层板开孔层间多元分柱Mo-W-V氧化物/粘土催化剂构筑及其在催化甘油脱水氧化中的抗积碳调控机制研究

催化甘油脱水氧化反应制丙烯酸有重大产业需求，申请人前期和国内外研究表明，催化剂积碳失活是制约其工业化应用的瓶颈；核心难点是催化剂需孔道超级开放和表面酸、氧化、抗积碳等多元活性组分共存，且要“对症”积碳机制能给予调控。由此，本项目提出利用蒙脱石、皂石粘土矿物二维层板和层间理化特性，设计采用层板酸适度剪切和开口、层间引入“分体式”多元组分层柱的新策略，创制超级开孔且酸、氧化、抗积碳性均可调变的系列Mo-W-V复合氧化物/粘土催化剂，通过碳质精细分析、碳质前驱物表面吸附、表面反应和同位素示踪等方法，解析碳质本质，表征认识催化剂微结构和表面酸、氧化、抗积碳等多元活性位数量、类型、分布、键合状态影响积碳的本质，揭示积碳关键因素、形成机理和催化剂组成结构间的内在关系，进而明确“对症”调控开孔和表面多元活性组分的机制及优选原则，确立新催化剂制备化学，为高活性抗积碳催化剂理性设计和走向产业提供科学基础。

Catalytic dehydration-oxidation of glycerol is needed for producing acrylic acid in industry. Previous studies of the applicant and literature survey have indicated that the rapid deactivation of catalyst caused by coking is the bottleneck hindering the new process to be used in industry. The core issues are that the suitable catalysts need super-opening porosity and coexistence of multiple active components for proper surface acidity, oxidation and coking-resistance. Meanwhile, those factors should be tuned based on the nature of coking. Hence, by taking advantage of the peculiar physical and chemical properties of the layer and interlayer of two-dimensional layered montmorillonite and saponite clay minerals, a new creative strategy is here proposed. The super-porosity will be created by proper acid treatment of the clay layers. And multiple active components will then be individually introduced into the interlayer spaces. In this way, a series of novel Mo-W-V oxides/acidified clay catalysts can be successfully prepared with individually adjustable active sites of acidity, oxidation and coking-resistance. The coke will be chemically analyzed, and the coke precursors and coking reactions will be probed by surface adsorption, surface reactions, and isotope labelling and tracking experiments to unveil the nature of coking. The catalysts will be characterized to get the detailed information on the micro-structure, number, type, distribution, bonding of active sites of acidity, oxidation and coking-resistance on the Mo-W-V oxides/clay catalysts. Their roles in the coking will be examined and revealed. As such, the inherent relationship of the critical factors and the formation mechanism of coke and catalyst composition-structure will be disclosed. Such information will then be used with clear aims to tune the porosity of the catalysts and the multiple active components on the surface of the catalysts during the preparation. Thus, the preparation chemistry of new catalysts can be established according to the unveiled laws and optimization of principle. The proposed study will provide a scientific basis for the rational design of a high active and anti-coking catalyst, pushing it into industrial practice.