From cellulose to tar: Analysis of tar formation pathway with distinguishing the primary and secondary reactions

Tar problem seriously hinders the development of biomass gasification. The tar formation of biomass is greatly influenced by cellulose. In this work, PY-GC/MS was employed for providing a precise insight into the formation of primary and secondary products, and a tar contribution index was introduced to evaluate the potential of tar formation from different origins. Combined with statistical analysis and corroboration by DFT analysis, key intermediates for tar formation are recognized, and corresponding influence is confirmed. A new framework from cellulose to tar was built. The secondary reaction acts a more important role for tar formation. The aromatic precursors and high-activity small-molecular gases are two key compounds responding to tar formation, and the existence of high-activity small-molecular gases could significantly reduce the energy barrier during tar formation. For furans, the energy barrier can be reduced from 100.2 kcal/mol to 74.2 kcal/mol in the presence of ethylene.