Abstract

A numerical model has been developed to compute stable carbon isotope variations
in natural gas methane. calculating ch4 generation as a set of parallel first-order
reactions of primary cracking. The goal of this work was to combine the
description of isotope fractionation with established kinetic models for gas
generation. Stable carbon isotope ratios of methane from sedimentary organic
matter are characterized by the initial carbon isotope ratio of methane precursors
within the organic matter and by a constant difference in activation energy between
12C- and 13C-methane generation from corresponding precursor sites. Methane
generation is calculated separately for 12C- and 13C-methane.

Introduction

Stable isotopes of natural gas components have been used to identify source rocks
and to recognize possible secondary alterations of the gas.. Since these early
milestones a variety of such empirical relationships has been developed serving as
important tools to solve applied geological problems Faber, 1987; Berner and
Faber, Ž 1988; Shen et al., 1988; Berner, 1989 . However, . these models have
severe limitations, because they are not based on a fundamental understanding of
what controls isotopic fractionation and are therefore not generally applicable to all
types of sedimentary basins, source rocks, and thermal histories. Rate coefficients
of chemical reactions are usually strongly temperature-dependent. If k 12 and k 13
have even slightly different temperature dependences, then, according to Eq. 1 the
KIE will also be Ž . temperature-dependent. Based on experimental evidence from
non-isothermal open system pyrolysis we present a conceptual model which
explicitly takes into account the temperature dependence of the KIE. In this context
it was our main objective to combine the reaction kinetic fractionation concept for
a set of parallel first-order reactions

Temperature dependence of reaction rate and KIE

Isotope values of methane measured during open-system pyrolysis experiments can
be explained by temperature-dependent kinetic isotope fractionation from a set of
parallel first-order reactions with assumed equal initial carbon isotope
compositions of methane precursors.The best match between measured carbon
isotope ratios of methane generated during open-system pyrolysis experiments and
model predictions was obtained by applying a difference in activation energy
between 12C- and 13C-methane generation of rock samples. This difference in
activation energy was assumed to be equal for all parallel reactions
Conclusion

Isotope values of methane measured during open-system pyrolysis experiments can

be explained by temperature-dependent kinetic isotope fractionation from a set of
parallel first-order reactions with assumed equal initial carbon isotope
compositions of methane precursors. The best match between measured carbon
isotope ratios of methane generated during open-system pyrolysis experiments and
model predictions was obtained by applying a difference in activation energy .