全氟磺酸树脂改性ZSM-5催化剂用于环己烯水合研究

doi:10.3969/j.issn.1000-1565.2025.01.007

河北大学学报(自然科学版) ›› 2025, Vol. 45 ›› Issue (1): 60-69.DOI: 10.3969/j.issn.1000-1565.2025.01.007

全氟磺酸树脂改性ZSM-5催化剂用于环己烯水合研究

牛立博¹,薛宇恋¹,张倩²,王亚涛²,徐肇中²,陈毅¹,吕运开¹

收稿日期:2024-10-23 出版日期:2025-01-25 发布日期:2025-02-25
通讯作者: 吕运开(1967—)
作者简介:牛立博(1984—),男,河北大学副教授,主要从事纳米催化剂的制备及性能研究.E-mail:niulibohbu@hotmail.com
基金资助:
河北省省级科技计划项目(22281403Z)

Perfluorosulfonic acid resin modified ZSM-5 zeolite as catalyst for cyclohexene hydration

NIU Libo¹, XUE Yulian¹, ZHANG Qian², WANG Yatao², XU Zhaozhong², CHEN Yi¹, LYU Yunkai¹

1.College of Chemistry and Materials Science, Hebei University, Baoding 071002, China; 2.Kailuan Energy Chemical Co., Ltd., Tangshan 063018, China

Received:2024-10-23 Online:2025-01-25 Published:2025-02-25

摘要/Abstract

摘要： 采用浸渍法将全氟磺酸树脂(HNF-5W)负载到ZSM-5分子筛表面以及孔道内部制备了磺酸树脂-分子筛复合催化剂xHNF/ZSM-5(x代表磺酸树脂在催化剂中的质量分数),应用于环己烯水合制备环己醇反应.利用BET、XED、TEM和吡啶红外等测试手段对所制备催化剂的物理化学性质进行了表征,同时考察了反应条件对所制备催化剂作用下环己烯水合反应的影响.实验结果表明:当反应温度125 ℃,氮气压力0.4 MPa的条件下,反应120 min,在最优催化剂20HNF/ZSM-5作用下环己烯的转化率为12.9%,环己醇选择性达到99%以上;同时,20HNF/ZSM-5催化剂经5次套用,环己烯的转化率仍保持在10%以上,表明该催化剂具有良好的稳定性.

关键词: ZSM-5, 全氟磺酸树脂, 环己烯水合, 环己醇

Abstract: A series xHNF/ZSM-5(where x represents the mass fraction of sulfonic acid resin in the catalyst)composite catalysts were prepared by loading perfluorosulfonic acid resin on ZSM-5 using the impregnation method and applied in the hydration of cyclohexene to produce cyclohexanol. The physicochemical properties of corresponding catalysts were studied by BET, XRD, TEM, and Py-IR. In addition, the influence of reaction condition was also investigated in this work. It was found that with reaction temperature of 125 ℃, 0.4 MPa of nitrogen pressure and the reaction time of 120 min, a 12.9% cyclohexene conversion with the selectivity of cyclohexanol over 99% could achieved with 20HNF/ZSM-5, which is the optimal catalyst in this reaction. Meanwhile, the conversion rate of cyclohexene remained above 10% for the 20HNF/ZSM-5 catalyst with five cycles, indicating its excellent stability during reaction.

Key words: ZSM-5, perfluorosulfonic acid resin, cyclohexene hydration, cyclohexanol

中图分类号:

O643.36

牛立博,薛宇恋,张倩,王亚涛,徐肇中,陈毅,吕运开. 全氟磺酸树脂改性ZSM-5催化剂用于环己烯水合研究[J]. 河北大学学报(自然科学版), 2025, 45(1): 60-69.

NIU Libo, XUE Yulian, ZHANG Qian, WANG Yatao, XU Zhaozhong, CHEN Yi, LYU Yunkai. Perfluorosulfonic acid resin modified ZSM-5 zeolite as catalyst for cyclohexene hydration[J]. Journal of Hebei University(Natural Science Edition), 2025, 45(1): 60-69.

参考文献

[1] KARIMI ESTAHBANATI M R, FEILIZADEH M, BABIN A, et al. Selective photocatalytic oxidation of cyclohexanol to cyclohexanone: A spectroscopic and kinetic study [J]. Chem Eng J, 2020,382:122732. DOI:10.1016/j.cej.2019.122732.
[2] ZHU Y F, GAO L, WEN L Y. Cyclohexene esterification-hydrogenation for efficient production of cyclohexanol [J]. Green Chem, 2021, 23(3): 1185-1192. DOI:10.1039/d0gc03020a.
[3] YANG M Y, WANG Y Q, LIU W R, et al. Synthesis of hierarchical ZSM-11 nanorods aggregates and catalytic properties in cyclohexene hydration to cyclohexanol[J]. Chemistryselect, 2023, 8(4):e202203642. DOI:10.1002/slct.202203642.
[4] 彭胜,李洪娟,贾伟艺,等.无有机模板剂制备ZSM-5分子筛及其环己烯水合应用 [J].工业催化, 2020, 28(6): 40-45.DOI: 10.3969/j.issn.1008-1143.2020.06.007.
[5] 郭志武,靳海波,佟泽民.环己酮、环己醇制备技术进展 [J].化工进展, 2006(8): 852-859.DOI: 10.16085/j.issn.1000-6613.2006.08.002.
[6] NAGAHARA H, ONO M, KONISHI M, et al. Partial hydrogenation of benzene to cyclohexene[J]. App Surf Sci, 1997, 121: 448-451. DOI: 10.1016/S0169-4332(97)00325-5.
[7] WANG Y Q, WANG S G, MENG F J, et al. Effect of NaOH treatment on catalytic performance of ZSM-5 in cyclohexene hydration [J]. Trans Tianjin Univ, 2017, 23: 43-50.DOI:10.1007/S12209-016-0020-3.
[8] ZAPATA P A, FARIA J, RUIZ M P, et al. Hydrophobic zeolites for biofuel upgrading reactions at the liquid-liquid interface in water/oil emulsions [J]. J Am Chem Soc, 2012, 134(20): 8570-8578. DOI:10.1021/ja3015082.
[9] CROSSLEY S, FARIA J, SHEN M, et al. Solid nanoparticles that catalyze biofuel upgrade reactions at the water/oil interface [J]. Science, 2010, 327(5961): 68-72. DOI:10.1126/science.1180769.
[10] MELKI S, BIGUENET F, DUPUIS D. Hydrophobic properties of textile materials: robustness of hydrophobicity [J]. J Text Inst, 2019, 110(8): 1221-1228. DOI:10.1080/00405000.2018.1553346.
[11] PERA-TITUS M, LECLERCQ L, CLACENS J-M, et al. Pickering interfacial catalysis for biphasic systems: from emulsion design to green reactions [J]. Angew Chem Int Ed Engl, 2015, 54(7): 2006-2021. DOI:10.1002/anie.201402069.
[12] LI Y, YU J H. New stories of zeolite structures: their descriptions, determinations, predictions, and evaluations [J]. Chem Rev, 2014, 114(14): 7268-7316. DOI:10.1021/cr500010r.
[13] WANG C, LENG S, GUO H, et al. Quantitative arrangement of Si/Al ratio of natural zeolite using acid treatment [J]. Appl Surf Sci, 2019, 498:143874. DOI:10.1016/j.apsusc.2019.143874.
[14] 李宏博,桑雅丽,安静,等.全氟磺酸树脂催化玉米芯水解条件的优化 [J].辽宁化工, 2021, 50(8): 1119-1123.DOI: 10.3969/j.issn.1004-0935.2021.08.004.
[15] HARMER M A,FARNETH W E,SUN QUN. High surface area Nafion resin silica nanocomposites:A new class of solid acid catalyst[J]. J Am Chem Soc, 1996, 118(33): 7708-7715. DOI: 10.1021/ja9541950.
[16] TIAN H, LIU S, HAN Y C, et al. Acid treatment to adjust zeolite hydrophobicity for olefin hydration reaction [J]. J Porous Mater, 2022, 29(3): 713-722. DOI:10.1007/s10934-022-01199-0.
[17] FELICE V, TAVARES A C. Faujasite zeolites as solid electrolyte for low temperature fuel cells [J]. Solid State Ion, 2011, 194(1): 53-61. DOI:10.1016/j.ssi.2011.05.006.
[18] LIANG X, XU Y, TAN X, et al. Heavy metal adsorbents mercapto and amino functionalized palygorskite: Preparation and characterization [J]. Colloids Surf A-Physicochem Eng Aspects, 2013, 426: 98-105. DOI:10.1016/j.colsurfa.2013.03.014.
[19] ZHAN X, LI J D, FAN C, et al. Pervaporation separation of ethanol/water mixtures with chlorosilane modified silicalite-1/PDMS hybrid membranes [Z]. Chin J Polym Sci, 2010,28(4): 625-639. DOI:10.1007/s10118-010-9136-4.
[20] MAO L, MISHRA A K, KIM N H, et al. Poly(2,5-benzimidazole)-silica nanocomposite membranes for high temperature proton exchange membrane fuel cell [J]. J Membr Sci, 2012, 411/412: 91-98. DOI:10.1016/j.memsci.2012.04.018.
[21] SHAIKH R A, HEGDS S G, BEHLEKAR A A, et al. Enhancement of acidity and paraselectivity by the silynation in pentasil zeolites [J]. Catal Today, 1999, 49(1): 201-209. DOI: 10.1016/S0920-5861(98)00425-8.
[22] TOSHEVA L, VALTCHEV V, STERTE J. Silicalite-1 containing microspheres prepared using shape-directing macrotemplates [J]. Microporous Mesoporous Mater, 2000, 36: 621-629. DOI: 10.1016/S1387-1811(99)00256-5.
[23] VISWANADHAM N, KAMBLE R, SINGH M, et al. Catalytic properties of nano-sized ZSM-5 aggregates [J]. Catal Today, 2009, 141(1-2): 182-186. DOI:10.1016/j.cattod.2008.03.026.
[24] LIU S, SUN D H, TIAN H. Novel hydrophobic catalysts to promote hydration at the water-oil interface [J]. Rsc Adv, 2021, 11(30): 18299-18307. DOI:10.1039/d1ra01188j. (

全氟磺酸树脂改性ZSM-5催化剂用于环己烯水合研究

Perfluorosulfonic acid resin modified ZSM-5 zeolite as catalyst for cyclohexene hydration

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 4

编辑推荐

Metrics

本文评价

[1]	温昕,董洁,舍添添,白国义. 苯酚加氢研究进展[J]. 河北大学学报(自然科学版), 2018, 38(3): 239-247.
[2]	彭绍辉,杜忠文,冯俊娜,董玉环,陈华. 微波辐射合成苹果酸丁酯[J]. 河北大学学报(自然科学版), 2013, 33(5): 502-507.
[3]	白国义,贾春伟,宁慧森. 基于钨基催化剂的环己醇氧化反应[J]. 河北大学学报(自然科学版), 2008, 28(6): 635-639.
[4]	马志广,邹于梅,张爱平. ZSM-5分子筛负载钯-壳聚糖配合物催化苯丙酮加氢的反应动力学[J]. 河北大学学报(自然科学版), 2008, 28(5): 494-498,506.