褐煤Car-Cal键合结构的催化活化及其导向控制部分解聚制低环芳烃

The depolymerization production of high value fine organic chemicals with low aromatic structure from Inner Mongolia lignite，containing a large proportion of facile depolymerization and degradable oil-likeable component content，is the optimal way to use their sub-quality. Increasing of the low aromatic structure monomer is crucial to the yield of high value fine organic chemicals. Based on the structure characteristics of Car-Cal bridge linkages or side bonds，metal component will be prepared and screened according to catalysis tests. The key reaction activated sites，formed Metal-Bridge Cluster linking the metal and Car-Cal，and their transformation process under mild depolymerization reaction will be studied by GC/MS，UV-vis spectra，FT-IR spectra，Synchronous Fluorescence spectra，FT-ICR MSFTIR，XRD，HRTEM，SEM，XPS，13C NMR，EELS and NEXAFS/XANES. The inherent relationship and characterizations of depolymerization reaction will be revealed based on the dependence of reactivity on the Metal-Bridge Cluster microstructure and their transformation during the reaction process. The catalytic mechanism of the selected metal compound on the depolymerization reaction will be cleared in the presentation of mechanism catalytic model. The result will greatly improve the production of low aromatic structure monomer from Inner Mongolia lignite under mild depolymerization reaction. The precise activation of Car-Cal bond by the metal component during mild depolymerization reaction will make sure the route of depolymerization reaction controlled by the cleavage of bridge linkages，removing of side to aromatic ring，retention of aromatic ring and suppression of polymerization among produced low aromatic structure monomer. The theoretical discovery of this project will provide a theoretical basis and technical support for the development and utilization of production of high value fine organic chemicals from Inner Mongolia lignite.

褐煤中高含量的1~3低环芳香(杂环)结构体，主要由Car-Cal键合结构连接，制取低芳环高价值精细有机化学品是其分质利用的最佳途径，而提高解聚过程低环芳香单体数量至关重要。项目基于内蒙褐煤富含的Car-Cal键合结构特性及其与金属组分的键合能力，制备及筛选金属催化组分，研究其与Car-Cal键合结构所形成Metal-Bridge Cluster微结构形态特征、温和解聚反应过程中Metal-Bridge Cluser微结构特征转化规律，揭示内蒙褐煤解聚反应性与Metal-Bridge Cluster微结构特征之间的内在关系及金属组分催化作用机理，建立金属组分对其解聚反应的催化作用机理模型。对Car-Cal键合结构进行精准活化，使其在温和反应条件下，沿着“断桥去侧，留环抑聚”途径进行反应，促进低环芳香结构单体生成，进而制备低芳环高价值精细有机化学品，可为褐煤高效梯级利用提供理论依据与技术支持！

基于褐煤等低阶煤组成中富含芳香结构和酸性含氧官能团，围绕固有矿物质对其气化反应过程的催化作用，针对Ca在褐煤气化反应的催化机理与其热反应过程结构演变特性之间的关系进行了深入系统的研究，揭示了Ca对胜利褐煤气化反应的催化机制并建立相应的催化气化反应机理模型；同时，提出利用褐煤等低阶煤或其衍生物中酸性含氧官能团构建金属-有机复合催化剂的新思路，围绕褐煤的定向解聚和解聚物利用，探索解聚方法与解聚工艺条件的优化，研究褐煤定向解聚以获得低环芳香结构等解聚产物、解聚产物分离的新方法，并将(分离/不分离)解聚产物用于构筑“类MOFs结构”的“金属-解聚物/残留物架构催化剂”，系统研究了温和条件下褐煤解聚物、褐煤原煤/酸洗褐煤、褐煤氧化解聚产物构建催化剂的具体制备工艺基础路线，回避褐煤热处理或褐煤解聚物产物难以分离的困难，制备路线具有条件温和、工艺路线简单的优点，优化条件下所制备金属-解聚物/残留物架构催化剂”在生物质衍生分子的催化转化反应表现出优良的催化性能。本项目为褐煤等低阶煤非能源利用的提供了新思路、新途径。