TY - JOUR
T1 - A pathway to cyclic carbonates: Cycloaddition of of carbon dioxide to epoxidized methyl oleate on grafted heterogeneous catalysts
AU - Pérez-Sena, Wander Y.
AU - Ciccarelli, Fabrizio
AU - Eränen, Kari
AU - Di Serio, Martino
AU - Russo, Vincenzo
AU - Salmi, Tapio
PY - 2025/1
Y1 - 2025/1
N2 - The conversion of CO
2 into value-added cyclic carbonates via cycloaddition to bio-derived epoxides presents a sustainable approach for CO
2 utilization. However, the production of cyclic carbonates from bio-sources such as epoxidized vegetable oils (EVOs) have significant challenges due to the low reactivity of CO
2 and the steric hindrance of internal epoxides in these bulky substrates. Consequently, the majority of systems for CO
2 fixation to bio-based epoxides rely on homogeneous catalysis. This study investigated the conversion of epoxidized methyl oleate, a model compound for EVOs, into its corresponding cyclic carbonate using heterogeneous 4-pyrrolidinopyridine-based catalysts. The influence of various catalytic parameters, such as the halide counter anions (Cl, Br, I) and incorporated metal Lewis acid centra, was explored within the catalyst. Among the halide counter anions, bromide exhibited a superior performance, achieving 65 % conversion and 59 % cyclic carbonate yield by the end of the experiment, while the effect of various metal centra was less pronounced, with an overall improvement in the cyclic carbonate yield of less than 10 % compared to the metal-free catalyst. A comprehensive study of reaction parameters, including the temperature (100–170°C), the CO
2 pressure (20–40 bar), and the catalyst loading (2.9–10.7 wt%), was conducted in a laboratory-scale autoclave reactor to elucidate the behavior of the reaction system.
AB - The conversion of CO
2 into value-added cyclic carbonates via cycloaddition to bio-derived epoxides presents a sustainable approach for CO
2 utilization. However, the production of cyclic carbonates from bio-sources such as epoxidized vegetable oils (EVOs) have significant challenges due to the low reactivity of CO
2 and the steric hindrance of internal epoxides in these bulky substrates. Consequently, the majority of systems for CO
2 fixation to bio-based epoxides rely on homogeneous catalysis. This study investigated the conversion of epoxidized methyl oleate, a model compound for EVOs, into its corresponding cyclic carbonate using heterogeneous 4-pyrrolidinopyridine-based catalysts. The influence of various catalytic parameters, such as the halide counter anions (Cl, Br, I) and incorporated metal Lewis acid centra, was explored within the catalyst. Among the halide counter anions, bromide exhibited a superior performance, achieving 65 % conversion and 59 % cyclic carbonate yield by the end of the experiment, while the effect of various metal centra was less pronounced, with an overall improvement in the cyclic carbonate yield of less than 10 % compared to the metal-free catalyst. A comprehensive study of reaction parameters, including the temperature (100–170°C), the CO
2 pressure (20–40 bar), and the catalyst loading (2.9–10.7 wt%), was conducted in a laboratory-scale autoclave reactor to elucidate the behavior of the reaction system.
U2 - 10.1016/j.jcou.2024.103005
DO - 10.1016/j.jcou.2024.103005
M3 - Article
SN - 2212-9820
VL - 91
JO - Journal of CO2 utilization
JF - Journal of CO2 utilization
M1 - 103005
ER -