DEHP degradation and dechlorination of polyvinyl chloride waste in subcritical water with alkali and ethanol: A comparative study

Abstract

In this study, subcritical water-NaOH (CW–NaOH) and subcritical water-C2H5OH (CW–C2H5OH) processes were developed for diethylhexyl phthalate (DEHP) degradation and dechlorination of polyvinyl chloride (PVC) waste. The introduction of NaOH or C2H5OH in subcritical water had a noticeable influence on the mechanism of DEHP degradation and dechlorination. For both CW-NaOH and CW-C2H5OH treatments, the increase in temperature could increase dechlorination efficiency (DE) of PVC. The DE of CW-NaOH is much higher than that of CW-C2H5OH under the same conditions. The DE of CW-NaOH could exceed 95% at 300 °C. Hydroxyl nucleophilic substitution was the main dechlorination mechanism in CW-NaOH, while nucleophilic substitution and direct dehydrochlorination were equally important in CW-C2H5OH. In CW-NaOH treatment, 2-ethyl-1-hexanol, benzaldehyde, and toluene were obtained by hydrolysis and reduction reactions of DEHP. Acetophenone was produced by the further cyclization, dehydrogenation and rearrangement reactions of 2-ethyl-1-hexanol. Transesterification was the main degradation pathway of DEHP in CW-C2H5OH at 300 °C. The cyclization and dehydration of 2-ethyl-1-hexanol resulted in producing a high level of ethyl-cyclohexane and 1-ethyl-cyclohexene in CW-C2H5OH at 350 °C. Furthermore, high concentration of ethyl palmitate and ethyl stearate could be prepared in CW-C2H5OH system by the strong reactivity of C2H5OH with the lubricants in PVC.