石油炼制与化工 ›› 2023, Vol. 54 ›› Issue (6): 1-6.

• 加工工艺 •    下一篇

Pd/Al2O3催化双环戊二烯原位加氢反应研究

伏朝林,赵杰,陶志平,舒兴田   

  1. 中石化石油化工科学研究院有限公司
  • 收稿日期:2022-11-07 修回日期:2023-01-31 出版日期:2023-06-12 发布日期:2023-05-29
  • 通讯作者: 赵杰 E-mail:156459719@qq.com

IN-SITU HYDROGENATION OF DICYCLOPENTADIENE OVER Pd/Al2O3 CATALYST

  • Received:2022-11-07 Revised:2023-01-31 Online:2023-06-12 Published:2023-05-29
  • Contact: Jie ZHAO E-mail:156459719@qq.com

摘要: 以Pd/Al2O3为催化剂,以甲酸替代H2作为供氢试剂,进行双环戊二烯(DCPD)两步加氢反应,制备用于高密度喷气燃料和精细化学品生产的桥式四氢双环戊二烯。该过程避免了使用H2时所存在的高压、易燃易爆风险以及对设备的高要求,在普通容器中即可完成。试验中考察了甲酸加入方式、反应时间、反应温度、反应溶剂、底物浓度对反应的影响,结果发现,分步平均加入甲酸有利于四氢双环戊二烯的生成,在160 ℃下,经过10 h反应,收率可达98%。在异丙醇、乙醇或四氢呋喃溶剂中,DCPD质量分数为40%~60%时,更有利于四氢双环戊二烯的生成。同时,考察了催化剂的稳定性,发现经过5次循环使用后,催化剂依然能够保持较好的催化活性,有利于DCPD原位加氢反应的进一步放大。

关键词: 供氢试剂, 甲酸, 双环戊二烯, 四氢双环戊二烯, 原位加氢

Abstract: Two-step hydrogenation of dicyclopentadiene(DCPD) was carried out over Pd/Al2O3 as catalyst and formic acid as hydrogen donor instead of H2. The hydrogenation products could be further used to prepare high density jet fuel and fine chemicals. This process avoids the high pressure, flammable and explosive risk and the high requirements for the equipment when using H2 as the hydrogen source, and can be completed in an ordinary container. The effects of formic acid adding mode, reaction time, reaction temperature, reaction solvent and substrate concentration were investigated. The results showed that adding formic acid by interval with average weight was beneficial for the formation of endo-tetrahydrodicyclopentadiene, the yield of which could be up to 99% after reaction 10 h at 160 ℃. In isopropanol, ethanol or tetrahydrofuran solvent, DCPD concentration of 40%-60% could effectively promote the formation of endo-tetrahydrodicyclopentadiene. At the same time, the stability of the catalyst was investigated, and it was found that the catalyst could still maintain high catalytic activity after five cycles, which meant good potential for industrialization.

Key words: hydrogen donor, formic acid, dicyclopentadiene, endo-tetrahydrodicyclopentadiene, in-situ hydrogenation