Department of Applied Chemistry, School of Engineering, University of Toyama, Gofuku 3190, Toyama 930-8555, Japan.
J Am Chem Soc. 2010 Jun 16;132(23):8129-36. doi: 10.1021/ja101882a.
Dimethyl ether (DME) is an industrially important intermediate, as well as a promising clean fuel, but the effective production through traditionally consecutive steps from syngas to methanol and then to DME has been hindered by the poorly organized structure of the conventional physical mixture catalyst. Here, a novel zeolite capsule catalyst possessing a core-shell structure (millimeter-sized core catalyst and micrometer-sized acidic zeolite shell) was proposed initially through a well-designed aluminum migration method using the core catalyst as the aluminum resource and for the first time was applied to accomplish the DME direct synthesis from syngas. The selectivity of the expected DME on this zeolite capsule catalyst strikingly exceeded that of the hybrid catalyst prepared by the traditional mixing method, while maintaining the near-zero formation of the unexpected alkanes byproduct. The preliminary methanol synthesis reaction on the core catalyst and the following DME formation from methanol inside the zeolite shell cooperated concertedly and promoted mutually. This zeolite capsule catalyst with a synergetic confinement core-shell structure can be used to efficiently realize the combination of two and more sequential reactions with many synergistic effects.
二甲醚(DME)是一种重要的工业中间体,也是一种有前途的清洁燃料,但通过传统的从合成气到甲醇再到 DME 的连续步骤有效生产受到传统物理混合催化剂结构不合理的阻碍。在这里,我们首次通过设计良好的铝迁移方法提出了一种具有核壳结构(毫米级核催化剂和微米级酸性沸石壳)的新型沸石胶囊催化剂,该方法以核催化剂为铝源,并首次应用于从合成气直接合成 DME。在这种沸石胶囊催化剂上,预期的 DME 的选择性明显超过了通过传统混合方法制备的混合催化剂的选择性,同时保持了副产物烷烃的形成接近零。核催化剂上的初步甲醇合成反应和随后在沸石壳内从甲醇形成 DME 协同作用并相互促进。这种具有协同限域核壳结构的沸石胶囊催化剂可用于高效实现具有许多协同效应的两个或更多个连续反应的组合。