Institute of Sustainability for Chemicals, Energy and Environment, Agency for Science, Technology and Research, 1 Pesek Road, Jurong Island, Singapore 627833, Singapore.
Molecules. 2023 Apr 8;28(8):3316. doi: 10.3390/molecules28083316.
Liquid-phase dehydration of glycerol to acrolein was investigated with solid acid catalysts, including H-ZSM-5, HPO-modified H-ZSM-5, HPWO·14HO and CsHPWO, in the presence of sulfolane ((CH)SO) as a dispersing agent under atmospheric pressure N in a batch reactor. High weak-acidity H-ZSM-5, high temperatures and high-boiling-point sulfolane improved the activity and selectivity for the production of acrolein through suppressing the formation of polymers and coke and promoting the diffusion of glycerol and products. Brønsted acid sites were soundly demonstrated to be responsible for dehydration of glycerol to acrolein by infrared spectroscopy of pyridine adsorption. Brønsted weak acid sites favored the selectivity to acrolein. Combined catalytic and temperature-programmed desorption of ammonia studies revealed that the selectivity to acrolein increased as the weak-acidity increased over the ZSM-5-based catalysts. The ZSM-5-based catalysts produced a higher selectivity to acrolein, while the heteropolyacids resulted in a higher selectivity to polymers and coke.
在间歇式反应器中,在常压 N2 存在下,以环丁砜((CH)SO)作为分散剂,使用 H-ZSM-5、HPO 改性 H-ZSM-5、HPWO·14HO 和 CsHPWO 等固体酸催化剂,研究了甘油液相脱水制丙烯醛反应。高弱酸性 H-ZSM-5、高温和高沸点环丁砜通过抑制聚合物和焦炭的形成以及促进甘油和产物的扩散,提高了丙烯醛生成的活性和选择性。通过吡啶吸附的红外光谱,充分证明了 Brønsted 酸位是甘油脱水生成丙烯醛的原因。Brønsted 弱酸位有利于丙烯醛的选择性。结合氨的催化和程序升温脱附研究表明,随着 ZSM-5 基催化剂上弱酸性的增加,丙烯醛的选择性增加。ZSM-5 基催化剂对丙烯醛的选择性更高,而杂多酸则导致聚合物和焦炭的选择性更高。