(27a) Pyrolysis Kinetics for Small-Molecule Intermediates of Cellulose Pyrolysis
AIChE Annual Meeting
2013
2013 AIChE Annual Meeting
Catalysis and Reaction Engineering Division
Reaction Path Analysis
Sunday, November 3, 2013 - 3:30pm to 3:50pm
Pyrolysis experiments on glycolaldehyde, glyceraldehyde, and 1,3-dihydroxyacetone reveal products that provide new insights into biomass pyrolysis chemistry. Pyrolysis starting from these small molecules helps in constructing a reliable reaction mechanism that can clarify the details of cellulose pyrolysis (1-4). The compounds studied here appear in glucose and cellulose pyrolysis; therefore, the research gives some detail on secondary reactions that happen in the gas phase once volatile compounds start to form from glucose and cellulose pyrolysis.
In this work, flash pyrolysis was conducted (CDS Analytical, Pyroprobe® Model 5200) with analysis by comprehensive two-dimensional gas chromatography-mass spectrometry (LECO Corp., Pegasus® 4D GCxGC-TOFMS), supplemented by computational quantum chemistry for theoretically predicting products that may be formed from the pyrolysis. The pyrolysis was conducted at different temperatures so that the formation temperature of different species can be mapped. The detailed temperature-resolved measurement can help in identifying optimal temperature of operation under real pyrolysis conditions. Initial results showed both decomposition and molecular-weight growth in the cases of glyceraldehyde and 1,3-dihydroxyacetone. Considerable isomerization between glyceraldehyde and 1,3-dihydroxyacetone was also observed. No reaction of glycolaldehyde was detected at the flash-pyrolysis conditions.
References
- Vikram Seshadri and Phillip R. Westmoreland, “Concerted reactions and mechanism of glucose pyrolysis and implications for cellulose kinetics,” J. Phys. Chem. A, 116 (2012) 11997-12013.
- Heather B. Mayes and Linda J. Broadbelt, “Unraveling the reactions that unravel cellulose,” J. Phys. Chem. A, 116 (2012) 7098-7106.
- Rajeev S. Assary and Larry A. Curtiss, “Thermochemistry and Reaction Barriers for the Formation of Levoglucosenone from Cellobiose,” ChemCatChem, 4(2) (2012) 200-205.
- Vishal Agarwal, Paul J. Dauenhauer, George W. Huber, Scott M. Auerbach, “Ab Initio Dynamics of Cellulose Pyrolysis: Nascent Decomposition Pathways at 327 and 600 °C,” J. Am. Chem. Soc., 134 (2012) 14958−14972.
Contact Information
Vikram Seshadri
Department of Chemical and Biomolecular Engineering
North Carolina State University
Box 7905
Raleigh, NC 27695-7905
Patrick Fahey
Department of Chemical and Biomolecular Engineering
North Carolina State University
Box 7905
Raleigh, NC 27695-7905
Xinglian Geng
Department of Chemical and Biomolecular Engineering
North Carolina State University
Box 7905
Raleigh, NC 27695-7905
Phillip R. Westmoreland*
Executive Director, Institute for Computational Science and Engineering
Professor, Department of Chemical and Biomolecular Engineering
North Carolina State University
Box 7905
Raleigh, NC 27695-7905
*To whom correspondence should be addressed.