Hydrogen-rich gas generation from enhanced catalytic cracking of biomass tar and related model compounds on Ni-Fe/ASA@HZSM-5 catalyst: Pathways and mechanisms

Abstract

This study focused on the design of complex tar model compounds (CTMC) and synthesized a highly efficient aluminum dross (ASA) combined with HZSM-5 molecular sieve co-loaded bimetallic Ni-Fe catalyst (Ni-Fe/ASA@HZSM-5), comprehensively evaluated the catalytic cracking of real tar and its model compound by adjusting the injection amount and injection state of tar, and catalyst types to obtain hydrogen-rich gas with high H₂ and low CO₂ content. The results showed under the conditions of the injection amount of 0.6 mL/min, pyrolysis temperature of 600 °C, reforming temperature of 800 °C in the liquid phase, Ni-Fe/ASA@HZSM-5 displays excellent catalytic cracking performance with CTMC conversion efficiency of 87.80 % (79.46 % of gas yield and 34.20 vol% of H₂ yield). The possible cracking paths between different components of CTMC in the Ni-Fe catalytic system were summarized by the experimental data and product distribution, the catalytic mechanism of Ni–Fe based catalysts can be attributed to the formation of a Ni-Fe alloy and the synergistic effect of ASA and HZSM-5 co-carrier. Further, the catalytic cracking pathway of CTMC was enhanced in the gas phase, the higher CTMC conversion efficiency of 93.68 %, gas yield (a mass fraction of 82.51 %) and H₂ (a volume fraction of 33.59 %) were obtained from catalytic cracking of CTMC, the liquid yield decreased by 12.39 %, significantly improved the cracking degree and gas production capacity of CTMC. The real tar showed the same catalytic pyrolysis path and product distribution. Under the same cracking conditions, the yields of gas, liquid and char were 84.85 %, 12.00 % and 3.15 % respectively, and obtained the hydrogen yield of 55.29 mL/g. The CTMC simplifies the cracking process and reduces polymerization, provides insights into the cracking mechanisms of heavy components in biomass tar. Furthermore, the synergy of Ni and Fe contributed to greater activity for CTMC and real tar cracking, ASA combined with HZSM-5 molecular sieve co-loaded bimetallic Ni-Fe catalysts have a promising application potential as highly efficient catalysts for tar removal and reutilization.