催化甘油脱水氧化连续反应的酸碱位共存粘土基催化剂研究

设计制备同时具有酸性位和碱性金属氧化物位的无机固体催化剂，是研发催化甘油脱水氧化连续反应制丙烯酸新过程中的关键问题。基于申请者对甘油脱水和氧化反应的前期研究，项目提出Cu-Al-Mg碱性阴离子粘土和酸性皂石阳离子粘土片层解离再组装的新思路，在酸性皂石片层间原位生成Cu-Al-Mg碱性复合氧化物，制成酸位和碱位共存的固体材料，表征认识碱、酸位的形态、组成、形成机制和催化甘油脱水氧化行为；主要研究调控片层解离和组装的方法及作用原理，考察前驱体片层组成、电荷密度、尺度等因素对催化剂中酸性位和碱性复合氧化物活性位数量、类型、分布、微结构、键合状态及催化性的影响；重点揭示催化剂中皂石片层酸性和碱性复合氧化物活性位的调控机制，认识其催化甘油脱水氧化连续反应生成丙烯酸的匹配条件及内在原因，弄清制备、结构与催化作用特征之间的相互关系。该思路和内容在国内外尚未有报道，系催化、粘土和生物基化学品化工交叉研究。

The preparation of well-designed inorganic solid catalysts combining acidic sites and basic metal oxide sites is a primary issue for the novel process of heterogeneously catalytic consecutive dehydration-oxidation of glycerol to produce acrylic acid. Based on previous studies on the catalysts for catalytic dehydration of glycerol and catalytic oxidation of glycerol, the present proposal suggests an innovative novel methodology for the preparation of coexisting acid-base solids catalysts from the combination of anionic clay layers and cationic clay layers by means of delamination and then the re-assembly, following by in situ transformation of the anionic Cu-Al-Mg clay nanolayers in the interlayer space of acidic saponite clay into basic Cu-Al-Mg oxides. In this way, a type of solid catalysts with coexisting acidic and basic sites for catalytic dehydration and oxidation of glycerol can be obtained. In particular, physicochemical approaches to the delamination and re-assembly of saponite layers and anionic Cu-Al-Mg clay layers in a layer-by-layer way will be developed and the formation mechanism will be examined. And the effects of the composition, the layer charge density, the size of layers of the layered precursors on the amount, type, distribution of surface acidity and basicity, microstructure, chemical bonds and catalytic performances of the resulting catalysts will be investigated. Emphasis will be put on revealing the formation mechanism, the tuning methods and principles of acidic sites from saponite layers and basic sites from Cu-Al-Mg oxides in the resulting catalysts. The well-matched recation conditions for the consecutive dehydration-oxidation of glycerol to produce acrylic acid.the will be identified. For such catalysts, the correlation among the preparation factors, the structural parameters and the catalytic properties in the heterogeneously catalytic consecutive dehydration-oxidation of glycerol will be disclosed and the inherent reasons will be theoretically elaborated. To our knowledge, such a preparation route to the catalysts with coexisting acidic and basic sites for catalytic oxidation and dehydration of glycerol and scientific investigation therein have not yet been reported at home and abroad. It belongs to a multidisciplinary topic involving in catalysis, clay minerals and the processing of bioresource-based chemical feedstocks.