Dechlorination of a real plastic waste pyrolysis oil by adsorption with zeolites

Abstract

The adsorptive dechlorination of a pyrolysis oil coming from real plastic waste was investigated using different Na-zeolites (4A, 13X, and Y) as adsorbents. The dechlorination experiments were performed in a fixed bed trap under inert atmosphere operating at moderate temperatures (< 180 °C). The dechlorination efficiency of the adsorbents was significantly improved by performing a dehydration pre-treatment due to the removal of water molecules physisorbed on the zeolite surface. Among the zeolitic materials tested, 13X zeolite showed the best dechlorination efficiency, which was related to its high content of Lewis acid sites (attributed to the presence of Na+ cations ionically interacting with the zeolite framework), acting as chemisorption sites, as well as the high accessibility of the FAU-zeolitic topology to the Cl-containing compounds. For that sample, a detailed study of the adsorption temperature (from 30 to 180 °C) and time on stream (1–6 h) was further carried out. The maximum chlorine removal efficiency was achieved, reducing the chlorine content of the pyrolysis oil from 421 to 45 ppm, at temperatures of about 150 – 180 °C. Interestingly, under these conditions, thermal or catalytic cracking effects of the zeolite on the feedstock were not observed. However, the study of the time on stream showed that, after 3 h, the chlorine removal efficiency of the zeolite started to decrease. Thus, different regeneration treatments were evaluated proving that, after a combustion at 600 °C, the zeolite recovered its initial dechlorination efficiency. This research reveals the potential of the adsorptive dechlorination process with Na-zeolites to reduce the chlorine content in plastic pyrolysis oils under mild operating conditions.