Assessing the feasibility of chemical recycling via steam cracking of untreated plastic waste pyrolysis oils: Feedstock impurities, product yields and coke formation

Chemical recycling of plastic waste to base chemicals via pyrolysis and subsequent steam cracking of pyrolysis oils shows great potential to overcome the limitations in present means of plastic waste recycling. In this scenario, the largest concern is the feasibility. Are plastic waste pyrolysis products acceptable steam cracking feedstocks in terms of composition, product yields and coke formation? In this work, steam cracking of two post-consumer plastic waste pyrolysis oils blended with fossil naphtha was performed in a continuous bench-scale unit without prior treatment. Product yields and radiant coil coke formation were benchmarked to fossil naphtha as an industrial feedstock. Additionally, the plastic waste pyrolysis oils were thoroughly characterized. Analyses included two dimensional gas chromatography coupled to a flame ionization detector for the detailed hydrocarbon composition as well as specific analyses for heteroatoms, halogens and metals. It was found that both pyrolysis oils are rich in olefins (∼48 wt%) and that the main impurities are nitrogen, oxygen, chlorine, bromine, aluminum, calcium and sodium. Steam cracking of the plastic waste derived feedstocks led to ethylene yields of ∼23 wt% at a coil outlet temperature of 820 °C and ∼28 wt% at 850 °C, exceeding the ethylene yield of pure naphtha at both conditions (∼22 wt% and ∼27 wt%, respectively). High amounts of heavy products were formed when steam cracking both pyrolysis oils, respectively. Furthermore, a substantial coking tendency was observed for the more contaminated pyrolysis oil, indicating that next to unsaturated hydrocarbons, contaminants are a strong driver for coke formation.