(621dj) Fundamental Study of Cellulose Pyrolysis Kinetics and Chemistry

Authors: 
Krumm, C., University of Minnesota Twin Cities
Paulsen, A. D., University of Minnesota Twin Cities
Zhu, C., University of Minnesota Twin Cities
Maduskar, S., University of Minnesota
Dauenhauer, P., University of Minnesota

During the high temperature pyrolysis of biomass, long chain biopolymers transform to a liquid intermediate before depolymerizing and volatilizing into a condensable bio-oil product for upgrading into fuels and chemicals [1]. A major challenge in the study of biomass pyrolysis chemistry is the complexity of the problem – hundreds of products are formed on a millisecond timescale and reaction kinetics are convoluted by heat and mass transfer [2,3]. Current experimental kinetic models are “lumped”, grouping products together and providing limited insight into chemistry and reaction mechanisms [4].  In this work, a novel method for the study of biomass pyrolysis chemistry provides the first-ever rates of formation of individual chemical species from cellulose pyrolysis. Kinetics of cellulose chemistry provide insight into the mechanisms of formation of classes of compounds, such as furans. Kinetic rate measurements provide the first experimental insight into the length scales relevant toward transport limitations within pyrolyzing cellulose. Development of a detailed experimental kinetic model of cellulose pyrolysis will direct the development of detailed kinetic input-output models for biomass pyrolysis as well as the directed design of pyrolysis reactors for improved chemical and fuel yields and quality from pyrolysis reactors.

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

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

[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] Bridgwater, A. V., Meier, D., Radlein, D., Organic Geochemistry, 1999, 30, 1479-1493,