Evolution of lignin pyrolysis heavy components through the study of representative lignin monomers

Seven typical lignin monomers with different number of methoxyl groups and different 4-substituted patterns were pyrolyzed at 500 degrees C and 700 degrees C for 120 s to simulate the secondary polymerization and side chain con-version reactions of primary pyrolytic lignin monomers. The pyrolytic heavy oil components were identified at molecular scale with Fourier transform-ion cyclotron resonance mass spectrometry (FT-ICR-MS) and analyzed with Kendrick mass defect (KMD) and van Krevelen diagrams. The detected heavy components were typically phenolic oligomers formed dominantly through the radical coupling reactions of phenol radicals (C6H4O) and methoxyl radicals (OCH2). Model compounds with C--C type 4-substituted groups were prone to produce more phenolic oligomers with more aromatic units. For the C--O type model compounds, the number of methoxyl groups have significant influence on the generation of heavy components, thereby affecting the char yields. Rising temperature promotes the generation of heavy components through three main routes, namely the ad-ditions of CH2, OCH2 and C6H4O. These routes were mapped on van Krevelen diagrams, shedding light on the evolution patterns of both polymerization and side chain conversion reactions during the secondary pyrolysis of lignin.