Process and Catalysis Research, Institute of Chemical and Engineering Sciences, Agency for Science, Technology and Research, 1 Pesek Road, Jurong Island, Singapore 627833, Singapore.
Dalton Trans. 2022 Oct 25;51(41):15912-15932. doi: 10.1039/d2dt02527b.
We have deeply investigated KNO-derived silica-supported potassium lactate catalysts for the vapour-phase dehydration of lactic acid (LA) to acrylic acid (AA) by catalytic testing, IR spectroscopic monitoring, ammonia temperature-programmed desorption, isopropyl amine temperature-programmed desorption, IR spectroscopy of pyridine adsorption and thermogravimetric analysis (TGA). A combination of catalytic and acid property studies illustrates that the acidic KNO/silica systems are not favourable for catalytic selectivity and stability for the production of AA whereas the neutral KNO/silica systems favour catalytic selectivity and stability for the production of AA. A combination of catalytic and TGA studies indicates that the interaction between KNO and silica has a strong promotional effect on catalytic stability for the production of AA. A combination of IR monitoring and catalytic studies suggests that the effects of the surface acidity and the interactions between the potassium salt or base and silica on the catalytic performance are associated with the content and stability of potassium lactate as the catalytic active species. The catalyst stabilization and deactivation under LA dehydration conditions are discussed in detail. The neutral KNO/silica systems enable the formation of potassium lactate to become dominant whereas the unsupported KNO and acidic KNO/silica systems lead to the formation of poly(potassium acrylate), catalyst deactivation. This contribution includes for the first time that the dehydration of LA to AA proceeds smoothly with a neutral heterogeneous catalyst.
我们深入研究了 KNO 衍生的硅负载乳酸钾催化剂,通过催化测试、红外光谱监测、氨程序升温脱附、异丙胺程序升温脱附、吡啶吸附红外光谱和热重分析(TGA)对其进行了研究。催化和酸性质研究的结合表明,酸性 KNO/硅体系不利于 LA 气相脱水制备 AA 的催化选择性和稳定性,而中性 KNO/硅体系有利于 LA 气相脱水制备 AA 的催化选择性和稳定性。催化和 TGA 研究的结合表明,KNO 与硅之间的相互作用对 AA 生产的催化稳定性具有很强的促进作用。红外监测和催化研究的结合表明,表面酸度以及钾盐或碱与硅之间的相互作用对催化性能的影响与乳酸钾作为催化活性物种的含量和稳定性有关。详细讨论了 LA 脱水条件下催化剂的稳定和失活。中性 KNO/硅体系有利于形成乳酸钾,而无载体 KNO 和酸性 KNO/硅体系则导致多(聚丙烯酸钾)的形成,从而使催化剂失活。这一贡献首次表明,中性多相催化剂可使 LA 顺利脱水生成 AA。