(429e) Experimental Determination of Cellulose Pyrolysis Reaction Kinetics and Transport Phenomena

Biomass pyrolysis is a promising thermochemical method for producing fuels and chemicals from renewable sources. Development of a fundamental understanding of biomass pyrolysis chemistry is difficult due to the multi-scale and multi-phase nature of the process; biomass length scales span 11 orders of magnitude and pyrolysis phenomena include solid, liquid, and gas phase chemistry in addition to heat and mass transfer [1,2]. These complexities have a significant effect on chemical product distributions and lead to variability between reactor technologies [3,4]. A major challenge in the study of biomass pyrolysis is the development of kinetic models capable of describing hundreds of millisecond-scale reactions of biomass into lower molecular weight products. In this work, a novel technique for studying biomass pyrolysis provides the first-ever experimental determination of kinetics and rates of formation of the primary products from cellulose pyrolysis, providing insight into the millisecond-scale chemical reaction mechanisms. These findings highlight the importance of heat and mass transport limitations for cellulose pyrolysis chemistry and are used to identify the length scales at which transport limitations become relevant during pyrolysis. Combined knowledge of pyrolysis chemistry, kinetics, and heat and mass transport effects direct the design of the next generation pyrolysis reactors for tuning bio-oil quality and design of improved catalytic upgrading technology.

[1] Mettler, M. S., Vlachos, D., and Dauenhauer, P. J., Energy & Envrinmental Science, 2012, 5(7), 7797-7809

[2] Dauenhauer, P. J.; Colby, J. L.; Balonek, C. M.; Suszynski, W. J.; Schmidt, L. D., Green Chemistry, 2009, 11, (10), 1555-1561.

[3] Mettler, M.S., Mushrif, S.H., Paulsen, A.D., Javadekar, A.D., Vlachos, D.G., Dauenhauer, P.J., Energy & Envrinmental Science, 2011, 5, 5414-5424

[4] Paulsen, A. D., Mettler, M. S., and Dauenhauer, P. J., Energy & Fuels, 2013, 27(4), 2126-2134