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March 8, 2026ACS Catalysis2 citations

Impact of Nitrogen and Other Heteroatoms on Catalytic Cracking of Crude Waste Plastic Pyrolysis Oil for Light-Olefin Production

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XTXuan Tin TranTKTae Yong KimDMDae Hun Mun

Key Points

  • To examine how impurities in waste plastic pyrolysis oil affect the catalytic cracking process, particularly focusing on light olefin production.
  • Analyzed the effects of various impurities on catalytic cracking using a phosphorus-modified ZSM5 catalyst.
  • Investigated the deactivation effects of nitrogen compounds in WPPO.
  • Evaluated machine-learning potential calculations for steric hindrance and adsorption energy influence.
  • Conducted experiments under varying temperature and nitrogen concentration conditions.
  • Nitrogen-containing compounds cause severe catalytic deactivation in the order of toxicity: 2-methylpyridine > pyridine > quinoline > pyrrole > benzonitrile.
  • Introducing 2200 ppm of 2-methylpyridine reduces olefin and BTX yield from 68.7 to 55.7 wt %.
  • Coke deposition led to a decline in olefin yield but was reversible through catalyst regeneration.
  • Higher nitrogen concentrations intensified deactivation, while elevated temperatures reduced it.

Abstract

Waste plastic pyrolysis oil (WPPO), a feasible alternative to crude oil, is an important enabler of circular plastic economy. However, the types and levels of impurities in WPPO are distinct from those in crude oil and pose significant challenges for the direct utilization of WPPO in refining and petrochemical processes. A systematic investigation of the impact of these impurities on the catalytic cracking of WPPO over a microspherical phosphorus-modified steamed ZSM5 catalyst, with an emphasis on the production of light olefins, is reported. Under the tested conditions, sulfur-, chlorine-, and oxygen-containing compounds minimally affect the yield of C2–C4 olefins. In contrast, nitrogen-containing compounds cause severe catalytic deactivation in the following order: 2-methylpyridine > pyridine > quinoline > pyrrole > benzonitrile. Notably, the introduction of 2200 ppm 2-methylpyridine into WPPO significantly lowers the total yield of C2–C4 olefins and BTXs from 68.7 to 55.7 wt %. Although the poisoning effect is generally correlated with the proton affinity (PA) of the nitrogen-containing compounds, the PA alone cannot sufficiently explain the observed deactivation trend. Machine-learning potential calculations identified site-dependent steric hindrance as another factor that affects the adsorption energy of these compounds. Furthermore, nitrogen poisoning proves to be both concentration- and temperature-dependent. Higher nitrogen concentrations intensify deactivation, whereas elevated temperatures mitigate this effect. Coke deposition causes a gradual decline in the light-olefin yield; however, the catalytic activity is fully restored after regeneration. These findings highlight the feasibility of employing a circulating fluidized bed reactor with continuous regeneration for the industrially viable large-scale catalytic cracking of WPPO, even in the presence of high levels of diverse impurities.

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Cite This Study

Tran et al. (2026) studied this question.

synapsesocial.com/papers/69ada8dfbc08abd80d5bc452https://doi.org/10.1021/acscatal.5c08941
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