(251f) Advanced Analytical Methodologies Enable Feedstock Screening and Correlation to Pyrolysis Yields and Catalytic Upgrading

Pyrolysis of lignocellulosic biomass can serve as a powerful pathway for the generation of renewable fuels and industrial products. However, procurement of some biomass may be costly, especially when there is competition for alternative uses. Forestry and agricultural byproducts may serve as valuable pyrolysis feedstocks due to their high availability and low cost. Although waste products may fill demand for affordable pyrolysis feedstocks, they are often high in ash and extractives which contribute to unfavorable changes in pyrolysis vapor composition, as well as end products. The work presented here investigates the correlations between various pine anatomical fractions to understand their effect on pyrolysis oil composition for forest residues. Analytical pyrolysis coupled to direct analysis by molecular beam mass spectrometry (MBMS) provides real-time monitoring of pyrolysis vapor composition, even for compounds that are not amenable to gas chromatography. Statistical analysis of MBMS data from the fast pyrolysis (FP) of clean pine, cambium, twigs and branches, needles, bark, and a forest residue samples revealed that bark and needles made the greatest differences in the vapor composition of forest residues during pyrolysis and were enriched in resin acids, furfural derivatives, and ions that have been previously observed from catalysis corresponding to ash content. These results were also compared to catalytic fast pyrolysis (CFP) using a platinum on titania catalyst, and correlations between FP and CFP products were observed for the anatomical fractions. The forest residues and corresponding anatomical fractions from a stand of 23-year-old pine will be converted by fast pyrolysis in a bench-scale 2-inch fluidized-bed reactor, and statistical correlations between the bench-scale products and analytical-scale pyrolysis vapors will be shown. This work highlights the power of advanced analytical methodologies in determining the contributions of vapor components to catalytic pyrolysis outcomes for mixed feedstocks and demonstrates the use of analytical methodologies to better screen feedstocks prior to pyrolysis.