石油炼制与化工 ›› 2025, Vol. 56 ›› Issue (3): 8-17.

• 催化剂 • 上一篇    下一篇

Ni/yMnOx-ZrO2催化愈创木酚加氢制环己醇的性能

凤雏,涂椿滟,刘路含,刘春婷,黄伟   

  1. 太原理工大学化学与化工学院,省部共建煤基能源清洁高效利用国家重点实验室
  • 收稿日期:2024-09-14 修回日期:2024-11-09 出版日期:2025-03-12 发布日期:2025-02-25
  • 通讯作者: 涂椿滟 E-mail:tuchunyan@tyut.edu.cn

CATALYTIC PERFORMANCE OF Ni/yMnOx-ZrO2 FOR HYDROGENATION OF GUAIACOL TO CYCLOHEXANOL

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  • Received:2024-09-14 Revised:2024-11-09 Online:2025-03-12 Published:2025-02-25

摘要: 采用行星球磨法合成了不同Mn/Zr摩尔比的复合氧化物(yMnOx-ZrO2),并负载Ni制备了一系列的Ni/yMnOx-ZrO2催化剂。通过X射线衍射、氨气程序升温脱附、吡啶吸附红外光谱、N2物理吸附-脱附、氢气程序升温还原对催化剂进行了物化性质的表征。以愈创木酚为原料,考察了Ni/yMnOx-ZrO2系列催化剂在愈创木酚加氢转化反应中的催化性能。结果表明:Mn的掺杂促进了Ni/yMnOx-ZrO2催化剂弱酸及中强酸的形成,有利于愈创木酚通过脱甲氧基形成以苯酚为中间体的反应路径制备环己醇;升高反应温度和延长反应时间均有利于提高环己醇收率,但也会导致环己醇过度加氢转化为环己烷;当Mn/Zr摩尔比为0.20时,Ni/0.20MnOx-ZrO2催化剂表现出优异的催化性能,在反应温度为260 ℃、H2初始压力为2.0MPa、反应时间为1.5 h的条件下,愈创木酚转化率和环己醇选择性分别为100%和63.5%。

关键词: 复合氧化物, Ni基催化剂, ZrO2, Mn掺杂, 愈创木酚, 环己醇

Abstract: Ni/yMnOx-ZrO2 composite oxides with different Mn/Zr molar ratios were synthesized by planetary ball milling method, and a series of Ni/yMnOx-ZrO2 catalysts were prepared by loading nickel on them.The physicochemical properties of the catalysts were characterized by X-ray diffraction, NH3 temperature programmed desorption, pyridine infrared, N2 physical adsorption-desorption, and hydrogen temperature programmed reduction.The catalytic performance of Ni/yMnOx-ZrO2catalysts in the hydroconversion of guaiacol was investigated. The results showed that the doping of Mn promoted the formation of weak acid and medium-strong acid on Ni/yMnOx-ZrO2 catalysts, which was beneficial to the generation of cyclohexanolviathe reaction path of phenol intermediate formed via guaiacoldemethoxylation.Both increasing the reaction temperature and prolonging the reaction time were beneficial to improve the yield of cyclohexanol, but it could lead to excessive hydrogenation of cyclohexanol to cyclohexane.When the molar ratio of Mn/Zr was 0.20, the Ni/0.20MnOx-ZrO2 catalyst showed excellent catalytic performance. Under the reaction conditions of 260 ℃, 2.0MPa and 1.5 h, the conversion of guaiacol and the selectivity of cyclohexanol were 100% and 63.5%, respectively.

Key words: composite oxide, Ni-based catalyst, ZrO2, Mn doping, guaiacol, cyclohexanol