【作者】 陈景林；

【导师】 林青松； 吕连海；

【作者基本信息】 大连理工大学 ， 应用化学， 2001， 硕士

【摘要】 本论文对苯及低沸点取代芳烃的气相硝化反应进行了比较深入的研究，研究了各种因素对用硝酸作硝化剂的芳烃气相硝化反应的影响，并在参考大量国内外文献的基础上合成出自己的对芳烃气相硝化反应有效的新型固体酸催化剂—负载型杂多酸催化剂和负载型硫酸催化剂。 研究结果表明，对于苯与硝酸的气相硝化反应，反应的最佳摩尔比为2∶1，进行硝化反应的最佳反应温度为150～170℃，硝化反应催化剂的最佳载体为二氧化硅。 杂多酸负载型催化剂对苯和硝酸的气相硝化反应具有很好的催化活性和选择性。当苯与硝酸的摩尔比为2∶1，反应温度为170℃，空速为1200ml/g·h，反应压力为0.1MPa，催化剂为15％H₃PW₁₂O₄₀/SiO₂，硝基苯的产率为86％，硝基苯的时空收率为0.66kg-NB/kg-cat·h。ESR谱表明：杂多酸催化剂的钨在苯气相硝化反应中发生了还原反应。五价钨(W⁵⁺)的ESR谱在室温和液氮温度（77K）下都被观测到，在液氮温度（77K）下其g张量为：g_∥=1.95，g_⊥=1.94，在室温下其g张量为：g_∥=1.974，g_⊥=1.989，同时O₂^-自由基ESR谱（g₁=2.026，g₂=2.019，g₃=2.014）也被观测到。 硫酸负载型催化剂对苯和硝酸的气相硝化反应也具有好的催化活性和选择性。当苯与硝酸的摩尔比为2∶1，反应温度为160℃，空速为1200ml/g·h，反应压力为0.1MPa，硝基苯的产率为98％，硝基苯的时空收率为0.75kg-NB/kg-cat·h。更多还原

【Abstract】 In this paper, vapor-phase nitration of benzene and other substitution aromatic hydrocarbons with low boiling point was studied and many factors that affect vapor-phase nitration of aromatic hydrocarbons were investigated. New solid acid catalysts are effective on the vapor-phase nitration of aromatic hydrocarbons were synthesized by ourselves, which are supported heteropoly acid and supported sulfuric acid.The results show that the molar ratio of benzene and HNO3, 2:1 and the optimum reaction temperature, 150~170癈 and the best support, the silica for the vapor-phase nitration benzene and diluted nitric acid (60~70%).Supported heteropoly acid catalysts give fairly high catalytic activity and selectivity on vapor-phase nitration of benzene and diluted nitric acid and were characterized by ESR. Under conditions of molar ratio of benzene and HNO3, 2:1 and reaction temperature, 170癈 and space velocity, 1200ml/g h and reaction pressure, 0.1 MPa and the catalyst, 15%H3PW12O40/SiO2(by weight), the yield and the space-time yield (STY) of nitrobenzene (NB) are 86% and 0.66 kg NB/(kg cath) respectively. ESR spectrum show that reduced of heteropoly acid was occurred in vapor-phase nitration reaction of benzene. The ESR signals of W5+ are observed, which have g=1.94 and g//=1.95 at room temperature and have g=1.989 and g//=1.974 at 77K. And ESR of O2 with g1=2.026, g2=2.0 19 and g3=2.0 14 were observed simultaneously.Supported sulfuric acid catalyst exhibits also very high catalytic activity and selectivity on vapor-phase nitration ofbenzene and diluted nitric acid. Under conditions of molar ratio of benzene and HNO3, 2:1 and reaction temperature, 160 癈 and space velocity, 1200ml/g h and reaction pressure, 0.1 MPa and the catalyst, 10%H2SO4/SiO2(by weight), the yield and the space-time yield (STY) of nitrobenzene (NB) are 98% and 0.75 kg NB/(kg cath) respectively.更多还原