EAGER: Directed Ozonolysis in Liquid Carbon Dioxide

EAGER：液态二氧化碳中的定向臭氧分解

• 批准号: 1128186
• 负责人: Bala Subramaniam
• 金额: $ 9.99万
• 依托单位: University of Kansas Center for Research Inc
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2011
• 资助国家: 美国
• 起止时间: 2011-04-15 至 2012-03-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1128186&HistoricalAwards=false
• 关键词: EAGER; Directed; Ozonolysis; Liquid; Carbon

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.

PI：Bala subramanian机构：堪萨斯大学研究中心Inc.Proposal编号：1128186Title：急切：液态二氧化物碳二氧化碳和目标中的臭氧碳酸盐：这个渴望的项目旨在奠定基础，以建立ozonsyssy作为生产工业化学物质的可行技术和燃料。最近的发现表明，与常规溶剂相比，液体CO2中的O3溶解度显着提高。这一发现促使这项研究旨在探索是否可以使用广泛的底物进行液体二氧化碳中的臭氧溶解。因此，特定的目标是调查（a）在诸如密集二氧化碳之类的惰性溶剂中的臭氧混乱和稳定性，旨在建立适当的臭氧溶解培养基； （b）脂肪酸甲酯和芳香族结构（包含C = C键）在液体CO2中获得的转化和选择性。SSSINGICENISS：ozonylysys能够通过氧化剂（例如羧酸和醛）产生丰富的有价值的中间体（例如） C = C键和线性碳氢化合物的裂解，例如木质素。但是，由于保护反应中间体免受进一步氧化并找到对臭氧惰性的可行溶剂的挑战，因此相对较少的工业应用程序。研究活动：将使用一系列复杂性的模型基板来实现上述目标。初始底物将包括：（a）Stilbene和Cyclohexene； （b）硬脂酸甲酸甲酯和甲基油酸酯作为饱和和不饱和脂肪酸的模型； （c）代表源自木质素的天然产物中常见功能的芳香化合物。实验研究将由最先进的研究基础设施支持，其中包括配备原位UV-VIS光谱的高压视图单元，启用超声混合的混合和在线抽样功能，以执行反应和相位平衡研究。智能优点：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，其以下属性可以促进可持续性：相对温和的条件下（数十个棒和近距离温度）的过程强化，有效的O3，有效的O3利用最大化所需产品，废物最小化和固有的安全性。与脂肪酸甲基酯和多疗法底物相关的结果将为迄今未探索的反应途径，将木质纤维素生物量和天然油转化为燃料和化学物质的影响。Boader的影响。环境催化中心（CEBC）有望在CEBC的多样性招聘工作中招募各种各样的训练有素的学生干部。 PI有培训来自代表性不足团体的学生的历史，其中包括与Prairie View A＆M大学和波多黎各大学的持续合作伙伴关系招募的妇女和少数民族学生。技术成果将纳入正在进行的研究生课程中，名为“可持续化学过程的发展”，该过程是由化学家和工程师教授的团队。