CuO/Al-SBA-15催化剂的合成及其对苯酚羟基化反应的催化性能

doi:10.3724/SP.J.1095.2014.30205

摘要/Abstract

摘要： 采用不同硅铝比的介孔分子筛（Al-SBA-15）作为载体负载不同量的铜元素作为催化剂（CuO/Al-SBA-15），通过小角X射线衍射、氮气吸附脱附等温线表征其结构性质,并以苯酚羟基化的反应为模型反应考察了材料的催化性能。研究发现，高的铜负载量不利于介孔材料结构的保持，在较低的铜负载量(3%)的情况下就可以使苯酚羟基化达到61.2%的高转化率。通过对Al-SBA-15和SBA-15作为载体的催化剂的循环套用分析，发现Al-SBA-15作为载体经过5次套用之后依然保持着57.9%的高转化率，而SBA-15经5次套用后的转化率仅有43.6%。这种结果应该得益于载体中的铝元素增加了材料表面的电荷，使铜离子与载体的相互作用加强，在循环套用中的铜离子在材料表面的分散更均匀。

Abstract: A series of catalysts, mesoporous molecular sieves(Al-SAB-15) supported copper oxide(CuO/Al-SBA-15) with different copper content and Si/Al mass ratios, was characterized by small X-ray diffraction, N2 adsorption-desorption and the catalytic activity in the phenol hydroxylation reaction. The mesostructure was found to become disordered with the copper content increasing. High catalytic conversion up to 61.2% was achieved with 3% copper. A 57.9% conversion for the phenol hydroxylation with the catalyst supported on Al-SAB-15 is higher than the 43.6% conversion with the catalyst supported on SBA-15 after 5 recycles. This may be attributed to the increased surface charges associated with Al cations and the resulted uniformly dispersed Cu.

Key words: phenol hydroxylation, mesoporous molecular sieves, CuO/Al-SBA-15

中图分类号:

O643

刘慧慧, 蒋天龙, 王艳芹. CuO/Al-SBA-15催化剂的合成及其对苯酚羟基化反应的催化性能[J]. 应用化学, DOI: 10.3724/SP.J.1095.2014.30205.

LIU Huihui*, JIANG Tianlong, WANG Yanqin . Synthesis of CuO/Al-SBA-15 Catalysts and Their Catalytic Performance for Hydroxylation of Phenol[J]. Chinese Journal of Applied Chemistry, DOI: 10.3724/SP.J.1095.2014.30205.

参考文献

[1] LV Aixia,FU Zaihui,TANG Chunlin,et al. Preparation of Iron Complexes-encapsulated HMS Catalysts by Microwave Irradiation Method and Their Catalytic Performance in Phenol Hydroxylation[J]. Ind Catal,2012,20(5):58-63(in Chinese).

吕爱霞,伏再辉,唐春林,等. 微波法制备HMS包络合铁配合物催化剂催化苯酚羟基化反应[J]. 工业催化,2012,20(5):58-63.

[2] DONG Yonglu. Hydroxylation of Phenol into Dihydroxybenzene over Hydrotalcite-like Compounds with Copper[J]. Sci Technol Enterprise,2012,(9):280-281(in Chinese).

董永路. 含铜类水滑石催化苯酚羟基化合成苯二酚[J]. 科技与企业,2012,(9):280-281.

[3] Zhang G Y,Long J L,Wang X X,et al. Catalytic Role of Cu Sites of Cu/MCM-41 in Phenol Hydroxylation[J]. Langmuir,2010,26(2): 1362–1371.

[4] Tanev P T,Chibwe M,Pinnavaia T J. Titanium-containing Mesoporous Molecular Sieves for Catalytic Oxidation of Aromatic Compounds[J]. Nature,1994,368:321-323.

[5] Ahn W S,Kim N K,Jeong S Y. Synthesis, Characterization, and Catalytic Properties of Ti-containing Mesoporous Molecular Sieves Prepared Using a Fluorosilicon Compound[J]. Catal Today,2001,68:83-88.

[6] Corma A,Navrro M T,Perez-Pariente J. Synthesis of an Ultralarge Pore Titanium Silicate Isomorphous to MCM-41 and Its Application as a Catalyst for Selective Oxidation of Hydrocarbons[J]. J Chem Soc Chem Commun,1994,2:147-148.

[7] Notari B. Synthesis and Catalytic Properties of Titanium Containing Zeolites[J]. Stud Surf Sci Catal,1988,37:413-425.

[8] Parida K M,Rath D. Surface Characterization and Catalytic Evaluation of Copper-promoted Al-MCM-41 toward Hydroxylation of Phenol[J]. J Colloid Interface Sci,2009,340:209-217.

[9] Wang L P,Kong A G,Chen B,et al. Direct Synthesis, Characterization of Cu-SBA-15 and Its High Catalytic Activity in Hydroxylation of Phenol by H2O2[J]. J Mol Catal A,2005,230:143-150.

[10] Jiang T L,Tao H X,Ren J W,et al. Fluoride Ions Assistant Synthesis of Extremely Hydrothermal Stable Al-SBA-15 with Controllable Al Content[J]. Micropor Mesopor Mater,2011,142:341-346.

[11] Yin A Y,Guo X Y,Dai W L,et al. Effect of Si/Al Ratio of Mesoporous Support on the Structure Evolution and Catalytic Performance of the Cu/Al-HMS Catalyst[J]. J Phys Chem C,2010,114:8523-8532.

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