›› 2020, Vol. 22 ›› Issue (4): 1-9.

• Scientific Research • 上一篇    下一篇

HTS分子筛催化甲苯无有机溶剂条件下的氧化溴化反应研究

彭欣欣,夏长久,林民,朱斌,罗一斌,舒兴田   

  1. 中国石化石油化工科学研究院
  • 收稿日期:2020-08-06 修回日期:2020-10-19 出版日期:2020-12-30 发布日期:2020-12-30
  • 通讯作者: 彭欣欣 E-mail:pengxx.ripp@sinopec.com
  • 基金资助:
    10万吨/年双氧水法制环氧丙烷成套技术

Investigation on Organic Solvent Free Toluene Oxidative Bromination Reaction Catalyzed by HTS Zeolite

Peng Xinxin,XIA Chang-Jiu,Lin Min,Zhu Bin,Luo Yibin,Shu Xingtian   

  1. SINOPEC Research Institute of Petroleum Processing
  • Received:2020-08-06 Revised:2020-10-19 Online:2020-12-30 Published:2020-12-30
  • Contact: Peng Xinxin E-mail:pengxx.ripp@sinopec.com

摘要: 本文研究了双氧水和溴化氢溶液体系中,空心钛硅分子筛(HTS)催化甲苯在无有机溶剂条件下的氧化溴化反应。在优化的反应条件下,甲苯转化率可达90.7%,一溴甲苯选择性达99.0%。采用UV-Raman光谱对甲苯溴化反应的机理进行了研究。结果表明,HTS分子筛可高效催化溴化氢和双氧水氧化反应并生成大量的活性溴物种,该溴物种可通过亲电取代反应进一步促进甲苯溴代制备一溴甲苯。基于拉曼光谱的研究结果,提出了基于HTS分子筛催化的活性溴物种“产生-存储-反应”的甲苯溴化两步反应机理。

关键词: 钛硅分子筛, 氧化溴化, 无有机溶剂, H2O2/HBr, 多溴离子

Abstract: Hollow titanium silicalite (HTS) zeolite catalyzed toluene oxidative bromination in aqueous medium without the need for organic solvent under mild conditions by employing H2O2 and HBr was investigated. A high toluene conversion (90.7%) and high selectivity of mono-bromotoluene (99.0%) was achieved under optimal reaction conditions. UV-Raman spectroscopy was applied for the mechanism study and the result reveals that HTS is efficient for catalyzing the HBr and H2O2 oxidation reaction and producing abundant active bromine species, which further facilitate the toluene electrophilic bromination reaction. A two-step toluene bromination reaction mechanism involving HTS catalyzed active bromine species “generation-storage-utilization” process is proposed based on the Raman results.

Key words: titanium silicalite, oxidative bromination, organic solvent free, H2O2/HBr, polybromine ion