GOALI: Studies of Acidity in Solid Acid

摘要Raymond Gorte CTS-9403909研究沸石和其他固体酸的酸性和酸催化化学。目标是对反应速度和选择性的预测能力。使用的主要方法包括分子筛中含有羰基分子的碳-13核磁共振(NMR)，以表征位置强度、位置动力学和位置；对具有一系列潜在反应物和产物的沸石进行微量热分析，结果与酸中心的质子亲和模型相关联；以及对大单晶中的吸附物进行二次谐波产生(SHG)测量，以确定ZSM-5中的位置。核磁共振工作还补充了酸性环境中含羰基分子化学位移各向异性的理论计算。用磺化氧化锆等复合固体酸对酸中心表征技术进行了测试。这是宾夕法尼亚大学和杜邦公司之间的产学合作研究项目。在化学品生产中，用非均相固体酸取代溶液相酸，为化工、纺织和制药行业节省了大量下游成本。除了经济效益外，与液体酸相比，固体酸的职业安全问题通常要小得多。这项研究为选择酸并将其纳入工艺设计提供了一个概念性/知识性框架。***

ABSTRACT Raymond Gorte CTS-9403909 This is a study of acidity and acid-catalyzed chemistry in zeolites and other solid acids. The objectives is a predictive capability for reaction rates and selectivities. The principal approaches used include carbon-13 nuclear magnetic resonance (NMR) of carbonyl-containing molecules in zeolites to characterize site strengths, site dynamics, and site locations; microcalorimetry on zeolites with a range of potential reactants and products, with the results correlated to a proton-affinity model of the acid sites; and second-harmonic-generation (SHG) measurements of adsorbates in large single crystals to determine locations of sites in ZSM-5. The NMR work is complemented with theoretical calculations of the chemical-shift anisotropy of carbonyl-containing molecules in an acidic environment. The techniques for acid site characterization are tested with complex solid acids such as sulfonated zirconia. This is an industry-university cooperative research project between the University of Pennsylvania and the DuPont Company. The replacement of solution-phase acids with heterogeneous, solid acids in the production of chemicals offers major downstream savings to the chemical, textile, and pharmaceutical industries. Besides their economic benefits, solid acids are usually much less of an occupational safety problem than liquid acids. This study provides a conceptual/intellectual framework for selecting acids and incorporating them into process design. ***