EAGER: Directed Ozonolysis in Liquid Carbon Dioxide

项目负责人：Bala Subramanian机构：堪萨斯大学研究中心提案编号：1128186标题：EAGER：液态二氧化碳的定向臭氧分解目标和目的：该EAGER项目旨在为建立臭氧分解作为生产工业化学品和燃料的可行技术奠定基础。最近的研究表明，与传统溶剂相比，O3在液态CO2中的溶解度显着提高。这一发现促使本研究旨在探索是否可以在广泛的底物中进行受控的液态CO2臭氧分解。因此，具体目标是调查(a)臭氧在惰性溶剂（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)脂肪酸甲酯和芳香结构（含C=C键）在液态CO2中臭氧分解时的转化率和选择性。意义：臭氧分解能够通过氧化裂解C=C键和木质素等多芳结构的线性碳氢化合物，产生丰富多样的有价值的中间体，如羧酸和醛。然而，由于保护反应中间体免受进一步氧化和寻找对臭氧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模型饱和和不饱和脂肪酸；(c)代表木质素衍生的天然产物中常见功能的芳香族化合物。实验研究将由最先进的研究基础设施提供支持，包括配备了原位紫外可见光谱的高压观察细胞，超声波混合和在线采样功能，用于进行反应和相平衡研究。知识价值：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，具有以下促进可持续性的特性：在相对温和的条件下（几十巴和接近环境温度）强化过程，有效利用臭氧以最大化所需产品，尽量减少废物和固有安全性。脂肪酸甲酯和多芳香族底物的相关结果将为将木质纤维素生物质和天然油脂转化为燃料和化学品提供迄今尚未探索的反应途径。更广泛的影响：在环境催化中心（CEBC）的跨学科设置中，教师，学生和工业研究人员之间的协同互动预计将通过CEBC招募的受过独特训练的学生的多元化骨干。美国的多元化招聘努力。PI有从弱势群体中培训学生的历史，包括从与Prairie View a&m大学和Puerto Rico大学的持续合作中招募的女性和少数民族学生。技术成果将被整合到一门正在进行的研究生课程中，该课程名为“可持续化学过程的发展”，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.