Low-temperature catalytic dechlorination of model plastic pyrolytic oil over zeolite catalysts

Abstract

Catalytic dechlorination of model plastic pyrolytic oil was investigated over different types of zeolites and ion-exchanged 13X zeolites at the low temperatures of 20–120 °C. Among different types of parent zeolites (13X, β, MCM-41), 13X had the highest catalytic dechlorination performance. After ion exchange of 13X with Ag+, its catalytic dechlorination performance was significantly enhanced, and the chlorine removal over Ag-13X reached 97.2 % after reaction for 5 h at 120 °C. The characterization results indicated that the acidity of the zeolite governed its catalytic dechlorination performance, and higher acid amount and stronger acid strength are preferred. Different types of chlorinated compounds followed different dechlorination mechanisms. The primary chlorinated alkanes (e.g., 1-chlorooctane) underwent nucleophilic substitution by the surface –OH groups or H2O to form alcohols and HCl, or dehydrochlorination reaction to produce olefins and HCl, while higher chlorinated alkanes with adjacent hydrogen (e.g., chlorocyclohexane) mainly underwent dehydrochlorination reaction to produce olefins and HCl. Chlorinated aromatics (e.g., chlorobenzene) was removed mainly by physical adsorption. Ag-13X showed good stability, and the chlorine removal still retained 72.1 % after 102 h on stream. After four dechlorination-regeneration cycles, the chlorine removal had only a slight decrease due to the partial collapse of its structure and slight loss of its acid amount.