Comparative study on the two-step and one-step pyrolysis of lignin: effects of pyrolysis temperature and residence time on the product distribution

To explore a new way of utilizing lignin and deepen the understanding of mechanism of two-step pyrolysis (TSP) of biomass, the effects of the first step pyrolysis temperature (T1) and residence time (RT1) on TSP of lignin were studied by using pyrolysis gas chromatography/mass spectrometry (Py-GC/MS). TSP of lignin was also compared with one-step pyrolysis (OSP) of lignin. The results indicated that higher pyrolysis temperature promoted the break of ether linkage among the structural elements of lignin and the removal of side chains. With T1 increasing, the contents of monophenols (MPs), catechols (CPs), monocyclic aromatic hydrocarbons (MAHs), and polycyclic aromatic hydrocarbons (PAHs) increased in the first step, while the contents of methoxyphenols with double bond in the side-chain (MPBSs) and methoxyphenols with no double bond in the side-chain (MPSs) increased firstly and then decreased. In the second step, with T1 increasing the contents of MPs and CPs increased firstly and then decreased, the contents of MAHs and PAHs increased significantly, and the contents of MPBSs and MPSs decreased. Higher T1 increased the yields of the most identified compounds of the first step, but decreased the yields of MPs, CPs, MPBSs, and MPSs in the second step. RT1 had great effects on the pyrolysis behaviors and product distribution of TSP of lignin, and the content of MAHs and PAHs in the second step increased significantly with RT1 increasing. Compared with OSP, the yields of MAHs and PAHs could increase in the second step. TSP of lignin could improve the selectivity of value-added chemicals remarkably, such as guaiacol, vanillin, acetovanillone in the first step, and the selectivity of benzene, toluene, m-xylene, phenol, o-cresol, and p-cresol in the second step.