EAGER: Directed Ozonolysis in Liquid Carbon Dioxide

主要研究者：巴拉萨勃拉曼尼亚机构：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：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。最近的研究结果表明，O3的溶解度显着提高，在液体CO2相比，传统的溶剂。这一发现促使这项调查，旨在探索是否控制臭氧分解液体CO2可以进行广泛的基板。因此，具体目标是研究（a）臭氧在惰性溶剂如浓CO2中的溶解性和稳定性，旨在建立臭氧分解的合适介质;（B）在脂肪酸甲酯和芳族结构的臭氧分解期间获得的转化率和选择性（含有C=C键）。臭氧分解能够通过从聚芳结构（如木质素）氧化裂解C=C键和线性烃来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于进一步氧化和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：上述目标将追求一套日益复杂的模型基板。初始基质将包括：（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;和（c）芳香族化合物，其代表通常在衍生自木质素的天然产物中发现的官能团。实验研究将得到最先进的研究基础设施的支持，包括配备原位紫外-可见光谱仪的高压观察池、超声波混合和在线取样功能，用于进行反应和相平衡研究。该项目的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）进行工艺强化，有效利用O3以最大限度地提高所需产品，最大限度地减少废物和固有安全性。与脂肪酸甲酯和多环芳烃底物相关的结果将为木质纤维素生物质和天然油转化为燃料和化学品提供一条迄今尚未探索的反应途径。在环境催化中心（CEBC）的跨学科环境中，教师，学生和工业研究人员之间的协同互动预计将产生一批训练有素的学生，是通过CEBC招募的的多样性招聘工作。PI有培训来自代表性不足群体的学生的历史，包括从与Prairie View A M大学和波多黎各大学的持续伙伴关系中招募的妇女和少数民族学生。技术成果将被整合到一个正在进行的研究生课程，名为可持续化学工艺的发展，这是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.