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: 1630100
• 负责人: Friederike Jentoft
• 金额: $ 18.6万
• 依托单位: University of Massachusetts Amherst
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2015
• 资助国家: 美国
• 起止时间: 2015-09-01 至 2018-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1630100&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.：Friederike C. 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点是有效去除氧气，理想情况下不会显着损失碳。一种方法是采用多种催化转化工艺来实现这一目标，从而使每种工艺都可以在所用催化剂方面进行优化。多元醇是具有多个OH官能团的分子，可以通过已知的转化过程从纤维素生物质中容易地获得。俄克拉荷马大学的首席研究员 Friederike C. Jentoft 和 Kenneth M. Nicholas 提议开发新型多相催化剂，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，即分别通过还原和脱水同时除去氧和水。在牺牲还原剂的帮助下，可以实现多元醇中两个羟基的净损失，并获得多用途的烯烃产品。该项目的主要目标是开发负载型含氧金属络合物作为多元醇脱氧脱水成烯烃产品的催化剂，以确定这些过程中涉及的反应性含氧金属物种并阐明反应机理。化学与生物化学系的 Nicholas 小组与化学、生物和材料工程学院的 Jentoft 小组之间的协同互动将促进该项目目标的实现。该小组将有机金属化学和均相催化方面的专业知识与多相催化和光谱学方面的专业知识相结合。 PI将探索一系列催化剂组合物，其中氧化络合物的候选过渡金属是铼、钼和钒，载体的候选材料是活性炭、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对多元醇脱氧脱水的催化活性、选择性和稳定性。通过光谱监测脱氧脱水还原剂和二醇与活性负载的含氧金属配合物的相互作用，可以阐明催化脱氧脱水过程的关键步骤。该研究项目的成功执行将：1）建立一种新的、潜在有用的纤维素和乙醇原料化学转化方法，用于可持续制备增值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、负载金属氧物质、实用还原剂和合适反应介质的化学反应的基础知识和理解； 3）为本科生、研究生以及博士后研究人员提供催化关键学科前沿的跨学科教育和技术培训。

项目成果

Fundamental Insights into Deactivation by Leaching during Rhenium-Catalyzed Deoxydehydration

铼催化脱氧脱水过程中浸出失活的基本见解

• DOI: 10.1021/acscatal.9b02806
• 发表时间: 2019
• 期刊: ACS Catalysis
• 影响因子: 12.9
• 作者: Sharkey, Bryan E.;Jentoft, Friederike C.
• 通讯作者: Jentoft, Friederike C.

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.