【作者】 余雁；

【导师】 伏再辉； 尹笃林；

【作者基本信息】 湖南师范大学 ， 有机化学， 2004， 硕士

【摘要】 发展绿色催化工艺的核心是研制高效的环境友好催化剂。鉴于目前有关邻苯二酚与甲醇醚化反应，所使用的催化剂主要为固体B酸催化剂，选择性较差，有的催化剂在运转过程中还不太稳定，使用寿命短等缺点，本文首次尝试用改性固体L酸来催化邻苯二酚与甲醇合成愈创木酚的反应。 结果表明：ZnCl₂改性的Al₂O₃和NaY固体L酸是该类醚化反应的优良催化剂。他们的催化活性，特别是选择性都明显优于HY B酸催化剂。ZnCl₂的改性作用在于增加催化剂的酸性，从而大大提高催化剂的活性，特别是愈创木酚的选择性，也改善了催化剂的稳定性。进一步比较ZnCl₂／Al₂O₃与ZnCl₂／NaY两类固体L酸催化剂，发现前者虽然显示较好的催化活性和目标产物的选择性（优化条件下转化率和选择性分别为81.8％和90.9％），但是它的稳定性较差（催化剂运转30h就有明显的失活），其失活主要是因为该类催化剂的ZnCl₂在运转过程中的流失造成的。而后者在催化活性和选择性上有更进一步的提高（优化条件下转化率和选择性分别为86.7％和99.3％），而且催化剂的稳定性有明显的改善（催化剂运转70h才出现失活）。其稳定性改善的原因是该类催化剂的活性组分在运转过程中不易流失，失活的主要原因则是催化剂表面的积炭造成的。 为了进一步寻求使用寿命更长的催化剂，我们就NaY原粉中非骨架铝对本反应的催化作用以及助剂对该类型的催化剂的调变性能进行研究。发现含有非骨架铝的NaY分子筛也是该类反应的一个有效催化剂（邻苯二酚转化率76.4％，愈创木酚选择性91.9％，催化剂的稳定性20h），而加入一定的助剂后，它的催化活性有了明显的上升，而且催化剂的稳定性有了明显改善（邻苯二酚转化率94.0％，愈创木酚选择性90.4％，催化剂的稳定性100h）。 三类催化剂在催化此反应时均表现出了较好的催化活性，如果能进一步提高它们的使用寿命，它们将是很有发展前途的催化剂。上述工作为今后固体酸在有机合成中的应用提供了研究基础。更多还原

【Abstract】 The core of the developing green catalysizing technology is that the study on the friendly catalysts both protects environment and improves economic efficiency.At present, the solid B acid catalysts have been used widely for the etheriflcation of catechol with methanol. But, their selectivity, especially the catalytic stability, is still need to be improved. Therefore, we try to use the ZnCl2 modified solid L acid catalysts to catalyze this reaction for the first time.The results have shown that the ZnCl2 modified Al2O3 or NaY catalysts has great efficiency to the reaction, which precede to the HY catalyst with B acid sites. The modifications of the ZnCl2 to A12O3 or NaY, which are to increase the acidity of the catalyst, increased the catalytic activities greatly, especially increased the selectivity for the guaiacul and also improved the stability of the catalysts. Further studies on the ZnCl2/Al2O3 and ZnCl2/NaY catalysts have shown that the former displayed the better catalytic activity and the selectivity for the guaiacul (at the optimum conditions, the conversion and selectivity are 81.5% and 90.9%, respectively), but its stability is worse (it will lose the activity after running 30 h), the cause is that the ZnCl2 active component of this catalyst is easy to lose in the running process; while the latter not only has the improved activity and selectivity (at the optimum conditions, theconversion and selectivity are 86.7% and 99.3%, respectively) , but also has a distinct improvement of the stability (it will lose the activity after running 70 h), the cause of its improved stability is that the active component of this catalyst is not easy to lose in the running process, the coke of the catalyst’ surface is the main reason for the inactivation.In order to look for a better catalyst with longer use-life, we have studied the catalytic interactions of the non-framework-aluminium in NaY to this reaction and the modifications of the accessory ingredient to this catalyst. After studying we found that the non-framework-aluminium NaY molecular sieve was very active to this reaction (catechol conversion: 76.4%, guaiacul selectivity: 91.9%, stability of the catalyst: 20h), after adding a small of accessory ingredient into the non-framework-aluminiu-m NaY we found its catalytic activity and stability have been improved distinctly (catechol conversion: 94.0%, guaiacul selectivity: 90.4%, stability of the catalyst: 100h).All the three kinds of catalysts have presented better catalytic activity. They will be used widely if their use-life can be prolonged. The previous works will provide research foundation for the application of the solid acid catalysts in the organic synthesis.更多还原