ABSTRACT
Depolymerization of lignin into valuable aromatic compounds is an important starting point for its valorization strategies, which requires the cleavage of C-O and C-C bonds between lignin monomer units. The catalytic cleavage of these bonds is still difficult and challenging. Our previous experimental investigation (Green Chem., 2018, 20: 3743) has shown that methyl p-hydroxycinnamate (MPC) can be produced from molecular tailoring of H unit in lignin by the cleavage of the γ-O ester bond. In this study, the mechanism of [Bmim][FeCl4]-catalyzed depolymerization of lignin was investigated by using the density functional theory (DFT) method. The results reveal that [FeCl4]- anion of the catalyst plays a decisive role in the whole catalytic process, where two possible activation modes including three different potential reaction pathways can realize the depolymerization of lignin model compound. The calculated overall barriers of the catalytic conversion along these potential routes show that the third potential pathway, i.e., methanol firstly activated by [Bmim][FeCl4], has the most probability with the lowest energy barrier, while the second pathway is excluded because the energy barrier is too high. Also, the results illustrate that the solvent effect is beneficial to the reduction of the relative energy for the reaction to form the transition states. Hence, the obtained molecular level information can identify the favorable conversion process catalyzed by metallic ionic liquids to a certain extent, and it is desirable to enhance the utilization of biomass as a ubiquitous feedstock.
ABSTRACT
An efficient emulsion microreactor was constructed for selective conversion of lignosulfonate via hydrogen transfer reaction based on the self-surfactivity of this natural aromatic polymer. Industrial Raney Ni and isopropanol were used as catalyst and hydrogen donor, respectively. The results showed that the emulsion microreactor has a remarkable process intensification effect on the lignosulfonate depolymerization. Under mild condition of 473â¯K for 2.0â¯h, 116.1â¯mgâ¯g-1 of volatile phenolic monomer can be obtained, which is twice of that from other investigated processes without emulsion of this work. In particular, 39.3â¯mgâ¯g-1 of which is composed of 4-ethyl guaiacol, an important and versatile chemical currently from petrochemical industry. Furthermore, the solvent separates to two phases automatically after reaction due to the consumption of lignosulfonate, which makes handy products enrichment and separation. Additionally, the emulsion microreactor is significantly affected by hydrogen donor and is efficient for other lignin sources as well.
