Conversion of Bioethanol to Butadiene for Manufacture of Green Tires

以色列E.WachsProposal编号：1605805当今使用的许多重要化学品都是从不可再生的石油资源中提取的。一个重要的例子是丁二烯，它被转化为用于制造轮胎的合成橡胶。使轮胎生产更具可持续性的一种方法是寻找丁二烯的非石油替代品。可再生纤维素生物燃料和生物炼油厂生产的乙醇有可能成为合成橡胶生产的替代原料，如果能找到合适的催化剂将乙醇转化为丁二烯的话。该项目将在分子水平上寻求对乙醇与金属氧化物催化剂表面相互作用的基本了解，以发现将乙醇转化为丁二烯所需的最佳催化剂类型和最佳条件。这项拟议的研究有可能带来一条可行的途径，以较低的碳足迹从可持续的原料中生产合成橡胶。与该项目相关的教育活动包括在德国一家著名的催化剂研究所为学生提供研究的国际机会，以及开发可持续化学品和燃料的推广模块。该研究的总体目标是阐明生物乙醇催化转化为丁二烯的分子结构-反应性/选择性关系。这一目标将通过催化剂合成、表面化学光谱分析、分子计算和瞬时反应动力学分析的综合研究来实现。为了探索二氧化硅负载的活性金属氧化物相区大小、局域结构、氧化态、酸碱氧化还原特性以及活性金属氧化物之间的相互作用，我们将合成一系列明确的催化剂。在反应条件下，催化剂将通过原位光谱和操纵谱在分子水平上进行表征。乙醇的表面化学将通过程序升温表面反应(TPSR)光谱进行探索，而同位素标记将有助于揭示参与偶联反应生成丁二烯的特定分子官能团的反应途径。稳态同位素瞬时动力学分析(SSITKA)反应研究将提供有关反应网络和速率决定步骤的更多动力学细节。实验结果将得到理论计算的补充，以获得对每个催化步骤所需的活性中心的更深层次的分子水平的理解。所有这些信息将结合起来建立结构-活性/选择性关系，以指导生物乙醇转化为丁二烯的改进催化剂的分子设计。

PI Name: Israel E. WachsProposal Number: 1605805Many important chemicals in use today are derived from non-renewable petroleum resources. An important example is butadiene, which is converted to synthetic rubber used in manufacture of tires. One approach to make tire manufacture more sustainable is to find a non-petroleum substitute for butadiene. Ethanol produced from renewable cellulosic biofuel and bio-refinery operations is potentially an alternative feedstock for synthetic rubber production, if a suitable catalyst to drive the conversion of ethanol to butadiene can be found. This project will seek fundamental understanding of the interaction of ethanol with metal oxide catalyst surfaces at the molecular level to discover the best type of catalyst and the optimal conditions needed to convert ethanol to butadiene. The proposed research has the potential to lead to a viable pathway to produce synthetic rubber from sustainable feedstocks with a lower carbon footprint. The educational activities associated with the project include international opportunities for student research at a renowned catalyst research institute in Germany, as well as the development of modules for outreach on sustainable chemicals and fuels.The overall goal of the research is to elucidate the molecular level structure-reactivity/selectivity relationships for the catalytic conversion of bioethanol to butadiene. This goal will be accomplished through an integrated study of catalyst synthesis, spectroscopic analysis of surface chemistry, molecular calculations, and transient reaction kinetics analysis. A well-defined series of catalysts will be synthesized to explore the effects of the silica-supported active metal oxide phase domain size, local structure, oxidation state, acid-base-redox characteristics and interactions between the active metal oxides. The catalysts will be characterized at the molecular level with in situ and operando spectroscopy under reaction conditions. The ethanol surface chemistry will be probed with Temperature Programmed Surface Reaction (TPSR) spectroscopy, and isotopic labeling will assist in revealing the reaction pathways of specific molecular functionalities involving in the coupling reaction to yield butadiene. Steady State Isotopic Transient Kinetic Analysis (SSITKA) reaction studies will provide additional kinetic details about the reaction network and rate-determining-steps. The experimental findings will be complemented with theoretical calculations to get a deeper, molecular- level understanding of the active sites required for each catalytic step. All of this information will be combined to establish structure-activity/selectivity relationships to guide the molecular design of improved catalysts for the conversion of bioethanol to butadiene.