连续流微反应器中微纤结构化的Nafion/SiO2固体酸催化苯硝化反应  

Nitration of Benzene in a Continuous-Flow Microreactor Integrated with Microfiber-Structured Nafion/SiO_2 Solid Acid Catalyst

作　　者：杨九龙[1] 李剑锋[1] 路勇[1] 

机构地区：[1]华东师范大学化学系,上海市绿色化学与化工过程绿色化重点实验室,上海200062

出　　处：《物理化学学报》2009年第10期2045-2049,共5页Acta Physico-Chimica Sinica

基　　金：国家自然科学基金(20590366);国家高技术研究发展计划(863)项目(2007AA05Z101);教育部“新世纪优秀人才支持计划”(NCET-06-0423);上海市教委“曙光人才计划”(06SG28);上海市重点学科建设项目(B409)资助~~

摘　　要：采用溶胶-凝胶组装方法制备了Nafion/SiO2胶体,并涂附于烧结的316L不锈钢(SS-316L)金属微纤网络,形成了空隙率为60%-75%(φ,体积分数)的整体式微纤结构化的Nafion/SiO2固体酸催化剂.使用傅里叶变换红外光谱(FT-IR),热重分析(TGA),扫描电子显微镜(SEM)及NH3吸附法对微纤结构化的Nafion/SiO2催化剂进行了表征.结果显示,溶胶-凝胶组装方法可以明显促进Nafion的分散,导致酸性中心的暴露量显著增加;结构化的Nafion/SiO2催化剂以200-400nm颗粒堆积而成的多孔涂层形式存在.在一种集换热、混合、催化(反应)功能于一体的微反应器中,考察了整体式微纤结构化的Nafion/SiO2固体酸催化剂催化苯硝化的反应性能.Nafion在SiO2中的组装量为20%(w,质量分数),金属微纤网络上Nafion/SiO2担载量为36.3%(w)的优化催化剂上,75℃时苯转化率为44.7%,硝基苯选择性可达99.9%.相近转化率下,Nafion/SiO2固体酸单位酸中心的催化效能约为硫酸的600倍.We prepared novel monolithic microfiber-structured Nafion/SiO2 solid acid catalysts with 60%-75% （φ, volume fraction） void volume by coating Nafion/SiO2 sol-gel onto a sinter-locked stainless steel （SS-316L） microtibrous network. We characterized the microstructured Nafion/SiO2 catalysts using Fourier transform-infrared spectrometry （FT-IR）, thermogravimetric analysis （TGA）, scanning electron microscopy （SEM）, and NH3-chemisorption. Results show that the sol-gel technology results in highly dispersed Nation particles which significantly increase the number of accessible acid sites. The Nafion/SiO2 catalyst coating layer is made up of 200-400 nm particles and looks porous. The catalytic performance of the microstructured Nation/SiO2 catalysts was tested using the nitration of benzene in a continuous-flow microreactor that integrated heat-exchange, mixture, and catalytic reactions. The best catalyst had a loading capacity of 36.3% （w, mass fraction） for the Nafion/SiO2 composite in which the Nation content was 20% （w）. At a reaction temperature of 75 ℃, this optimized microstructured solid acid catalyst resulted in a benzene conversion of 44.7% with a nitrobenzene selectivity of 99.9%. At an equivalent conversion level, the activity per acid site of the microstructured Nafion/SiO2 catalyst is nearly 600 times as that of liquid sulfuric acid.

关 键 词：溶胶-凝胶 微纤 微反应器 全氟磺酸树脂 固体酸 苯 硝化 硝基苯 

分 类 号：O643.32[理学—物理化学]