化工进展 ›› 2020, Vol. 39 ›› Issue (3): 1021-1028.DOI: 10.16085/j.issn.1000-6613.2019-0767

• 工业催化 • 上一篇    下一篇

碱性添加剂在钛硅分子筛/H2O2催化丙烯环氧化反应中的作用

宋万仓1(),熊光2,臧甲忠1,于海斌1,王祥生2   

  1. 1.中海油天津化工研究设计院有限公司催化技术重点实验室,天津 300131
    2.大连理工大学化工与环境生命学部化工学院,精细化工国家重点实验室,辽宁 大连 116024
  • 收稿日期:2019-05-13 出版日期:2020-03-05 发布日期:2020-04-03
  • 通讯作者: 宋万仓
  • 作者简介:宋万仓(1985—),男,博士,研究方向为分子筛合成、改性及催化选择性氧化。E-mail:songcwjin@163.com
  • 基金资助:
    国家自然科学基金(21473016);中海油集团公司科技项目

Effect of basic additive in feedstock on propylene epoxidation catalyzed by TS-1/H2O2

Wancang SONG1(),Guang XIONG2,Jiazhong ZANG1,Haibin YU1,Xiangsheng WANG2   

  1. 1.Key Laboratory of Catalysis Technology, CNOOC Tianjin Chemical Research and Design Institute Co. , Ltd. , Tianjin 300131, China
    2.State Key Laboratory of Fine Chemicals, Faculty of Chemical, Environmental and Biological Science and Technology, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, Liaoning, China
  • Received:2019-05-13 Online:2020-03-05 Published:2020-04-03
  • Contact: Wancang SONG

摘要:

考察了反应溶液中碱性添加剂{氨水(NH4OH)、氢氧化钠(NaOH)、碳酸钠(Na2CO3)、碳酸铵[(NH4)2CO3]和四甲基氢氧化铵(TMAOH)}及其浓度对钛硅分子筛(TS-1)催化丙烯环氧化反应性能的影响,并采用紫外拉曼光谱(UV-Raman)与气相色谱(GC)联用原位分析(Raman-GC)碱性添加剂的作用机理。结果表明:反应体系中添加碱性添加剂可有效改善TS-1催化丙烯环氧化反应的选择性。不同碱性添加剂对TS-1催化丙烯环氧化活性和稳定性影响不同,NaOH、Na2CO3和TMAOH的添加造成催化活性和稳定性降低。NH4OH或(NH4)2CO3作为添加剂改善环氧化反应选择性的同时提高了反应稳定性,其中以(NH4)2CO3效果最佳。添加(NH4)2CO3浓度为8.0×10-4mol/L时,TS-1催化丙烯环氧化在固定床反应器上连续运行336h时,X(H2O2)仍保持在90%以上。原位Raman-GC分析发现,反应体系中NH4OH和(NH4)2CO3添加可加快反应活性中间体Ti-OOH(η2)基团的生成,促进反应产物从活性中心快速扩散,从而提高丙烯环氧化反应选择性和稳定性。

关键词: 催化, 丙烯环氧化, 钛硅分子筛, 碱性添加剂, 原位拉曼光谱气相色谱分析, 稳定性

Abstract:

NH4OH, NaOH, Na2CO3, (NH4)2CO3 and TMAOH were selected as the basic additive in the feedstock of propylene epoxidation reaction and their effects on the performance of TS-1 catalysis were evaluated by in-situ Raman spectrometry-gas chromatography. The experimental results suggested that the performance of the TS-1 catalyst was influenced significantly by the composition of feedstock. However, the presence of NH4OH or (NH4)2CO3 at a suitable concentration could improve the catalytic activity, selectivity and the stability of the TS-1 catalyst. When (NH4)2CO3 concentration in feedstock was 8.0×10-4mol/L, the best catalytic performance was obtained. The X(H2O2) still remained above 90% after a long-term run of 336h in a fixed-bed reactor. In-situ Raman-GC showed that the basic additive promoted the formation of the reactive intermediates Ti-OOH(η2) and accelerated the diffusion of reaction products from active centers.

Key words: catalysis, propylene epoxidation, TS-1 molecular sieves, basic additive, in-situ UV-Raman, stability

中图分类号: 

京ICP备12046843号-2;京公网安备 11010102001994号
版权所有 © 《化工进展》编辑部
地址:北京市东城区青年湖南街13号 邮编:100011
电子信箱:hgjz@cip.com.cn
本系统由北京玛格泰克科技发展有限公司设计开发 技术支持:support@magtech.com.cn