化工学报 ›› 2021, Vol. 72 ›› Issue (5): 2616-2625.DOI: 10.11949/0438-1157.20210191

• 催化、动力学与反应器 • 上一篇    下一篇

中空Pt/ZSM-5催化剂用于愈创木酚加氢脱氧合成环烷烃

牛晓坡1,2(),徐爽1,2(),李晓雪1,2,冯富祥1,2,王庆法1,2()   

  1. 1.天津大学化工学院先进燃料与化学推进剂教育部重点实验室,天津 300072
    2.天津化学化工协同创新中心,天津 300072
  • 收稿日期:2021-01-31 修回日期:2021-03-09 出版日期:2021-05-05 发布日期:2021-05-05
  • 通讯作者: 王庆法
  • 作者简介:牛晓坡(1995—),男,博士研究生,xiaoponiu@tju.edu.cn|徐爽(1996—),女,硕士研究生,shuangxu@tju.edu.cn
  • 基金资助:
    国家自然科学基金项目(21476169)

Hollow Pt/ZSM-5 catalysts for highly selective hydrodeoxygenation of guaiacol to cycloalkanes

NIU Xiaopo1,2(),XU Shuang1,2(),LI Xiaoxue1,2,FENG Fuxiang1,2,WANG Qingfa1,2()   

  1. 1.Key Laboratory for Advanced Fuel and Propellant of Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China
    2.Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin University, Tianjin 300072, China
  • Received:2021-01-31 Revised:2021-03-09 Online:2021-05-05 Published:2021-05-05
  • Contact: WANG Qingfa

摘要:

采用溶解-重结晶方法合成了不同硅铝比具有级孔壳的中空ZSM-5分子筛,并对其负载Pt催化剂(Pt/HZ-x)催化愈创木酚加氢脱氧制备环烷烃性能进行了探究。通过X射线晶体衍射(XRD)、场发射扫描电子显微镜(SEM)、场发射透射电子显微镜(TEM)、氮气吸附脱附(N2-BET)、氨气程序升温脱附(NH3-TPD)和X射线光电子能谱(XPS)对合成的系列催化剂进行了物化性质表征。得益于特殊的中空级孔结构,中空ZSM-5分子筛具有高外比表面积和介孔孔容,有利于促进活性金属Pt的分散和增强反应物的传质。Pt/HZ-x催化剂表现出了优异的催化性能和愈创木酚加氢脱氧活性,在220℃的低温即可以达到100%的环烷烃选择性。另外,随着分子筛载体酸性的减弱,愈创木酚加氢脱氧产物的二次反应程度降低,增大了环己烷的选择性。

关键词: 中空分子筛, 生物燃料, 催化, 愈创木酚, 加氢脱氧, 合成, 环烷烃

Abstract:

Hollow ZSM-5 zeolites with different Si/Al molar ratios and hierarchical porous shell were fabricated via employing dissolution-recrystallization strategy, and utilized as support to load precious Pt (Pt/HZ-x) for hydrodeoxygenation of guaiacol to cycloalkanes. The physicochemical properties of the as-synthesized catalysts were characterized by powder X-ray crystalline diffraction (XRD), field emission scanning electron microscope (SEM), field emission transmission electron microscope (TEM), nitrogen adsorption and desorption (N2-BET), ammonia temperature program desorption (NH3-TPD) and X-ray photoelectron energy spectroscopy (XPS). Benefit from the special hollow structure, hollow ZSM-5 zeolites exhibited a larger external specific surface area and mesoporous volume, which was favorable to promote the dispersion of metallic Pt and mass transfer of reactants. The Pt/HZ-x catalysts showed excellent catalytic performance and hydrodeoxygenation activity for guaiacol, and could reach 100% selectivity to cycloalkanes at a low temperature of 220℃. In addition, as the acidity of the molecular sieve carrier weakens, the degree of secondary reaction of the guaiacol hydrodeoxygenation product decreases, which increased the selectivity to cyclohexane.

Key words: hollow zeolite, biofuel, catalysis, guaiacol, hydrodeoxygenation, synthesis, cycloalkanes

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