UiO-66基催化剂的酸调控及其在丁烯双键异构反应中的应用

石油炼制与化工 ›› 2022, Vol. 53 ›› Issue (5): 21-27.

UiO-66基催化剂的酸调控及其在丁烯双键异构反应中的应用

王宪飞,刘伟,田林宇,李潘之,陈小平,任万忠

烟台大学化学化工学院

收稿日期:2021-07-06 修回日期:2022-01-14 出版日期:2022-05-12 发布日期:2022-04-24
通讯作者: 陈小平 E-mail:chemxp@163.com
基金资助:
国家自然科学基金项目

ACID MODULATION OF UiO-66-BASED CATALYSTS AND ITS APPLICATION IN THE DOUBLE-BOND ISOMERIZATION OF BUTENE

Received:2021-07-06 Revised:2022-01-14 Online:2022-05-12 Published:2022-04-24

摘要/Abstract

摘要： 通过添加盐酸和乙酸调节剂成功合成了含有缺陷位点的UiO-66-HCl和UiO-66-HAC催化剂。X射线衍射、傅里叶变换红外光谱、热重分析、扫描电镜、N₂吸附-脱附和NH₃程序升温脱附等表征结果表明，催化剂的结晶度、粒径、形貌和孔结构得到优化，酸量提高。丁烯原料的评价结果表明：添加调节剂制备的含有较多缺陷位点的UiO-66显著提高了2-丁烯双键异构生成1-丁烯的催化性能；当反应温度为360 ℃、体积空速为12 h^-1时，UiO-66-HAC催化丁烯双键异构生成1-丁烯的收率高达12.7%，选择性高达97%。

关键词: UiO-66, 调节剂, 2-丁烯, 1-丁烯, 双键异构

Abstract: UiO-66-HCl and UiO-66-HAC catalysts containing defect sites were successfully synthesized by adding hydrochloric acid and acetic acid modifier. The results of XRD, TG, SEM, BET and TPD showed that the crystallinity, particle size, morphology and pore structure of the catalyst had been optimized, and the acid content has been increased. The evaluation results of butene as raw material showed that UiO-66 with many defect sites could significantly improve the catalytic performance of 2-butene double-bond isomerization to 1-butene. When the reaction temperature was 360 ℃ and the volume space velocity was 12 h^-1, UiO-66-HAC catalyzed double-bond isomerization of 2-butene to 1-butene with a yield of 12.7% and a selectivity of 97%.

Key words: UiO-66, modifier, 2-butene, 1-butene, double-bond isomerization

王宪飞刘伟田林宇李潘之陈小平任万忠. UiO-66基催化剂的酸调控及其在丁烯双键异构反应中的应用[J]. 石油炼制与化工, 2022, 53(5): 21-27.

参考文献

[1]Park Y-K, Kim S J, You N, et al.MoO3SiO2 catalysts for double bond migration of 2-butene[J].Journal of Industrial and Engineering Chemistry, 2011, 17(2):186-190 [2]You N, Yim J H, Lee S J, et al.Positional isomerization of butene-2 over nanoporous MCM-48 catalysts[J].J Nanosci Nanotechnol, 2007, 7(11):3800-3804 [3]Jeon J-K, Park Y-K, Yim J-H.Cyclodextrin-modified MCM-41 for selective double bond migration[J].Research on Chemical Intermediates, 2010, 36(6-7):661-667 [4]Destefano M R, Islamoglu T, Garibay S J, et al.Room-Temperature Synthesis of UiO-66 and Thermal Modulation of Densities of Defect Sites[J].Chemistry of Materials, 2017, 29(3):1357-1361 [5]Wu H, Chua Y S, Krungleviciute V, et al.Unusual and highly tunable missing-linker defects in zirconium metal-organic framework UiO-66 and their important effects on gas adsorption[J].J Am Chem Soc, 2013, 135(28):10525-10532 [6]Vermoortele F, Bueken B, Le Bars G, et al.Synthesis modulation as a tool to increase the catalytic activity of metal-organic frameworks: the unique case of UiO-66(Zr)[J].J Am Chem Soc, 2013, 135(31):11465-11468 [7]韩素英, 韩新华, 曹运祥, 等.金属有机框架材料-吸附分离性能研究[J].石油炼制与化工, 2018, 49(05):43-48 [8]李伦西, 龙军, 吴巍, 等.金属有机骨架材料用于芳烃吸附分离的探索研究[J].石油炼制与化工, 2018, 49(08):32-37 [9]Winarta J, Shan B, Mcintyre S M, et al.A Decade of UiO-66 Research: A Historic Review of Dynamic Structure,Synthesis Mechanisms,and Characterization Techniques of an Archetypal Metal–Organic Framework[J].Crystal Growth & Design, 2019, 20(2):1347-1362 [10]Xiao W, Dong Q, Wang Y, et al.Time modulation of defects in UiO-66 and application in oxidative desulfurization[J].CrystEngComm, 2018, 20(38):5658-5662 [11] Zhao W W, Zhang C Y, Yan Z G, et al.Separations of substituted benzenes and polycyclic aromatic hydrocarbons using normal- and reverse-phase high performance liquid chromatography with UiO-66 as the stationary phase[J]. J Chromatogr A, 2014, 1370: 121-128. [12] Ou R, Zhu W, Li L, et al.Boosted capture of volatile organic compounds in adsorption capacity and selectivity by rationally exploiting defect-engineering of UiO-66(Zr)[J]. Separation and Purification Technology, 2021, 266. [13]Yang P, Liu Q, Liu J, et al.Correction: Interfacial growth of a metal–organic framework (UiO-66) on functionalized graphene oxide (GO) as a suitable seawater adsorbent for extraction of uranium(vi)[J].Journal of Materials Chemistry A, 2018, 6(17):8121-8121 [14]Kandiah M, Nilsen M H, Usseglio S, et al.Synthesis and Stability of Tagged UiO-66 Zr-MOFs[J].Chemistry of Materials, 2010, 22(24):6632-6640 [15]Wei J, Zhang W, Pan W, et al.Experimental and theoretical investigations on Se(iv) and Se(vi) adsorption to UiO-66-based metal–organic frameworks[J].Environmental Science: Nano, 2018, 5(6):1441-1453 [16]Liang W, Coghlan C J, Ragon F, et al.Defect engineering of UiO-66 for CO2 and H2O uptake - a combined experimental and simulation study[J].Dalton Trans, 2016, 45(11):4496-4500 [17]Katz M J, Brown Z J, Colon Y J, et al.A facile synthesis of UiO-66,UiO-67 and their derivatives[J].Chem Commun (Camb), 2013, 49(82):9449-9451 [18]Ragon F, Horcajada P, Chevreau H, et al.In situ energy-dispersive X-ray diffraction for the synthesis optimization and scale-up of the porous zirconium terephthalate UiO-66[J].Inorg Chem, 2014, 53(5):2491-2500 [19]Shearer G C, Chavan S, Bordiga S, et al.Defect Engineering: Tuning the Porosity and Composition of the Metal–Organic Framework UiO-66 via Modulated Synthesis[J].Chemistry of Materials, 2016, 28(11):3749-3761 [20]Schaate A, Roy P, Godt A, et al.Modulated synthesis of Zr-based metal-organic frameworks: from nano to single crystals[J].Chemistry, 2011, 17(24):6643-6651 [21]Liu L, Chen Z, Wang J, et al.Imaging defects and their evolution in a metal-organic framework at sub-unit-cell resolution[J].Nat Chem, 2019, 11(7):622-628 [22]Yuan L, Tian M, Lan J, et al.Defect engineering in metal-organic frameworks: a new strategy to develop applicable actinide sorbents[J].Chem Commun (Camb), 2018, 54(4):370-373 [23]Valenzano L, Civalleri B, Chavan S, et al.Disclosing the Complex Structure of UiO-66 Metal Organic Framework: A Synergic Combination of Experiment and Theory[J].Chemistry of Materials, 2011, 23(7):1700-1718 [24]Shearer G C, Chavan S, Ethiraj J, et al.Tuned to Perfection: Ironing Out the Defects in Metal–Organic Framework UiO-66[J].Chemistry of Materials, 2014, 26(14):4068-4071 [25] Zango Z U, Sambudi N S, Jumbri K, et al.Experimental and molecular docking model studies for the adsorption of polycyclic aromatic hydrocarbons onto UiO-66(Zr) and NH2-UiO-66(Zr) metal-organic frameworks[J]. Chemical Engineering Science, 2020, 220. [26] Cliffe M J, Wan W, Zou X, et al.Correlated defect nanoregions in a metal-organic framework[J]. Nat Commun, 2014, 5: 4176. [27]Saidi M, Samimi F, Karimipourfard D, et al.Upgrading of lignin-derived bio-oils by catalytic hydrodeoxygenation[J].Energy Environ. Sci., 2014, 7(1):103-129 [28]Yang J, Williams C L, Ramasubramaniam A, et al.Aqueous-phase hydrodeoxygenation of highly oxygenated aromatics on platinum[J].Green Chem., 2014, 16(2):675-682