【作者】 李辉；

【导师】 魏东炜；

【作者基本信息】 天津大学 ， 化学工艺， 2013， 硕士

【摘要】 苯二酚是重要的有机化工中间体。邻苯二酚主要用于农药、香料和医药行业，也可用作电镀槽添加剂、抗氧化剂等特种化学品以及合成酚醛树脂的原料。对苯二酚主要用于感光材料、橡胶工业和染料行业，还可作为某些树脂或橡胶单体贮运过程的阻聚剂、发动机燃料特别是含四乙基铅燃料的胶质抑制剂以及石油抗凝剂及氮肥工业的催化脱硫剂等。苯酚过氧化氢羟基化工艺是一种“绿色工艺”，也是目前最具前景的苯二酚生产工艺。本文首先分别以氢氧化钠和尿素为沉淀剂，以H-ZSM-5为载体制备了负载型氧化铁催化剂，并分别对这两种制备方法的工艺条件进行了优化，考察了它们在苯酚羟基化反应中的作用。结果表明，以氢氧化钠为沉淀剂所制备的催化剂催化效果优于以尿素为沉淀剂的均匀沉淀法所制备的催化剂。为了提高苯酚转化率和苯二酚选择性，以氢氧化钠为沉淀剂，以H-ZSM-5为载体制备了负载型二元过渡金属氧化物催化剂，其中负载型铁-钴二元氧化物催化剂的催化效果最好，催化苯酚羟基化的活性和选择性都有明显提高。比较了未负载的过渡金属氧化物与H-ZSM-5负载的过渡金属氧化物在苯酚羟基化反应中的催化效果。结果表明，H-ZSM-5负载的过渡金属氧化物的催化效果明显优于未负载的过渡金属氧化物。在反应温度60oC，苯酚/过氧化氢摩尔比为1.25，催化剂/苯酚质量比为0.05，溶剂水和苯酚的质量比为3，反应时间1h的条件下，H-ZSM-5负载铁-钴混合氧化物作催化剂，苯酚转化率为51.82%，苯二酚选择性为92.47%，过氧化氢有效利用率为59.90%。最后，考察了在初始反应体系中加入邻苯二酚、对苯二酚和酸的作用，考察了反应温度、苯酚/过氧化氢摩尔比、催化剂/苯酚质量比以及反应时间对苯酚羟基化反应的影响。更多还原

【Abstract】 Dihydroxybenzene is important organic chemical intermediate. Catechol is mainlyused for pesticides, perfume and pharmaceutical industry. In addition, it can be usedas specialty chemicals like plating bath additives and antioxidants. It is also one of theraw material for the synthesis of phenolic resin. Hydroquinone is widely used for thephotosensitive material, rubber and dye industry. Besides, it also can be used aspolymerization inhibitor during the storage of some resin or rubber monomer, guminhibitor of engine fuel, oil anticoagulant and catalytic desulfurization agent in theNitrogen Fertilizer Industry.The hydroxylation of phenol by hydrogen peroxide is a kind of "green technology"and the most promising process for the manufacture of dihydroxybenzene. In thisarticle, H-ZSM-5supported iron oxide catalyst was prepared by precipitation andhomogeneous precipitation with sodium hydroxide and urea as precipitating agentrespectively. The catalytic properties were tested by the reaction of phenolhydroxylation. The result shows that the catalyst prepared with sodium hydroxide asprecipitating agent has better catalytic properties.In order to improve the conversion of phenol and the selectivity todihydroxybenzene, H-ZSM-5supported binary transition metal oxide catalysts wereprepared with sodium hydroxide as precipitating agent, among which the iron-cobaltbinary oxide catalyst showed the best activity and selectivity. H-ZSM-5supportedcatalysts showed better activity and selectivity than transition metal oxide. UsingH-ZSM-5supported iron-cobalt binary oxide as catalyst, under the conditions thatm(catalyst)/m(phenol)=0.05with water as solvent, reaction temperature60oC，n(Phenol)/n(H2O2)=1.25and reaction time1h, the conversion of phenol was51.82%，the total selectivity of dihydroxbyenzene was92.47%and the effectiveutilization of hydrogen peroxide reached59.90%.The effect of catechol, hydroquinone and acid in the initial reaction system,reaction temperature, molar ratio of phenol to hydrogen peroxide, mass ratio ofcatalyst to phenol and reaction time to the hydroxylation of phenol was investigated.更多还原