Catalytic pyrolysis of enzymatic hydrolysis lignin by transition-metal modified HZSM-5/MCM-41 core–shell catalyst for the enhancement of monocyclic aromatic hydrocarbons

Enzymatic hydrolysis lignin (EHL) is produced in large quantities during the fermentation of lignocellulosic biomass to produce ethanol, resulting in environmental pollution and resource waste. HZSM-5/MCM-41 core–shell zeolites (H/M) loaded with transition metal Mn, Fe, Co, Ni, Cu, and Zn at different loading levels (2, 4, 6, 8, and 10 wt%) were prepared as catalysts. Py-GC/MS was employed to investigate their effects on the selectivity for and relative abundance of monocyclic aromatic hydrocarbons (MAHs) in the catalytic pyrolysis products of EHL. On this basis, bimetal-loaded H/M catalysts were constructed, namely Fe-Zn@H/M, Fe-Co@H/M, Fe-Ni@H/M, Co-Zn@H/M, Co-Ni@H/M, and Zn-Ni@H/M. Co-Ni@H/M increased the selectivity for and relative abundance of MAHs by 11.68% and 28.01%, respectively, compared with the H/M catalyst. Moreover, Co-Ni@H/M induced a further increase in the selectivity for and abundance of MAHs compared with the corresponding monometal-loaded catalysts. The characterization results indicated that bimetallic Co and Ni loading were uniformly dispersed on the catalyst surface and did not change the structure of the parent catalyst but affected the pore characteristics and acidic site distribution of the catalyst. Further analysis of the pyrolysis products suggested that bimetallic Co and Ni loading enhanced the dealkylation capacity of the catalyst for furans, aldehydes and phenol derivatives. Oligomerization, cyclization and aromatization of short alkyl chains were promoted in the MAHs by Co-Ni@H/M. Meanwhile, bimetallic Co and Ni loading inhibited the polymerization of phenols and other oxygen-containing compounds by promoting dehydration, decarboxylation and decarbonylation, which indirectly reduced the formation of coke.