The conversion of a high concentration of lignin to cyclic alkanes by introducing Pt/HAP into a Ni/ASA catalyst

The recalcitrance of lignin with non-hydrolyzable C-O-C bonds, as well as the tendency for its phenolic fragments to polymerize into more recalcitrant polymers, leads to low-efficiency lignin deconstruction processes, such as low lignin concentrations during treatment. Herein, we developed a tandem catalytic approach for the conversion of highly concentrated lignin to stable cyclic alkanes by introducing Pt/HAP into a Ni/ASA catalyst in dodecane media. The incorporated Pt/HAP changes the simultaneous hydrogenation and hydrogenolysis of lignin on Ni/ASA into tandem reactions on a physically mixed Pt/HAP and Ni/ASA catalyst, involving the initial selective lignin depolymerization over Pt/HAP and the following hydrodeoxygenation of phenols over Ni/ASA, as evidenced by kinetic studies. In this tandem approach, the preferred initial lignin depolymerization, instead of lignin hydrogenation, originates from the strong adsorption and high C-O cleavage selectivity of lignin on the introduced Pt/HAP, as confirmed by UV-Vis, gel permeation chromatography (GPC), 2D-heteronuclear single quantum coherence nuclear magnetic resonance (2D-HSQC NMR), and catalytic tests. The rates of lignin depolymerization and the hydrodeoxygenation of depolymerized phenols are matched when the mass ratio of Pt/HAP and Ni/ASA is set at 1 : 1, allowing this approach to proceed with the highest lignin concentrations (150 g L^-1) so far reported, with conversion to cyclic alkanes with 42 wt% yield without coke formation in dodecane at 300 °C in the presence of 6 MPa H₂. Promisingly, the developed approach may lay a solid foundation for future industrial applications relating to lignin valorization.