固体超强酸SO_4^(2-)/TiO_2-ZrO_2催化合成己二酸二丁酯

SYNTHESIS OF DIBUTYL ADIPATE OVER SOLID SUPER ACID CATALYST SO_4^(2-)/TiO_2-ZrO_2

研究了SO_4^(2-)/TiO_2-ZrO_2型催化剂的制备及其催化合成己二酸二丁酯反应。考察了催化剂焙烧温度、原料配比、反应时间及催化剂用量等因素对酯化反应的影响,较佳反应条件为:催化剂焙烧温度500℃,催化剂用量5%(以己二酸质量为基准),n(己二酸):n(正丁醇)=1:2．5,正丁醇为带水剂、在回流温度下反应4 h,酯化率可达99．35%。结果表明,SO_4^(2-)/TiO_2-ZrO_2在产物颜色、出水率和催化剂回收等方面明显优于对甲苯磺酸、浓硫酸催化剂。

Esterfication of adipic acid catalyzed with SO4^2-/TiO2-ZrO2 solid superacid was studied. The results showed that calcination temperatures of the catalysts, catalyst dosage, ratios of reactants and reaction time had influences on the esterfication reaction. The optimal conditions were found as follows. catalyst calcination temperature 500 ℃, the ratio of solid superacid to adipic acid 0.05, n（adipic acid） ＂ n（n butanol） = 1 ： 2.5, n-butanol as water carrying agent, and esterfication time 4 h under boiling temperature. Under these conditions, the esterfication ratio of adipic acid was 99.35 %. At the same times, concentrated sulfuric acid and p-toluene sulfonic acid were also tested as catalysts for preparing dibutyl adipate, and their catalytic activities were compared with SO4^2-/TiO2-ZrO2 . It was found that the solid super acid had more advantages than common protonic acidic catalysts in terms of product color, washing time and the recyclability.