SusChEM: Defining a Disruptive Biorefinery Concept

主要研究者：Mascal，Mark建议编号：1335646机构：加州大学戴维斯分校标题：SusChEM：定义一个破坏性的生物精炼厂概念该提案描述了一个完全化学催化生物精炼厂的概念，不涉及发酵或热生物质加工方法。该项目的第一部分研究了操作简单、不可逆的C-C偶联反应，这些反应导致糖中碳主链的延伸。生物质衍生的戊糖和己糖的电化学偶联得到C10-12糖醇被提出;一个工业相关的反应，使用尽可能便宜的试剂-电子。PI还将研究C6酸葡萄糖酸的阳极脱羧，这可以导致C10宏糖，以及相应的二酸盐（葡萄糖二酸盐）的柯尔贝电解的产物。这些分子，当进行下述加氢脱氧方案时，将得到直链C10+烃，其是柴油燃料和大量石油基化学品的原料的主要成分。这里的领先优势在于，目标偶联产物（还原性和氧化性）先前已经作为其他反应的副产物被观察到。该项目的第二部分在温和的条件下将扩展的糖醇催化还原为直链烷烃，不会导致C-C键断裂。由于糖醇在酸性条件下形成环醚的强烈倾向，以及环醚在强酸存在下通过氢化可以相对容易地还原裂解，这成为一种可能。在研究基础设施和多样性方面的更广泛的影响在于该计划？的跨学科性质，包括在各个点有机电化学，催化，两相反应动力学，并与电力系统工程师的互动。该提案的教育目标与PI密切相关？的研究以及他在教学创新的兴趣。

PI: Mascal, MarkProposal Number: 1335646Institution: University of California-DavisTitle: SusChEM: Defining a Disruptive Biorefinery ConceptThis proposal describes the concept of a fully chemical-catalytic biorefinery, involving at no point either fermentative or thermal biomass processing methods. The outcome will be an exceptionally efficient, versatile system for converting biomass into renewable, drop-in automotive fuels, chemicals, and combustible solids for power generation.The first part of the project examines operationally simple, irreversible C-C coupling reactions that lead to extended carbon backbones in sugars. The electrochemical coupling of biomass-derived pentoses and hexoses to give C10-12 glycitols is proposed; an industrially relevant reaction that uses the cheapest possible reagent-the electron. The PI will also investigate the anodic decarboxylation of the C6 acid gluconate, which can lead to a C10 macrosugar, as well as the products of the Kolbe electrolysis of corresponding diacid salt (glucarate). These molecules, when submitted to the hydrodeoxygenation protocol described below, will give linear C10+ hydrocarbons, which are the main constituents of diesel fuel and feedstocks for a plethora of petroleum-based chemicals. A head-start advantage here is that the target coupling products, both reductive and oxidative, have previously been observed as side products of other reactions. The second part of the project catalytically reduces extended glycitols to linear alkanes under gentle conditions which do not lead to C-C bond cleavage. This becomes a possibility due to the powerful tendency of sugar alcohols to form cyclic ethers under acidic conditions, and the relative ease with which cyclic ethers can be reductively cleaved by hydrogenation in the presence of a strong acid. The broader impacts in terms of research infrastructure and diversity lie in the program?s interdisciplinary nature, encompassing at various points organic electrochemistry, catalysis, biphasic reaction dynamics, and interactions with power systems engineers. The educational goals of the proposal are closely linked to the PI?s research as well as his interests in pedagogical innovations.