(432e) Molecular-Level Simulation of Thermogravimetric Analysis (TGA): A Cellulose Pyrolysis Example

Authors: 
Lucio-Vega, J., University of Delaware
Horton, S. R., University of Delaware
Klein, M. T., University of Delaware

Molecular-level
Simulation of Thermogravimetric Analysis (TGA):

A Cellulose Pyrolysis Example

Juan C. Lucio-Vega,
Scott R. Horton, and Mike T. Klein

Department of
Chemical and Biomolecular Engineering, University of Delaware

Thermogravimetric analysis (TGA) of cellulose pyrolysis was
simulated using a molecular-level kinetics model.  A temperature ramp between 600-1000°C was
imposed in order to achieve the TGA simulation. 
The underlying celllose pyrolysis model accounted
for polymer polydispersity whose decomposition was described using Flory-Stockmayer statistics and the degree of polymerization [1].
A recursive optimization method was utilized to calculate the degree of polymerization
of the starting cellulose from literature bulk properties [1, 2]. The model’s
primary reaction pathways for the decomposition allowed for the clipping of the
active cellulose by thermolysis in order to create levoglucasan (LGA) and glucose. The chemistry proposed by
Lin et al [2] was then applied as secondary reactions where the LGA molecules
reacted to produce intermediates and levoglucosenone
(LGO). Further breakdown of the LGO molecules formed volatiles, furans,
aldehyde, ketones, and char through a series of complex reactions. Linear free
energy relationships were applied to minimize the number of model kinetic
parameters. Executing the cellulose pyrolysis model in TGA mode provided a
prediction of the mass loss, which in turn allowed the model parameters to be optimized
to literature TGA data [2]. The optimized model showed good agreement with the
experimental trends.

[1] Scott R. Horton, Rebecca J. Mohr, Yu Zhang, Francis P. Petrocelli, and Michael T. Klein. "Molecular-Level
Kinetic Modeling of Biomass Gasification." Energy & Fuels 30.3
(2016): 1647-1661.

[2] Yu-Chuan Lin, Joungmo Cho, Geoffrey
A. Tompsett, Phillip R. Westmoreland, and George W.
Huber, “Kinetics and Mechanism of Cellulose Pyrolysis” Journal of Physical
Chemistry 113 (2009): 20097–20107.