Tandem catalysis enables chlorine-containing waste as chlorination reagents

Tandem catalysis enables chlorine-containing waste as chlorination reagents

May 2024 | Mingyang Liu, Xinbang Wu & Paul J. Dyson
This article presents a sustainable method for converting chlorine-containing hydrocarbon waste into valuable chlorination reagents using a tandem catalytic approach involving copper (Cu) and palladium (Pd) catalysts with a sodium nitrate (NaNO₃) promoter. Chlorinated waste, including chlorinated polymers and solvents, is oxidized to release chlorine in the presence of N-directing arenes, yielding valuable aryl chlorides such as the FDA-approved drug vismodegib. The remaining hydrocarbon component is mineralized to produce CO, CO₂, and H₂O. The generated CO and CO₂ can be further utilized, making chlorine-containing hydrocarbon waste a viable chlorination reagent without producing hazardous by-products or requiring specialty reagents. This method effectively manages a wide range of chlorine-containing hydrocarbon wastes in a safe and sustainable manner. The study addresses the challenges of disposing of chlorinated hydrocarbon waste, which is persistent in the environment and can release toxic compounds. Traditional methods like landfill and incineration produce hazardous by-products, while catalytic hydrocracking often leads to catalyst deactivation. The proposed method overcomes these limitations by efficiently converting chlorinated waste into useful products. It was tested on various chlorinated waste types, including PVC, polyvinylidene chloride (PVDC), polyepichlorohydrin (PECH), and rubber, achieving high yields of chlorinated products. The method was also applied to the synthesis of the drug vismodegib, demonstrating its potential in pharmaceutical applications. The reaction mechanism involves dechlorination, depolymerization, and chlorination steps. The Cu/NOx catalyst promotes the oxidation of the hydrocarbon component, while the Pd catalyst facilitates C–H bond chlorination. The method was evaluated for its environmental impact through life cycle assessment (LCA), showing lower carbon emissions compared to traditional chlorination methods. The study highlights the potential of this approach for sustainable waste management and the valorization of chlorinated hydrocarbon waste.This article presents a sustainable method for converting chlorine-containing hydrocarbon waste into valuable chlorination reagents using a tandem catalytic approach involving copper (Cu) and palladium (Pd) catalysts with a sodium nitrate (NaNO₃) promoter. Chlorinated waste, including chlorinated polymers and solvents, is oxidized to release chlorine in the presence of N-directing arenes, yielding valuable aryl chlorides such as the FDA-approved drug vismodegib. The remaining hydrocarbon component is mineralized to produce CO, CO₂, and H₂O. The generated CO and CO₂ can be further utilized, making chlorine-containing hydrocarbon waste a viable chlorination reagent without producing hazardous by-products or requiring specialty reagents. This method effectively manages a wide range of chlorine-containing hydrocarbon wastes in a safe and sustainable manner. The study addresses the challenges of disposing of chlorinated hydrocarbon waste, which is persistent in the environment and can release toxic compounds. Traditional methods like landfill and incineration produce hazardous by-products, while catalytic hydrocracking often leads to catalyst deactivation. The proposed method overcomes these limitations by efficiently converting chlorinated waste into useful products. It was tested on various chlorinated waste types, including PVC, polyvinylidene chloride (PVDC), polyepichlorohydrin (PECH), and rubber, achieving high yields of chlorinated products. The method was also applied to the synthesis of the drug vismodegib, demonstrating its potential in pharmaceutical applications. The reaction mechanism involves dechlorination, depolymerization, and chlorination steps. The Cu/NOx catalyst promotes the oxidation of the hydrocarbon component, while the Pd catalyst facilitates C–H bond chlorination. The method was evaluated for its environmental impact through life cycle assessment (LCA), showing lower carbon emissions compared to traditional chlorination methods. The study highlights the potential of this approach for sustainable waste management and the valorization of chlorinated hydrocarbon waste.
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