Catalytic Deoxydehydration of Biomass-Derived Polyols to Olefins

生物质多元醇催化脱氧脱水制烯烃

• 批准号: 1160219
• 负责人: Friederike Jentoft
• 金额: $ 42.5万
• 依托单位: University of Oklahoma Norman Campus
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2012
• 资助国家: 美国
• 起止时间: 2012-08-01 至 2016-03-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1160219&HistoricalAwards=false
• 关键词: Catalytic; Deoxydehydration; Biomass; Derived; Polyols

ABSTRACT#1160219P.I.: Friederike C. JentoftThe key chemical transformations that are needed in the conversion of biomass into fungible fuels or useful chemical intermediates, such as olefins, are characterized by effectively removing oxygen ideally without significant loss of carbon. One approach would be to achieve this employing several catalytic conversion processes, allowing each to be optimized in terms of catalyst employed. Polyols, molecules with multiple OH functionalities, are easily obtainable from cellulosic biomass in known conversion processes. Principal investigators Friederike C. Jentoft and Kenneth M. Nicholas of the University of Oklahoma are proposing to develop novel, heterogeneous catalysts that will convert biomass-derived polyol substrates in liquid phase, hydrophilic media. The target reaction is a deoxydehydration, that is, oxygen and water will be removed simultaneously by reduction and dehydration, respectively. With the help of a sacrificial reducing agent, the net loss of two OH groups from the polyol can be effected, and a versatile olefinic product is obtained.The primary objectives of this project are to develop supported oxo-metal complexes as catalysts for the deoxydehydration of polyols to olefinic products, to identify the reactive oxo-metal species involved in these processes and to elucidate the reaction mechanism. Achievement of the project?s objective will be facilitated by the synergistic interaction between the Nicholas group in the Department of Chemistry & Biochemistry and the Jentoft group in the School of Chemical, Biological and Materials Engineering. The groups combine expertise in organometallic chemistry and homogeneous catalysis with expertise in heterogeneous catalysis and spectroscopy. The PIs will explore an array of catalyst compositions, with candidate transition metals for the oxo-complexes being rhenium, molybdenum and vanadium, and candidates for supports being activated carbon, ceria, and layered double hydroxides. The catalytic activity, selectivity and stability of these materials for deoxydehydration of polyols will be tested using sulfites and molecular hydrogen as reducing agents and a variety of conditions and solvents. The key steps in the catalytic deoxydehydration processes will be elucidated by spectroscopically monitoring the interaction of deoxydehydration reductants and glycols with active supported oxo-metal complexes. Successful execution of this research project will: 1) establish a new, potentially useful, chemical transformation of cellulosic- and glycolic feedstocks for the sustainable preparation of value-added unsaturated products and intermediates that can be further converted by existing processes; 2) provide fundamental knowledge and understanding of chemical reactions involving carbohydrate/polyol substances, supported metal-oxo species, practical reductants, and suitable reaction media; and 3) supply cutting-edge cross-disciplinary educational and technical training in the key discipline of catalysis for undergraduate and graduate students as well as for postdoctoral researchers.

摘要＃1160219p.i。：弗里德斯式C. Jentoft在生物质转化为可函数燃料或有用的化学中间体（例如烯烃）中所需的关键化学转化，其特征是有效地去除氧气，理想地不损失碳。一种方法是采用多个催化转化过程实现这一目标，从而使每个转化过程都可以根据所使用的催化剂进行优化。多元醇，具有多个OH功能的分子，在已知的转化过程中很容易从纤维素生物量中获得。俄克拉荷马大学的主要研究人员Friederike C. Jentoft和Kenneth M. Nicholas提议开发新型的异质催化剂，这些催化剂将在液相，亲水培养基中转换生物质衍生的多元元素。靶反应是一种脱氧脱水，即氧和水将分别通过还原和脱水同时去除。借助牺牲性还原剂，可以实现两组OH组的净损失，并获得多功能的烯烃产物。该项目的主要目标是将支持的氧化型络合物作为催化剂，作为脱氧氧化物的催化剂，以对氧化氧化产物的脱氧作用，以识别反应性氧化物，以识别这些过程，以识别这些过程中的这些方法和这些方法。化学，生物学和生物学和材料工程学院的尼古拉斯集团之间的协同互动将促进该项目目标的实现。两组结合了有机金属化学和同质催化的专业知识，以及异质催化和光谱方面的专业知识。 PIS将探索一系列催化剂组成，其中氧型复合物的候选过渡金属为rhenium，moleybdenum和vanadium，以及候选候选者，用于激活碳，ceria和分层双氢氧化物。这些材料对多元醇的脱氧脱水的催化活性，选择性和稳定性将使用亚硫酸盐和分子氢作为还原剂以及多种条件和溶剂进行测试。通过光谱监测脱氧脱氧水还原剂和乙二醇与主动支持的氧氧化型络合物的相互作用，将阐明催化脱氧脱氧过程的关键步骤。该研究项目的成功执行将：1）建立一种新的，潜在的有用的，化学的化学转化，对纤维素和乙醇原料的原料进行可持续制备，以实现增值不饱和产品和中间体，可以通过现有过程进一步转化； 2）提供涉及碳水化合物/多元醇物质，支持的金属氧化物种，实用还原剂和合适反应培养基的化学反应的基本知识和理解； 3）在本科和研究生以及博士后研究人员的催化关键学科中，提供尖端的跨学科教育和技术培训。

项目成果

New solid oxo-rhenium and oxo-molybdenum catalysts for the deoxydehydration of glycols to olefins

用于二醇脱氧脱水生成烯烃的新型固体氧代铼和氧代钼催化剂

• DOI: 10.1016/j.cattod.2017.05.090
• 发表时间: 2018
• 期刊: Catalysis Today
• 影响因子: 5.3
• 作者: Sharkey, Bryan E.;Denning, Alana L.;Jentoft, Friederike C.;Gangadhara, Raju;Gopaladasu, Tirupathi V.;Nicholas, Kenneth M.
• 通讯作者: Nicholas, Kenneth M.