Investigation into the Catalytic Co-Pyrolysis of Chlorella vulgaris and Eucalyptus Branches Using Bimetallic Ni-X (X = Mg, Cu, Fe) Modified HZSM-5: Product Characteristics and Bio-Oil Composition

The co-pyrolysis of Chlorella vulgaris (CV) and Eucalyptus branches (EP) offers a promising strategy to enhance bio-oil yield, improve resource utilization efficiency, and alleviate environmental pressures. In this study, the microwave-assisted co-pyrolysis of CV and EP at a mass ratio of 2:1 was investigated, focusing on the catalytic performance of Ni-X (X = Mg, Cu, Fe) bimetallic modified HZSM-5 zeolites. The effects of these catalysts on pyrolysis characteristics, product distribution, and bio-oil composition were systematically evaluated. Experimental results showed that the 15% Ni-Cu/HZSM-5 catalyst exhibited the best catalytic performance, achieving the highest bio-oil yield of 16.83%; it also elevated the Rm to 0.0687 wt.%/s and reduced Ts to 2084 s. Composition analysis revealed that Ni-Cu/HZSM-5 significantly promoted the formation of hydrocarbons, increasing their relative content from 11.59% (C2E1 Group) to 28.92%, while effectively suppressing the formation of nitrogen-containing compounds, reducing their content by 5.05%. Based on these results, a possible reaction pathway is proposed in which the Ni-Cu/HZSM-5 catalyst may enhance heteroatom removal through hydrodeoxygenation (HDO) at the Ni-Cu sites, followed by cracking and aromatization at the HZSM-5 acid sites. This effect may be complemented by preferential adsorption of oxygenated intermediates over nitrogen-containing species, which could help suppress the formation of nitrogenous heterocycles. This work provides theoretical guidance for the application of bimetallic zeolite catalysts in microalgae/lignocellulose co-pyrolysis, alongside a viable pathway for valorizing Eucalyptus by-products to produce high-quality bio-oil.