Kinetics of thermal de-chlorination of PVC under pyrolytic conditions

Although PVC-containing wastes are an important potential source of energy they are frequently disposed in landfill. In thermal treatment processes such as pyrolysis and gasification, the presence of poly(vinyl chloride) (PVC), a compound with 56.7% of chlorine, may cause problems concerned with environmental protection, as consequence of the formation of hydrochloric acid, chlorine gas and dioxins, as well as corrosion phenomena of the reactor/equipment materials. Thus, a possible solution may involve a previous removal of the chlorine from PVC containing waste through a pyrolysis process at low temperatures before the material being submitted to a subsequent thermal treatment, for energetic valorization. In this work, a kinetic model for the thermal decomposition of PVC has been developed, in view of its de-chlorination. DTA/TGA testing at different temperatures indicated a first order reaction and an activation energy of 133,800 J/mol. An almost completed de-chlorination reaction was obtained at 340 °C under an inert atmosphere. The resulted material is a CnHn type polymer with potential to be used in an energy recovery process. Validation test performed at laboratory scale indicate that the temperature of 340 °C enables the removal of ∼99.9% of the chlorine present in PVC. The chloride can be fixed in the form of an aqueous solution of HCl or calcium chloride, driving to an alternative full process with environmental benefits and reduction of the costs associated to the PCV – containing materials/wastes management.

► Several tests were performed in DTA/TGA for understanding the thermal behavior of pure PVC. ► We did a kinetic model for the de-chlorination of PVC molecule. ► A temperature of 340 °C was defined as the optimum temperature for breaking the bond of chlorine in the PVC molecule. ► The experimental validation of this temperature, led to a removal rate of 99.9% chlorine.