GOALI: Studies of Acidity in Solid Acid

摘要：本文研究了沸石和其他固体酸的酸性和酸催化化学。目标是反应速率和选择性的预测能力。使用的主要方法包括沸石中含羰基分子的碳-13核磁共振（NMR）来表征位点强度、位点动力学和位点位置；沸石的微热测定与一系列潜在的反应物和产物，其结果与酸位的质子亲和模型相关；以及大单晶中吸附物的二次谐波（SHG）测量，以确定ZSM-5中位点的位置。核磁共振工作补充了含羰基分子在酸性环境中的化学位移各向异性的理论计算。酸位表征技术用复合固体酸如磺化氧化锆进行了测试。这是宾夕法尼亚大学和杜邦公司的产学研合作项目。在化学品生产中，用非均相固体酸取代液相酸为化工、纺织和制药行业提供了主要的下游节约。除了经济效益外，固体酸通常比液体酸对职业安全的影响要小得多。本研究为选择酸并将其纳入工艺设计提供了一个概念/知识框架。＊＊＊

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. ***