Chlorinated contaminants mitigation during pyro-gasification of wastes using CaO reactant : experimental and life cycle assessment

Thermal treatment of municipal solid waste (MSW) attracts increasing attention due to the associated environmental and energy benefits. However, due to the chlorinated components of the MSW (salts, plastics) hydrogen chloride (HCl) is usually generated and may cause corrosion, toxic organic contaminants formation, acidification, etc. The present study focuses on the reactivity of a calcium oxide (CaO) reactant for in-situ mitigation of released HCl from thermal treatment of MSW. In this work, sorption of HCl gas in CaO reactive bed has been experimentally and theoretically studied. First, it is shown that the use of CaO is effective to remove released HCl gas, by forming a CaCl2 layer at the surface of CaO particles. However, temperature of the reactor is a key process parameter, since the removal capacity of HCl decreases significantly from 778.9 to 173.9 mg/g-CaO with the increase of temperature from 550°C to 850°C. A kinetics analysis has been developed by comparing experimental data with models describing the reaction at the particle surface. It has been concluded that the sorption of HCl at the CaO particle surface is firstly limited by the heterogeneous gas-solid reaction, followed by the HCl diffusion through this porous growing layer. To simulate the in-situ generation of HCl from organic source, pyro-gasification of PVC has been performed with or without CaO addition. The experimental data have been then used for the modeling of the different PVC decomposition steps. Although the average apparent activation energy of pseudo dehydrochlorination reaction is increased from 136.5 kJ/mol to 152.6 kJ/mol with the addition of CaO, the apparent activation energy of the overall PVC decomposition has been decreased from 197.3 to 148.9 kJ/mol by using CaO reactant. In-situ generation of HCl from organic and inorganic sources has also been conducted using simulated MSW. HCl mitigation has been evaluated together with the chemical speciation of the produced tars. Using CaO, the amount of oxygenated organic compounds has been reduced, improving the quality of the tars for a further bio-oil upgrading. To complete the aforementioned works, life cycle assessment (LCA) of three typical pyro-gasification and incineration processes is conducted to compare their overall environmental sustainability. Moreover, pyro-gasification-based WtE systems with different dehydrochlorination strategies are further modeled: 1) conventional gasification system; 2) novel gasification coupled with ex-situ high temperature dehydrochlorination system; and 3) hypothetical gasification coupled with in-situ dehydrochlorination system. The obtained results could be applied to optimize the current waste pyro-gasification systems, with special focus on developing strategies for in-situ dehydrochlorination purpose.