Characterization and impact of oxygenates in post-consumer plastic waste-derived pyrolysis oils on steam cracking process efficiency

Abstract

Mechanical recycling of mixed packaging waste has limitations due to challenging separation into pure polyolefin streams which often leads to low quality recyclates. A solution to improve overall recycling rates of polyolefins is chemical recycling. One promising approach is conversion into a liquid product via pyrolysis and subsequent steam cracking of the pyrolysis oil towards light olefins. In this study, distilled fractions of pyrolysis oils from PE and PP-rich waste were characterized via GC × GC including normal and reversed-phase column configurations with a special focus on oxygenated components. Distilled pyrolysis oils were subsequently steam cracked in 20/80 weight‐based blends with conventional naphtha. All pyrolysis oil samples contained substantial amounts of oxygenates (1–10 wt%) which poses a huge challenge for steam cracker feedstocks and it was found that ketones are the most prevailing oxygenate group. Steam cracking experiments showed slightly increased ethylene yields of the blends compared to pure fossil naphtha, with the PE-derived samples outperforming the PP-derived samples. Furthermore, diesel-range distillation cuts led to higher formation of heavy products compared to the naphtha-range cuts. Increased formation of CO was observed as a consequence of the substantial oxygen contamination which can be a deal-breaker in industrial steam crackers. This work shows that distilled pyrolysis oils with conventional naphtha are promising steam cracking feedstocks if intermediate processing steps are performed to remove the oxygenates and other impurities using, for instance, hydrotreatment. With the findings of this work, such upgrading processes can be designed in a more effective way.