应用化学 ›› 2020, Vol. 37 ›› Issue (9): 1038-1047.DOI: 10.11944/j.issn.1000-0518.2020.09.200055

• 研究论文 • 上一篇    下一篇

短孔道介孔分子筛Zr-Ce-SBA-15固载酸性离子液体催化合成双酚F

刘宁a*, 王丹凤b, 伍素云a, 刘水林a, 付琳b, 刘跃进b*   

  1. a湖南工学院材料与化学工程学院,建筑材料研究院 湖南 衡阳 421002;
    b湘潭大学化工学院,化工过程模拟与强化国家地方联合工程研究中心 湖南 湘潭 411105
  • 收稿日期:2020-02-28 出版日期:2020-09-01 发布日期:2020-09-09
  • 通讯作者: 刘宁,讲师; Tel:0734-3452196; E-mail:liuning0731@163.com; 研究方向:功能催化材料及生物质转化;刘跃进,教授; Tel:0731-85262016; E-mail:xdlyj@163.com; 研究方向:功能催化材料及生物质转化
  • 基金资助:
    国家自然科学基金项目(21878255)、湖南省自然科学基金(2020JJ5117,2019JJ50107,2016JJ4028)、湖南省教育厅优秀青年项目(18B465)、衡阳市科技计划项目(2019jh010626)、湖南工学院人才科研启动基金(HQ 17014,HQ 17011)、功能金属有机化合物湖南省重点实验室开放基金(MO20K02)和湖南省应用特色学科材料科学与工程学科(湘教通[2018]469号)资助

Catalytic Synthesis of Bisphenol F over Short-Channeled Mesoporous Molecular Sieve Zr-Ce-SBA-15 Supported Acidic Ionic Liquids

LIU Ninga*, WANG Danfengb, WU Suyuna, LIU Shuilina, FU Linb, LIU Yuejinb*   

  1. aDepartment of Materials and Chemical Engineering,New Building Materials Academy, Hunan Institute of Technology,Hengyang,Hunan 421002,China;
    bSchool of Chemical Engineering,National & Local United Engineering Research Centre for Chemical Process Simulation and Intensification,Xiangtan University,Xiangtan,Hunan 411105,China
  • Received:2020-02-28 Published:2020-09-01 Online:2020-09-09
  • Contact: LIU Ning, lecturer; Tel:0734-3452196; E-mail:liuning0731@163.com; Research interests:functional materials and biomass conversion;LIU Yuejin, professor; Tel:0731-85262016; E-mail:xdlyj@163.com; Research interests:functional materials and biomass conversion
  • Supported by:
    Supported by the National Natural Science Foundation of China(No.21878255.), the Hunan Provincial Natural Science Foundation of China(No.2020JJ5117, No.2019JJ50107, No.2016JJ4028), the Foundation of Hunan Educational Committee(No.18B465), the Talent Scientific Research Fund of Hunan Institute of Technology(No.HQ 17014,No.HQ 17011), the Foundation of Key Laboratory of Functional Metal-Organic Compounds of Hunan Province(No.MO20K02), and the Characteristic Application Discipline of Material Science and Engineering in Hunan(No.Xiang-Jiao-Tong[2018]369)

摘要: 通过化学键接的方式,将酸性离子液体(ILs)分别负载于两种不同的硅基载体上,成功制备了SBA-15-ILs(SILs)与Zr-Ce-SBA-15-ILs(ZCSILs)等两种固载化酸性离子液体。 通过傅里叶变换红外光谱仪(FT-IR)、热重分析仪(TG-DTG)、X射线衍射仪(XRD)、N2吸附-脱附比表面仪(BET)、透射电子显微镜(TEM)、扫描电子显微镜(SEM)与有机元素分析仪(OEA)等对所制备催化剂的物化性能进行了表征,并进一步研究了其在甲醛-苯酚合成二羟基二苯基甲烷(双酚F,BPF)中的催化活性。 结果表明:短孔道的ZCSILs具有较高比表面积、较多的离子液体负载量和相对优异的催化活性。 当m(催化剂)/m(甲醛)=0.36,n(苯酚)/n(甲醛)=30,反应时间90 min、反应温度90 ℃时,BPF收率可达95.6%,对4,4′-BPF的选择性达到44.8%,且所制备的ZCSILs重复使用5次后,依然显示优异的催化活性。

关键词: 短孔道, 酸性离子液体, Zr-Ce-SBA-15, 双酚F, 选择性

Abstract: Two supported acidic ionic liquids (ILs) consisting of SBA-15-ILs (SILs) and Zr-Ce-SBA-15-ILs(ZCSILs) were prepared by combining acidic ionic liquids with the silica-based support. The physio-chemical properties of the obtained catalysts were characterized by Fourier transform infrared (FT-IR) spectroscopy, thermalgravimetry-differential thermal gravimetry (TG-DTG), X-ray diffraction (XRD), Brunauer Emmett Teller (BET), transimition electron microscopy (TEM), scanning electron microscopy (SEM) and organic elemental analysis (OEA) measurements. The catalytic activity of the prepared catalysts was evaluated in the hydroxyalkylation of phenol and aqueous formaldehyde to bisphenol F. The effects of operating variables, such as type of catalysts, molar ratio of phenol to formaldehyde, reaction temperature, reaction time and addition of catalysts on the yield of BPF and selectivity were investigated. Under the optimum conditions (catalyst/formaldehyde mass ratio 0.36, phenol/formaldehyde molar ratio 30∶1, reaction temperature 80 ℃ and reaction time 60 min), a high bisphenol F yield of 95.6% with 44.8% selectivity to 4,4′-BPF can be achieved over the short-channeled ZCSILs catalyst with large specific surface area and high loading amount of ionic liquids and its catalytic activity is still good after being reused for 5 times.

Key words: short channeled, acid ionic liquids, Zr-Ce-SBA-15, bisphenol F, selectivity