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As the demand for PET plastic products continues to grow, developing effective processes to reduce their pollution is of critical importance. Pyrolysis, a promising technology to produce lighter and recyclable components from wasted plastic products, has therefore received considerable attention. In this work, the rapid pyrolysis of PET was studied by using reactive molecular dynamics (MD) simulations. Mechanisms for yielding gas species were unraveled, which involve the generation of ethylene and TPA radicals from ester oxygen−alkyl carbon bond dissociation and condensation reactions to consume TPA radicals with the products of long chains containing a phenyl benzoate structure and CO2. As atomistic simulations are typically conducted at the time scale of a few nanoseconds, a high temperature (i.e. >1000 K) is adopted for accelerated reaction events. To apply the results from MD simulations to practical pyrolysis processes, a kinetic model based on a set of ordinary differential equations was established, which is capable of describing the key products of PET pyrolysis as a function of time and temperature. It was further exploited to determine the optimal reaction conditions for low environmental impact. Overall, this study conducted a detailed mechanism study of PET pyrolysis and established an effective kinetic model for the main species. The approach presented herein to extract kinetic information such as detailed kinetic constants and activation energies from atomistic MD simulations can also be applied to related systems such as the pyrolysis of other polymers.
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Multiply Accelerated ReaxFF Molecular Dynamics: Coupling Parallel Replica Dynamics with Collective Variable Hyper Dynamics
To tackle the time scales required to study complex chemical reactions, methods performing accelerated molecular dynamics are necessary even with the recent advancement in high-performance computing. A number of different acceleration techniques are available. Here we explore potential synergies between two popular acceleration methods – Parallel Replica Dynamics (PRD) and Collective Variable Hyperdynamics (CVHD), by analysing the speedup obtained for the pyrolysis of n-dodecane. We observe that PRD + CVHD provides additional speedup to CVHD by reaching the required time scales for the reaction at an earlier wall-clock time. Although some speedup is obtained with the additional replicas, we found that the effectiveness of the inclusion of PRD is depreciated for systems where there is a dramatic increase in reaction rates induced by CVHD. Similar observations were made in the simulation of ethylene-carbonate/Li system, which is inherently more reactive than pyrolysis, indicate that the speedup obtained via the combination of the two acceleration methods can be generalised to most practical chemical systems.
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- Award ID(s):
- 1807740
- PAR ID:
- 10110480
- Date Published:
- Journal Name:
- Molecular simulation
- ISSN:
- 0892-7022
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/doi.org/10.1080/08927022.2019.1646911
