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.

摘要编号1160219 P.I.：弗里德里克角Jentoft将生物质转化为可替代燃料或有用的化学中间体（例如烯烃）所需的关键化学转化的特征是有效去除氧气，理想情况下不会显着损失碳。一种方法是采用几种催化转化方法来实现这一点，允许每种方法在所用催化剂方面进行优化。多元醇，具有多个OH官能团的分子，可以在已知的转化方法中容易地从纤维素生物质获得。首席研究员Friederike C. Jentoft和Kenneth M.俄克拉荷马州大学的Nicholas等人正在提议开发新型的多相催化剂，该催化剂将在液相亲水介质中转化生物质衍生的多元醇底物。目标反应是脱氧脱水，即氧气和水将分别通过还原和脱水同时去除。本项目的主要目的是开发负载型含氧金属配合物催化剂，用于多元醇脱氧脱水制烯烃产品，确定参与这些过程的活性含氧金属物种，并阐明反应机理。项目的成果？化学生物化学系的Nicholas小组和化学、生物和材料工程学院的Jentoft小组之间的协同作用将促进该项目的目标。这些小组将有机金属化学和均相催化的专业知识与多相催化和光谱学的专业知识相结合。PI将探索一系列催化剂组合物，其中氧代络合物的候选过渡金属是钼，钼和钒，载体的候选物是活性炭，二氧化铈和层状双氢氧化物。将使用亚硫酸盐和分子氢作为还原剂以及各种条件和溶剂来测试这些材料用于多元醇脱氧脱水的催化活性、选择性和稳定性。在催化脱氧脱水过程中的关键步骤将阐明通过光谱监测脱氧脱水还原剂和乙二醇与活性支持的氧代金属配合物的相互作用。该研究项目的成功实施将：1）建立一种新的，潜在有用的，纤维素和乙醇原料的化学转化，用于可持续地制备增值的不饱和产品和中间体，这些产品和中间体可以通过现有工艺进一步转化; 2）提供涉及碳水化合物/多元醇物质、负载的金属-含氧物质、实用还原剂的化学反应的基本知识和理解，和合适的反应介质; 3）为本科生和研究生以及博士后研究人员提供催化关键学科的前沿交叉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.