Catalytic Hydrodeoxygenation of Sugar Acids to Dicarboxylic Acids

糖酸催化加氢脱氧为二羧酸

• 批准号: 1817297
• 负责人: Yomaira Pagan Torres
• 金额: $ 30万
• 依托单位: University of Puerto Rico Mayaguez
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2018
• 资助国家: 美国
• 起止时间: 2018-02-01 至 2021-01-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1817297&HistoricalAwards=false
• 关键词: Catalytic; Hydrodeoxygenation; Sugar; Acids; Dicarboxylic

Exploratory research will be conducted to assess the feasibility of potentially transformative catalyst technology for manufacturing dicarboxylic acids from renewable sources of carbon such as lignocellulosic biomass. Current industrial processes for these acids - which are used widely in the production of polymers, pharmaceuticals, solvents, textiles, and plastics - rely on petrochemical feedstocks derived from fossil sources, and utilize relatively harsh conditions and energy-intensive separations. Biomass sources potentially offer a more direct synthesis route while contributing to energy sustainability. The study will address challenges associated with specific chemical reactions at oxygen-containing groups in the carbon structure, while also exploring catalyst formulations that decrease the need for expensive precious metal catalyst components. Recently, interest has surged in the production of dicarboxylic acids from renewable sources, mainly via fermentation of glucose or through further processing of waste byproducts from natural bio-processing such as tartaric acid from wine-making. Specifically, the study will target two model tartaric acid reactions: deoxydehydration to maleic acid and hydrodeoxygenation to succinic acid, both carried out in commonly available solvents. The study will address two overarching objectives, 1) the development of a heterogeneous catalyst comprised of rhenium oxide supported on gallium-promoted cerium dioxide, and 2) a study of the catalytic performance of the rhenium oxide catalysts, prepared in various ways, on the deoxydehydration and hydrodeoxygenation of vicinal diols in tartaric acid. A key aspect of the study is the extent to which supporting the rhenium oxide on the gallium-promoted cerium dioxide can enhance the stability of the catalyst while eliminating the need for common precious metal components such as palladium or iridium, thus paving the way for more durable and lower cost catalysts. Successful demonstration of the proposed catalyst formulation depends on the extent to which the gallium-promoted cerium oxide support can both stabilize isolated monomeric rhenium oxide species (of varying oxidation state) and achieve the facile dissociation of hydrogen gas, as required for the sequential hydrogenation reactions and for regeneration of the active rhenium site. Both of those functions are typically achieved through the incorporation of palladium in the catalyst synthesis. Data suggesting the possibility of eliminating the expensive noble metal component, while stabilizing the active rhenium species, would open a path to transformative catalyst technologies for producing dicarboxylic acids from biorenewable carbon feedstocks. The study also includes an education plan aimed at increasing the involvement of undergraduate Hispanic women in research, and enhancing undergraduate curricula at the PI's institution in key areas related to nanotechnology, engineering materials, and renewable energy.

将进行探索性研究，以评估从木质纤维素生物质等可再生碳源制造二羧酸的潜在变革性催化剂技术的可行性。目前这些酸的工业流程——广泛用于聚合物、药品、溶剂、纺织品和塑料的生产——依赖于来自化石资源的石化原料，并利用相对苛刻的条件和能源密集型分离。生物质资源可能提供更直接的合成途径，同时有助于能源的可持续性。该研究将解决与碳结构中含氧基团的特定化学反应相关的挑战，同时也将探索减少对昂贵的贵金属催化剂成分需求的催化剂配方。最近，人们对利用可再生资源生产二羧酸的兴趣激增，主要是通过葡萄糖发酵或通过进一步处理自然生物加工过程中的废弃副产品，如酿酒过程中的酒石酸。具体来说，该研究将针对两种模型酒石酸反应：脱氧脱水制马来酸和氢脱氧制琥珀酸，这两种反应都是在常用的溶剂中进行的。该研究将解决两个主要目标，1)开发一种由氧化铼支撑在镓促进的二氧化铈上组成的多相催化剂，2)研究以各种方式制备的氧化铼催化剂对酒石酸中邻二醇的脱氧脱水和加氢脱氧的催化性能。该研究的一个关键方面是在多大程度上支持氧化铼在镓促进的二氧化铈上可以提高催化剂的稳定性，同时消除对钯或铱等常见贵金属成分的需求，从而为更耐用和更低成本的催化剂铺平道路。所提出的催化剂配方的成功演示取决于镓促进的氧化铈载体在多大程度上既能稳定分离的单体氧化铼（不同氧化状态），又能实现氢气的易解离，这是连续氢化反应和活性铼位点再生所必需的。这两种功能通常都是通过在催化剂合成中加入钯来实现的。数据表明，在稳定活性铼的同时，消除昂贵的贵金属成分的可能性，将为从生物可再生碳原料中生产二羧酸的变革性催化剂技术开辟一条道路。这项研究还包括一项教育计划，旨在增加西班牙裔本科生妇女参与研究，并加强PI所在机构在纳米技术、工程材料和可再生能源等关键领域的本科课程。

项目成果

Selective C−O Bond Cleavage of Bio‐Based Organic Acids over Palladium Promoted MoO x /TiO 2

钯促进的 MoO x /TiO 2 上生物基有机酸的选择性 C–O 键断裂

• DOI: 10.1002/cctc.202001799
• 发表时间: 2020
• 期刊: ChemCatChem
• 影响因子: 4.5
• 作者: Nacy, Ayad;de Lima e Freitas, Lucas Freitas;Albarracín‐Suazo, Sandra;Ruiz‐Valentín, Génesis;Roberts, Charles A.;Nikolla, Eranda;Pagán‐Torres, Yomaira J.
• 通讯作者: Pagán‐Torres, Yomaira J.