EAGER: Directed Ozonolysis in Liquid Carbon Dioxide

PI：Bala Subramanian 机构：堪萨斯大学研究中心公司 提案编号：1128186 标题：EAGER：液体二氧化碳中的定向臭氧分解 目的和目标：该 EAGER 项目旨在为将臭氧分解建立为生产工业化学品和燃料的可行技术奠定基础。最近的发现表明，与传统溶剂相比，O3 在液态 CO2 中的溶解度显着增强。这一发现促使开展这项研究，旨在探索液态二氧化碳中的受控臭氧分解是否可以用多种底物进行。因此，具体目标是研究 (a) 臭氧在惰性溶剂（例如浓二氧化碳）中的混溶性和稳定性，旨在建立适当的臭氧分解介质； (b) 在液态CO2中脂肪酸甲酯和芳香族结构（含有C=C键）的臭氧解过程中获得的转化率和选择性。意义：臭氧解能够通过氧化裂解C=C键和来自多芳香族结构（例如木质素）的直链烃来生产多种有价值的中间体，例如羧酸和醛。然而，由于保护反应中间体免遭进一步氧化以及寻找对臭氧呈惰性的可行溶剂的挑战，工业应用相对较少。研究活动：上述目标将通过一套日益复杂的模型基质来实现。初始底物将包括： (a) 二苯乙烯和环己烯； (b) 硬脂酸甲酯和油酸甲酯作为饱和和不饱和脂肪酸的模型； (c) 代表木质素天然产物中常见功能的芳香族化合物。实验研究将得到最先进的研究基础设施的支持，其中包括配备原位紫外-可见光谱、超声波混合和在线采样功能的高压观察池，用于进行反应和相平衡研究。智力优点：成功完成将为臭氧在工业化学品和燃料加工中的广泛应用奠定基础，具有促进可持续性的以下属性：在相对温和的条件下（数十巴和接近环境温度）进行过程强化，有效利用氧气以最大化所需的产品、废物最小化和固有安全性。与脂肪酸甲酯和聚芳烃底物相关的结果将为将木质纤维素生物质和天然油转化为燃料和化学品提供迄今为止尚未探索的反应途径。更广泛的影响：环境催化中心（CEBC）跨学科环境中的教师、学生和工业研究人员之间的协同互动预计将培养出一支由经过独特培训的多样化学生组成的骨干队伍，这些学生是通过CEBC的多元化招聘工作招募的。 PI 拥有培训来自代表性不足群体的学生的历史，其中包括通过与 Prairie View A&M 大学和波多黎各大学持续合作招募的女性和少数族裔学生。这些技术成果将被纳入正在进行的名为“可持续化学工艺开发”的研究生课程中，该课程由化学家和工程师团队授课。

PI: Bala Subramanian Institution: University of Kansas Center for Research Inc.Proposal Numbers: 1128186Title: EAGER: Directed Ozonolysis in Liquid Carbon DioxideGoals and Objectives: This EAGER project is aimed at laying the foundation to establish ozonolysis as a viable technology for producing industrial chemicals and fuels. Recent finding indicate that O3 solubility is dramatically enhanced in liquid CO2 compared to conventional solvents. This finding has prompted this investigation aimed at exploring whether controlled ozonolysis in liquid CO2 can be performed with a broad range of substrates. Specific objectives are therefore to investigate (a) ozone miscibility and stability in inert solvents such as dense CO2 aimed at establishing appropriate media for ozonolysis; (b) the conversion and selectivities obtained during ozonolysis of fatty acid methyl esters and aromatic structures (containing C=C bonds) in liquid CO2.Significance: Ozonolysis is capable of producing a rich variety of valuable intermediates such as carboxylic acids and aldehydes by oxidative cleavage of C=C bonds and linear hydrocarbons from polyaromatic structures such as lignin. However, there are relatively few industrial applications because of the challenges to protect reaction intermediates from further oxidation and to find viable solvents that are inert to ozone. Research Activities: The aforementioned objectives will be pursued with a suite of model substrates of increasing complexity. Initial substrates will include: (a) stilbene and cyclohexene; (b) methyl stearate and methyl oleate as model saturated and unsaturated fatty acids; and (c) aromatic compounds representative of functionalities commonly found in natural products derived from lignin. The experimental investigations will be supported by a state-of-the-art research infrastructure that includes high-pressure view cells equipped with in situ UV-Vis spectroscopy, ultrasound-enabled mixing and in-line sampling features for performing the reaction and phase equilibrium studies.Intellectual Merit: Successful completion will lay the foundation for widespread applications of ozone in industrial chemicals and fuels processing, with the following attributes that promote sustainability: process intensification at relatively mild conditions (tens of bars and near-ambient temperatures), efficient O3 utilization for maximizing the desired products, waste minimization and inherent safety. The outcomes associated with fatty acid methyl esters and polyaromatic substrates will provide a hitherto unexplored reaction pathway for transforming lignocellulosic biomass and natural oils to fuels and chemicals.Broader Impacts: The synergistic interactions between faculty, students and industrial researchers in a cross-disciplinary setting at the Center for Environmentally Catalysis (CEBC) is expected to produce a diverse cadre of uniquely trained students, recruited through the CEBC?s diversity recruitment efforts. The PI has a history of training students from under-represented groups including women and minority students recruited from ongoing partnerships with Prairie View A&M University and the University of Puerto Rico. The technical outcomes will be integrated into an ongoing graduate course titled Development of Sustainable Chemical Processes, which is team-taught by chemists and engineers.