Tailored HZSM-5 catalyst modification via phosphorus impregnation and mesopore introduction for selective catalytic conversion of polypropylene into light olefins

The waste polyolefin composition varies regionally due to different sorting technologies, emphasizing the necessity for a robust catalyst capable of selectively converting pyrolysis vapors into valuable light olefins while maintaining stability. HZSM-5, a microporous catalyst, efficiently cracks polyethylene (PE) pyrolysis vapors rich in linear aliphatics. However, polypropylene (PP) pyrolysis typically yields branched olefins, potentially hindering effectiveness of HZSM-5 due to mass transfer constraints and coke blockage in micropores. This study modifies HZSM-5 through phosphorus impregnation, mesopore introduction, and steam treatment to evaluate the impact of acidity, pore size, and surface modifications on catalyst stability and light olefin selectivity during PP pyrolysis vapor cracking. Subsequent experiments reveal the superior stability of modified catalysts. Phosphorus-modified (P-HZSM-5ss) and mesoporous phosphorus-modified (P-mesoHZSM-5ss) catalysts retain 72% and 80% of their initial activity after 150 runs, respectively, while the parent HZSM-5 experiences a rapid 44% activity loss. P-mesoHZSM-5ss demonstrates the highest light olefin selectivity (63 wt.%) after 150 runs, attributed to improved accessibility of branched olefinic products to active sites within catalyst pores. Further optimization achieves exceptional light olefin selectivity of 84 wt.% at 117 ms contact time and 550 °C, surpassing maximum selectivity of the parent catalyst. Comparative analyses of PP, PE, and mixed polyolefinic waste pyrolysis vapor cracking revealed the influence of polyolefin type on optimal operational conditions, stressing the need for flexibility in operating conditions to scale up the proposed polyolefin recycling method. This study highlights the potential of tailored catalyst modifications and process optimization to efficiently convert PP into valuable light olefins, advancing sustainable polyolefin recycling technologies.