Initial Stages of the Pyrolysis of Polyethylene
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Abstract
An
experimental study of the kinetics of the initial stages of
the pyrolysis of high-density polyethylene (PE) was performed. Quantitative
yields of gas-phase products (C<sub>1</sub>–C<sub>8</sub> alkanes
and alkenes) and functional groups within the remaining polyethylene
melt (methyl, vinyl, vinylene, vinylidene, and branching sites) were
obtained as a function of time (0–20 min) at five temperatures
in the 400–440 °C range. Gas chromatography and NMR (<sup>1</sup>H and <sup>13</sup>C) were used to detect the gas- and condensed-phase
products, respectively. Modeling of polyethylene pyrolysis was performed,
with the primary purpose of determining the rate constants of several
critical reaction types important at the initial pyrolysis stages.
Detailed chemical mechanisms were created (short and extended mechanisms)
and used with both the steady-state approximation and numerical integration
of the differential kinetic equations. Rate constants of critical
elementary reactions (C–C backbone scission, two kinds of H-atom
transfer, radical addition to the double bond, and beta-scission of
tertiary alkyl radicals) were adjusted, resulting in an agreement
between the model and the experiment. The values of adjusted rate
constants are in general agreement with those of cognate reactions
of small molecules in the gas phase, with the exception of the rate
constants of the backbone C–C scission, which is found to be
approximately 1–2 orders of magnitude lower. This observation
provides tentative support to the hypothesis that congested PE melt
molecular environment impedes the tumbling motions of separating fragments
in C–C bond scission, thus resulting in less “loose”
transition state and lower rate constant values. Sensitivity of the
calculations to selected uncertainties in model properties was studied.
Values and estimated uncertainties of four combinations of rate constants
are reported as derived from the experimental results via modeling.
The dependence of the diffusion-limited rate constant for radical
recombination on the changing molecular mass of polyethylene was explicitly
quantified and included in the extended kinetic mechanism, which appears
critical for the agreement between modeling and experiment, particularly
the agreement between the experimental and the calculated activation
energies for product formation rates. Calculations were performed
to estimate the contribution to the overall rate of radical recombination
of the “reaction diffusion” phenomenon, where recombination
is driven not by the actual motion of the recombining radical sites
but rather by the migration of the radical site through PE melt due
to rapid hydrogen transfer; this contribution was shown to be negligible
for the conditions of the current work