Oxidation of benzyl alcohols to ketones and aldehydes by O3 process enhanced using high-gravity technology

doi:10.1016/j.cjche.2020.02.015

Abstract

Abstract: In this study, a practical process for ozonization of benzyl alcohols to ketones and aldehydes in a rotating packed bed (RPB-O₃) reactor has been developed. Using 1-phenylethanol as a model reactant, the performance of RPB-O₃ process in different solvents has been compared with the commonly used stirred tank reactor (STR-O₃). Ethyl acetate was the optimum solvent for the conversion of 1-phenylenthanol to acetophenone in RPB-O₃ process, with 78% yield after 30 min. In a parallel STR-O₃ experiment, the yield of acetophenone was 50%. Other experimental variables, i.e. O₃ concentration, reaction time, high-gravity factor and liquid flow rate were also optimized. The highest yield of acetophenone was obtained using O₃ concentration of 80 mg·L^-1, reaction time of 30 min, high gravity factor of 40 and liquid flow rate of 120 L·h^-1. Under the optimized reaction conditions, a series of structurally diverse primary and secondary alcohols was oxidized with (19%-92%) yield. The ozonization mechanism was studied by Electron Paramagnetic Resonance (EPR) spectroscopy, monitoring the radical species formed upon self-decomposition of O₃. The characteristic quadruple peak with the 1:2:2:1 intensity ratio that corresponds to hydroxyl radicals (·OH) was observed in the electron paramagnetic resonance (EPR) spectrum, indicating an indirect oxidation mechanism of alcohols via ·OH radical.

Key words: Ozone, Benzyl alcohols, Aldehydes and ketones, High-gravity technology

摘要： In this study, a practical process for ozonization of benzyl alcohols to ketones and aldehydes in a rotating packed bed (RPB-O₃) reactor has been developed. Using 1-phenylethanol as a model reactant, the performance of RPB-O₃ process in different solvents has been compared with the commonly used stirred tank reactor (STR-O₃). Ethyl acetate was the optimum solvent for the conversion of 1-phenylenthanol to acetophenone in RPB-O₃ process, with 78% yield after 30 min. In a parallel STR-O₃ experiment, the yield of acetophenone was 50%. Other experimental variables, i.e. O₃ concentration, reaction time, high-gravity factor and liquid flow rate were also optimized. The highest yield of acetophenone was obtained using O₃ concentration of 80 mg·L^-1, reaction time of 30 min, high gravity factor of 40 and liquid flow rate of 120 L·h^-1. Under the optimized reaction conditions, a series of structurally diverse primary and secondary alcohols was oxidized with (19%-92%) yield. The ozonization mechanism was studied by Electron Paramagnetic Resonance (EPR) spectroscopy, monitoring the radical species formed upon self-decomposition of O₃. The characteristic quadruple peak with the 1:2:2:1 intensity ratio that corresponds to hydroxyl radicals (·OH) was observed in the electron paramagnetic resonance (EPR) spectrum, indicating an indirect oxidation mechanism of alcohols via ·OH radical.

关键词: Ozone, Benzyl alcohols, Aldehydes and ketones, High-gravity technology

Wenqiang Gao, Lei Du, Weizhou Jiao, Youzhi Liu. Oxidation of benzyl alcohols to ketones and aldehydes by O₃ process enhanced using high-gravity technology[J]. Chinese Journal of Chemical Engineering, 2020, 28(3): 808-814.

Wenqiang Gao, Lei Du, Weizhou Jiao, Youzhi Liu. Oxidation of benzyl alcohols to ketones and aldehydes by O₃ process enhanced using high-gravity technology[J]. 中国化学工程学报, 2020, 28(3): 808-814.

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Oxidation of benzyl alcohols to ketones and aldehydes by O₃ process enhanced using high-gravity technology

Oxidation of benzyl alcohols to ketones and aldehydes by O₃ process enhanced using high-gravity technology

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