【作者】 高静；

【导师】 王延吉；

【作者基本信息】 河北工业大学 ， 化学工艺， 2008， 硕士

【摘要】 对氨基苯酚是一种用途广泛的重要化工原料和有机中间体,主要用于医药、染料、橡胶、饲料、石油和摄影等行业。硝基苯催化加氢合成对氨基苯酚是目前广泛采用的一种合成工艺。本文针对该工艺中存在的由于使用稀硫酸溶液而产生的腐蚀性强、污水治理量大等问题,制备了Pt-酸性离子液体双功能催化剂,去除了硫酸,使对氨基苯酚合成过程更加环境友好。制备了新型酸性离子液体N,N,N-三甲基-N-磺丁基-硫酸氢铵（[HSO₃-b-N（CH₃）₃]HSO₄）,并对其结构进行了表征。建立了Pt/SiO₂+（[HSO₃-b-N（CH₃）₃]HSO₄）催化体系。考察了工艺条件对该催化剂体系中硝基苯催化加氢合成对氨基苯酚反应性能的影响。并对Pt/SiO₂、离子液体（IL）质量浓度、氢气分压、反应温度及反应时间等工艺条件进行了优化。在Pt/SiO₂催化剂用量为硝基苯用量的5wt%时,N,N,N-三甲基-N-磺丁基-硫酸氢铵离子液体质量浓度为22.5%,氢气分压0.4MPa,反应温度85℃,反应时间4h,水为反应介质,十六烷基三甲基溴化铵（CTAB）为表面活性剂的条件下,硝基苯转化率为96.5%,对氨基苯酚选择性为70.3%,当选用二甲基亚砜为钝化剂时,硝基苯转化率为96.6%,对氨基苯酚选择性为81.4%。制备出了SiO₂负载的Pt-酸性离子液体双功能固体催化剂。离子液体采用[SO₃H-bmim]HSO₄（1-（4-磺酸基）丁基-3-甲基咪唑-硫酸氢盐）。考察了负载方法对催化剂性能的影响。顺序浸渍（先负载氯铂酸,后负载离子液体）法的效果好于同时浸渍法。乙醇/水中负载Pt和酸性离子液体,在优化条件下,硝基苯转化率为68.6%,PAP选择性为60.4%。更多还原

【Abstract】 p-Aminophenol（PAP） is an important raw material and organic intermediate, and it is widely used in medicine, dyestuff, rubber, feed, petroleum and photography, etc. At present the one-step synthesis of p-Aminophenol through catalytic hydrogenation of nitrobenzene（NB） is a widely used process. However, in the process the strong causticity and the large amount of sewage was caused by H₂SO₄ during the production. In order to overcome the shortcomings, Pt-acidic ionic liquid（IL） bifunctional catalyst was prepared and used as catalyst, which made the process more environmental friendly.A new acidic ionic liquid, N,N,N-trimethyl-N-sulfonic butyl hydrogen sulfate （[HSO₃-b-N（CH₃）₃]HSO₄）, was prepared and its structure was characterized.Pt/SiO₂+（[HSO₃-b-N（CH₃）₃]HSO₄） catalytic system was set up. The influence of reaction conditions, such as amount of catalyst, IL mass concentration, H₂ pressure, reaction temperature, reaction time, and etc, was investigated. The suitable reaction conditions were as follows: Pt/SiO₂ amount, 5wt% of NB; IL mass concentration, 22.5%; H₂ pressure, 0.4MPa; reaction temperature, 85℃; reaction time, 4h. When deioned water was used as the reaction solvent, and cetyltrimethyl ammonium bromide （CTAB） as the surface active agent, NB conversion and selectivity of PAP were 96.5% and 70.3%, respectively. When dimethyl sulphoxide （DMSO） was the deactivator, NB conversion and selectivity of PAP were 96.6% and 81.4%, respectively.Pt-[SO₃H-bmim]HSO₄/SiO₂ bifunction catalyst was prepared. Effect of preparation methods on catalytic activity was studied. The catalyst prepared by successive impregnation showed better activity than that of co-impregnation. When Pt-IL bifunction catalyst was prepared in Ethanol/H₂O, under the suitable condition, NB conversion and selectivity of PAP were 68.6% and 60.4%, respectively.更多还原