氧化铝负载硅钨酸催化合成油酸丁酯研究.doc

摘 要 杂多酸作为一种新型高效的固体催化剂取代硫酸已广泛应用于各类酯化反应。本文以负载型杂多酸H4SiW12O40/Al2O3为催化剂，油酸和正丁醇为原料合成了油酸正丁酯。通过单因素试验，较系统地研究了醇酸摩尔比、反应温度、催化剂的用量、反应时间等对油酸转化率的影响，并对酯化条件进行了优化。采用L9(34)正交设计进行优化实验。优化条件如下：10 g Al2O3负载1.0 g H4SiW12O40，油酸0.030 mol，正丁醇0.045 mol，催化剂0.006 g，反应温度130 ℃，反应时90 min。此条件下，酯化率达95%以上。动力学研究发现，油酸的反应级数为一级，100 ℃的反应速率常数k1=0.0105 min-1，140 ℃的反应速率常数k2=0.0221 min-1，反应的表现活化能Ea=67.2 kJ·mol-1。 关键词：硅钨酸；油酸丁酯；催化酯化；动力学  Abstract As a new type of highly efficient solid catalyst, the heteropolyacid replacing the sulfuric acid has been widely used in various types of esterification.The structure and character, the special nature, the research development and the preparation method of the heteropolyacids H4SiW12O40/Al2O3 were introduced. Esterification of oleic acid with batanol was studied by H4SiW12O40/Al2O3 as catalyst. The effects of the temperature of reactants, mole ratio of reactants, catalyst dosage and reaction time on the conversion and yield were studied, and the reactlion conditions were optimized. Used the orthogonal design L9 (34) to carry on the optimize experiments.The optimun conditions were as follows: 10 g Al2O3 load 1.0 g H4SiW12O40, oleie acid 0.030 mol, butanol 0.045 mol, catalyst dosage 0.004 g, reaction temperature 130 ℃, reaction time 90 min. Under the optimun conditions, the conversion of oleic acid was over 95%. Carry on dynamics researches to the reaction:the oleic acid order of reaction is one class,100 ℃ reaction velocity k1=0.0105 min-1,140 ℃ velocity k2=0.0221 min-1, the performance that respond activate the activation energy Ea=67.2 kJ mol-1. Keywords: H4SiW12O40; esterify; catalyst; butyl oleate; heteroplyacids; dynamics 1 前言 油酸丁酯用途极为广泛，可用于机械油油性添加剂PVC耐寒辅助增剂]，但酯化率不高；国内刘瑛等采用微乳凝胶固定化酶催化合成油酸丁酯[8]，酯化率达90%以上，但该方法存在反应速率慢，效率不高，成本较大等问题难以工业推广应用。有人使用Ti(SO4)2 作催化剂 ，催化台成油酸丁酯[ ]，该催化剂具有较好的催化活性 ，但它易吸潮，回收困难。目前，有关固体酸(超强酸)代替液体强酸作为酯合成催化剂的文献报道不断出现[17-19]，包括固体超强酸、杂多酸、离子交换树脂、无机盐等作为有机合成和石油化工中的催化剂愈来愈受到人们的关注，特别是杂多酸(盐)型催化剂，作为一种新型高效催化剂不论在均相还是非均相体系中均可作为性能优异的酸碱、氧化还原或双功能催化剂[9]，因此，本试验采用负载型杂多酸H