A detailed chemical kinetic model for pyrolysis of the lignin model compound chroman

James Bland; Gabriel da Silva; James Bland; Gabriel da Silva

doi:10.3934/environsci.2013.1.12

AIMS Environmental Science

2014, Volume 1, Issue 1: 12-25. doi: 10.3934/environsci.2013.1.12

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Research article

A detailed chemical kinetic model for pyrolysis of the lignin model compound chroman

James Bland ^1,2,
Gabriel da Silva ^{1
,
,}

1.
Department of Chemical and Biomolecular Engineering, The University of Melbourne, Victoria 3010, Australia;
2.
Department of Economics, Purdue University, West Lafayette, Indiana 47907, USA

Received: 11 November 2013 Accepted: 19 December 2013 Published: 19 December 2013

The pyrolysis of woody biomass, including the lignin component, is emerging as a potential technology for the production of renewable fuels and commodity chemicals. Here we describe the construction and implementation of an elementary chemical kinetic model for pyrolysis of the lignin model compound chroman and its reaction intermediate ortho-quinone methide (o-QM). The model is developed using both experimental and theoretical data, and represents a hybrid approach to kinetic modeling that has the potential to provide molecular level insight into reaction pathways and intermediates while accurately describing reaction rates and product formation. The kinetic model developed here can replicate all known aspects of chroman pyrolysis, and provides new information on elementary reaction steps. Chroman pyrolysis is found to proceed via an initial retro-Diels–Alder reaction to form o-QM + ethene (C₂H₄), followed by dissociation of o-QM to the C₆H₆ isomers benzene and fulvene (+ CO). At temperatures of around 1000–1200 K and above fulvene rapidly isomerizes to benzene, where an activation energy of around 270 kJ mol^-1 is required to reproduce experimental observations. A new G3SX level energy surface for the isomerization of fulvene to benzene supports this result. Our modeling also suggests that thermal decomposition of fulvene may be important at around 950 K and above. This study demonstrates that theoretical protocols can provide a significant contribution to the development of kinetic models for biomass pyrolysis by elucidating reaction mechanisms, intermediates, and products, and also by supplying realistic rate coefficients and thermochemical properties.
- Biomass,
- lignin,
- pyrolysis,
- kinetics,
- ab initio,
- transition state theory
Citation: James Bland, Gabriel da Silva. A detailed chemical kinetic model for pyrolysis of the lignin model compound chroman[J]. AIMS Environmental Science, 2014, 1(1): 12-25. doi: 10.3934/environsci.2013.1.12

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Abstract

The pyrolysis of woody biomass, including the lignin component, is emerging as a potential technology for the production of renewable fuels and commodity chemicals. Here we describe the construction and implementation of an elementary chemical kinetic model for pyrolysis of the lignin model compound chroman and its reaction intermediate ortho-quinone methide (o-QM). The model is developed using both experimental and theoretical data, and represents a hybrid approach to kinetic modeling that has the potential to provide molecular level insight into reaction pathways and intermediates while accurately describing reaction rates and product formation. The kinetic model developed here can replicate all known aspects of chroman pyrolysis, and provides new information on elementary reaction steps. Chroman pyrolysis is found to proceed via an initial retro-Diels–Alder reaction to form o-QM + ethene (C₂H₄), followed by dissociation of o-QM to the C₆H₆ isomers benzene and fulvene (+ CO). At temperatures of around 1000–1200 K and above fulvene rapidly isomerizes to benzene, where an activation energy of around 270 kJ mol^-1 is required to reproduce experimental observations. A new G3SX level energy surface for the isomerization of fulvene to benzene supports this result. Our modeling also suggests that thermal decomposition of fulvene may be important at around 950 K and above. This study demonstrates that theoretical protocols can provide a significant contribution to the development of kinetic models for biomass pyrolysis by elucidating reaction mechanisms, intermediates, and products, and also by supplying realistic rate coefficients and thermochemical properties.

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