Controlling Diels-Alder reactions in catalytic pyrolysis of sawdust and polypropylene by coupling CO₂ atmosphere and Fe-modified zeolite for enhanced light aromatics production

Producing value-added light aromatics (BTEX) from solid waste streams holds excellent promise for resource recovery. Here we present a thermochemical conversion approach that enhanced BTEX production by coupling CO₂ atmosphere and Fe-modified HZSM-5 zeolite to facilitate the Diels-Alder reactions in catalytic pyrolysis of sawdust and polypropylene. The Diels-Alder reactions between sawdust-derived furans and polypropylene-derived olefins could be controlled by tuning CO₂ concentration and Fe loading amount. Sufficient CO₂ (≥50%) with moderate Fe loading (10 wt%) were observed to produce more BTEX and fewer heavy fractions (C₉⁺aromatics). To deepen the mechanistic understanding, quantification of polycyclic aromatic hydrocarbons (PAHs) and catalyst coke was further conducted. The co-use of CO₂ atmosphere and Fe modification suppressed the appearance of low-, medium-, and high-membered ring PAHs by over 40%, decreased pyrolysis oil toxicity from 42.1 to 12.8 μg/g_oil TEQ, and transformed coke from "hard" to "soft". Based on the characterization of CO₂ adsorption behavior, it was deduced that the introduced CO₂ was activated by loaded Fe and reacted in situ with H₂ generated during aromatization to expedite H-transfer. Meanwhile, BTEX recondensation was prevented through the Boudouard reactions of CO₂ and water-gas reactions between the resulting water and carbon deposits. These synergistically enhanced the production of BTEX and suppressed the formation of heavy species, including PAHs and catalyst coke.