钛硅分子筛的改性对环己烷氧化反应的影响  

Effect of titanium silicalite modification on cyclohexane oxidation

作　　者：宋厚杰 齐骏鑫 郭舒隽 方嘉辉 陈晓晖[1] 黄清明[1] 

机构地区：[1]福州大学化肥催化剂国家工程研究中心,福建福州350002 [2]福州大学至诚学院,福建福州350002

出　　处：《工业催化》2016年第2期32-35,共4页Industrial Catalysis

基　　金：国家自然科学基金(20976030)资助项目

摘　　要：使用不同改性液H_2SO_4-H_2O_2、(NH_4)_2CO_3-H_2O_2、(NH_4)HF_2-H_2O_2和(NH_4)_2CO_3+(NH_4)HF_2-H_2O_2混合溶液对中空钛硅分子筛进行改性。采用XRD、UV-Vis和拉曼光谱进行表征分析,考察改性前后钛硅分子筛在环己烷氧化反应的催化性能。结果表明,改性过程没有破坏钛硅分子筛的MFI拓扑结构,但提高了钛硅分子筛相对结晶度,并脱除了部分锐钛矿相TiO_2;与未改性钛硅分子筛相比,环己醇和环己酮选择性及H_2O_2有效利用率明显提高,以改性液(NH_4)_2CO_3+(NH_4)HF_2-H_2O_2改性钛硅分子筛效果最佳,醇酮选择性提高12.78个百分点,H_2O_2有效利用率提高17.33个百分点;(NH_4)_2CO_3+(NH_4)HF_2-H_2O_2混合溶液改性钛硅分子筛显著降低H_2O_2用量,在己内酰胺生产过程中有很好的应用前景。Hollow titanium silicalite （HTS） was modified by different solutions of H2SO4-H2O2, （ NH4） 2CO3-H2O2, （ NH4 ） HF2-H2O2 and （ NH4 ） 2CO3 ＋ （ NH4 ） HF2-H2O2. The modified HTS samples were characterized by XRD, UV-Vis and Raman. The catalytic performance of HTS before and after modi- fication for cyclohexane selective oxidation were investigated. The results showed that the modification of HTS did not destroy its topological structure of MFI, improved the relative erystallinity of HTS, and partial anatase TiO2 was removed. Compared with the HTS, the selectivity to cyclohexanol and cyclohexanone, and the utilization rate of H2O2 over modified HTS were improved obviously. HTS modified by the solution of （NH4）2CO3 ＋ （NH,）HFz -H2O2 for cyclohexane selective oxidation exhibited optimal catalytic per- formance,and the selectivity to cyclohexanol and cyclohexanone was increased by 12.78 percentage point,the utilization rate of H2O2 was improved by 17.33 percentage point;HTS modified by the solution of （ NH4 ） 2CO3 ＋ （ NH4 ） HF2-H2Oz remarkably decreased H202 dosage ,which had good application pros- pect in the process of caprolactam production.

关 键 词：催化化学 环己烷氧化 H2O2 中空钛硅分子筛 改性 醇酮选择性 

分 类 号：TQ426.6[化学工程] O643.36[理学—物理化学]