石油炼制与化工 ›› 2014, Vol. 45 ›› Issue (5): 44-49.

• 催化剂 • 上一篇    下一篇

钛硅分子筛的表征及其催化丙烯环氧化连续反应的研究

阳辉1,靳鹏2,郑晓广2,3,王向宇3   

  1. 1. 河南新大新材料股份有限公司
      2. 中国平煤神马集团能源化工研究院
      3. 郑州大学化学与分子工程学院
  • 收稿日期:2013-09-16 修回日期:2014-01-16 出版日期:2014-05-12 发布日期:2014-04-22
  • 通讯作者: 阳辉 E-mail:yang12593@126.com

PREPARATION,CHARACTERIZATION AND PROPYLENE EPOXIDATION PERFORMANCE OF TITANIUM SILICALITE

  • Received:2013-09-16 Revised:2014-01-16 Online:2014-05-12 Published:2014-04-22

摘要: 以正硅酸乙酯为硅源、钛酸四丁酯为钛源、四丙基氢氧化铵为模板剂,采用水热合成法制备不同硅钛比的钛硅分子筛TS-1,并用有机碱对其进行了改性处理。利用X-射线粉末衍射(XRD)、紫外-可见吸收光谱(UV-Vis)、傅里叶变换红外光谱(FT-IR)和扫描电镜(SEM)等方法对TS-1的结构和形貌进行了表征。结果表明,所制备的钛硅分子筛样品具有典型的MFI结构,SiO2/TiO2摩尔比为70时钛硅分子筛(TS-1-70)基本上不含有非骨架锐钛矿型TiO2,以此为处理对象,发现采用有机碱四丙基氢氧化铵处理后的分子筛(TPAOH-TS-1-70)效果最好,不仅保持了原有的MFI拓扑结构,而且出现了2~6 nm之间的介孔,且孔径分布较广,呈现出多级孔的状态。在淤浆床反应器中研究了TPAOH-TS-1-70催化丙烯环氧化连续反应的性能,结果表明:催化剂运行160 h后,仍保持较高的催化活性,具有较好的稳定性。

Abstract: Titanium silicalite-1(TS-1) molecular sieves with different Si/Ti were hydrothermally synthesized with tetraethyl orthosilicate as Si source, tetrabutyl titanate as Ti source and tetrapropyl ammonium hydroxide as template and modified with organic base. The structure and morphology of TS-1 sieves were characterized by XRD, UV-Vis, FI-IR and SEM. The Si-Ti sieves prepared are proved to have the typical MFI structure. At Ti/Si of 70(TS-1-70), no non-framework anatase is observed. It is found that after treatment with propyl ammonium hydroxide for TS-1-70, hierarchical pores with 2-6 nm meso-pores appear with broad pore size distribution, while still retaining the original MFI topology. The propylene epoxidation with modified TS-1-70 was conducted in a continuous slurry bed reactor. Under the optimal conditions, the catalyst can steadily run for over 160 h with high activity, demonstrating the good stability of the modified catalyst.