Molecular Products and Radicals from Pyrolysis of Lignin

摘要

Thermal degradation of lignin under two reaction regimes (pyrolysis in N_2 and oxidative pyrolysis in 4% O_2 in N_2) has been investigated in a tubular, isothermal, flow-reactor over the temperature range 200-900 ℃ at a residence time of 0.2 s. Two experimental protocols were adopted: (1) Partial pyrolysis in which the same lignin sample was continuously pyrolyzed at each temperature and (2) conventional pyrolysis, in which new lignin samples were pyrolyzed at each pyrolysis temperature. The results identified common relationships between the two modes of experiments, as well as some differences. The majority of products from partial pyrolysis peaked between 300 and 500 ℃, whereas for conventional pyrolysis reaction products peaked between 400 and 500 ℃. The principal products were syringol (2,6-dimethoxy phenol), guaiacol (2-methoxy phenol), phenol, and catechol. Of the classes of compounds analyzed, the phenolic compounds were the most abundant, contributing over 40% of the total compounds detected. Benzene, styrene, and ^-xylene were formed in significant amounts throughout the entire temperature range. Interestingly, six ringed polycydic aromatic hydrocarbons were formed during partial pyrolysis. Oxidative pyrolysis did not result in large differences from pyrolysis; the main products still were syringol, guaiacol, phenol, the only significant difference being the product distribution peaked between 200 and 400 ℃. For the first time, low temperature matrix isolation electron paramagnetic resonance was successfully interfaced with the pyrolysis reactor to elucidate the structures of the labile reaction intermediates. The EPR results suggested the presence of methoxyl, phenoxy, and substituted phenoxy radicals as precursors for formation of major products; syringol, guaiacol, phenols, and substituted phenols.