Efficient Upcycling of Polyolefin Waste to Light Aromatics via Coupling C─C Scission and Carbonylation

The upcycling of waste polyolefins into light aromatics has great potential to generate hundreds of millions of tons of valuable aromatic carbon feedstock. However, the conventional high-temperature radical cracking method for aromatizing polyolefins on zeolites faces challenges in aromaticity control and rapid deactivation due to coke. Here, we present a unique strategy that integrates the traditional cracking-aromatization process of PE with CO insertion, a key step of Fischer-Tropsch synthesis, achieving a rise of yield of light aromatics by four times, with an absolute value up to 67% by weight at only 280 °C. The insertion of CO into the Ru-alkyl intermediates formed during polyolefin cracking facilitates the generation of active oxygenate species, guarantees an ideal C─C chain length range, and smooths the way for subsequent efficient aromatization on Hol-ZSM-5@S1 with a short b axis. According to the technical economic analysis, this low-carbon-footprint and economic approach can reduce approximately 1/3 of carbon emissions compared to traditional naphtha cracking technologies and holds promise for reshaping the global aromatic hydrocarbon cycle of the petrochemical industry through polyolefin degradation.