罗灿,张会平,鄢瑛

• 1:华南理工大学 化学与化工学院，广东 广州 510640

摘要(Abstract)：

采用化学气相沉积法（CVD）制备了微纤复合Cu-5A/PSSF和Cu-ZSM-5/PSSF分子筛膜催化剂，研究了异丙醇在两种微纤复合分子筛膜催化剂上的催化氧化性能。采用湿法造纸和现代烧结工艺制备了不锈钢微纤预载体，分别采用二次生长法和原位水热合成法在经过表面改性后的不锈钢微纤表面合成ZSM-5和5A分子筛膜，通过化学气相沉积法分子筛膜表面负载Cu元素，得到微纤复合Cu-ZSM-5/PSSF和Cu-5A/PSSF分子筛膜催化剂。N₂吸脱附曲线、XRD、SEM和XPS等表征结果表明：所制备的不锈钢微纤预载体形成了发达的三维网状结构，分子筛膜致密均匀地分布在不锈钢微纤载体表面，厚度分别为1.2和1.5 μm，CuO活性组分被均匀的分散在分子筛膜上，实际负载量约为（3.2~3.7）%（wt）。结合异丙醇催化氧化反应的T₉₀看，催化活性为：Cu-ZSM-5/PSSF > Cu-ZSM-5 > Cu-5A > Cu-5A/PSSF，其中Cu-ZSM-5/PSSF的T₉₀比Cu-ZSM-5降低了20℃，T₅₀降低了40℃，表明分子筛膜材料的三维网状结构加强了传热与传质；Cu-ZSM-5分子筛催化剂的活性要好于Cu-5A分子筛催化剂，表明ZSM-5比5A分子筛的孔道结构更有利于异丙醇的催化氧化。

关键词(KeyWords)： 微纤复合分子筛膜;化学气相沉积法;异丙醇;催化氧化

Abstract:

Keywords:

基金项目(Foundation): 国家自然科学基金（21776106）。

作者(Author): 罗灿,张会平,鄢瑛

DOI: 10.3969/j.issn.1003-9015.2018.01.027

参考文献(References)：

• [1] KONG Li-ming (孔黎明), ZHOU Tao (周涛), JIAN Pan-ming (菅盘铭), et al. Characterization of Cu-SBA-15 molecular sieve and its catalytic performance for oxidation of 4-nitrophenol in aqueous solutions (Cu-SBA-15分子筛的表征及其催化氧化水溶液中4-硝基苯酚的性能)[J]. Journal of Chemical Engineering of Chinese Universities (高校化学工程学报), 2012, 26(4):618-623.
  [2] Barakat T, Rooke J C, Tidahy H L, et al. Noble-metal-based catalysts supported on zeolites and macro-mesoporous metal oxide supports for the total oxidation of volatile organic compounds[J]. Chemsuschem, 2011, 4(10):1420-1430.
  [3] ZHANG Run-duo (张润铎), QUAN Xie (全燮), YANG Feng-lin (杨凤林), et al. Kinetics of selective catalytic reduction of NO with NH₃ on wire-mesh-honeycomb (蜂窝状筛网催化剂上NH₃选择性催化还原NO的动力学)[J]. Journal of Dalian University of Technology (大连理工大学学报), 2002, 42(2):158-162.
  [4] YANG Xiao-dan (杨晓丹), JIANG Chun-hai (姜春海), YANG Zhen-ming (杨振明), et al. Preparation and catalytic properties of SiC foam supported Co-based structured catalysts (泡沫SiC负载钴基结构化催化剂的制备及其催化性能)[J]. Acata Metallurgica Sinica (金属学报), 2014, 50(6):762-768.
  [5] Reichelt E, Heddrich M P, Jahn M, et al. Fiber based structured materials for catalytic applications[J]. Applied Catalysis A:General, 2014, 476(6):78-90.
  [6] Yuranov I, Renken A, Kiwi-Minsker L. Zeolite/sintered metal fibers composites as effective structured catalysts[J]. Applied Catalysis A:General, 2005, 281(1-2):55-60.
  [7] Beers A E W, Nijhuis T A, Aalders N, et al. BEA coating of structured supports-performance in acylation[J]. Applied Catalysis A:General, 2003, 243(2):237-250.
  [8] Chen H H, Zhang H P, Yan Y. Preparation and characterization of a novel gradient porous ZSM-5 zeolite membrane/PSSF composite and its application for toluene adsorption[J]. Chemical Engineering Journal, 2012, 209(20):372-378.
  [9] Lam F L Y, Hu X J. A new system design for the preparation of copper/activated carbon catalyst by metal-organic chemical vapor deposition method[J]. Chemical Engineering Science, 2003, 58(3-6):687-695.
  [10] Babu E S, Hong S K. Effect of indium concentration on morphology of ZnO nanostructures grown by using CVD method and their application for H₂ gas sensing[J]. Superlattices & Microstructures, 2015, 82:349-356.
  [11] Ding Z, Hu X J, Lu G, et al. Novel silica gel supported TiO₂ photocatalyst synthesized by CVD method[J]. Langmuir, 2000, 16(15):6216-6222.
  [12] XU Su (徐甦), ZHOU Ming-hua (周明华), ZHANG Xing-wang (张兴旺), et al. Preparation and evaluation of nanosized TiO₂ supported on activated carbon by metal-organic chemical vapor deposition (金属有机物化学气相沉积法制备负载型纳米TiO₂光催化剂及性能评价)[J]. Journal of Chemical Engineering of Chinese Universities (高校化学工程学报), 2005, 19(1):119-123.
  [13] Zhang D, Zhang H P, Yan Y. Synthesis of 5A zeolite coating/PSSF composites and the application for adsorption of methane from air[J]. RSC Advances, 2015, 5(68):54913-54919.
  [14] Melo C R, Riella H G, Kuhnen N C, et al. Synthesis of 4A zeolites from kaolin for obtaining 5A zeolites through ionic exchange for adsorption of arsenic[J]. Materials Science & Engineering:B, 2012, 177(4):345-349.
  [15] Huang A S, Wang N Y, Caro J. Synthesis of multi-layer zeolite LTA membranes with enhanced gas separation performance by using 3-aminopropyltriethoxysilane as interlayer[J]. Microporous & Mesoporous Materials, 2012, 164(1):294-301.
  [16] Seo C K, Choi B, Kim H, et al. Effect of ZrO₂ addition on de-NOx performance of Cu-ZSM-5 for SCR catalyst[J]. Chemical Engineering Journal, 2012, 191(19):331-340.
  [17] Nezamzadeh-Ejhieh A, Karimi-Shamsabadi M. Comparison of photocatalytic efficiency of supported CuO onto micro and nano particles of zeolite X in photodecolorization of methylene blue and methyl orange aqueous mixture[J]. Applied Catalysis A:General, 2014, 477(7):83-92.
  [18] Pan Y C, Liu Y Y, Zeng G F, et al. Rapid synthesis of zeolitic imidazolate framework-8(ZIF-8) nanocrystals in an aqueous system[J]. Chemical Communications, 2011, 47(7):2071-2073.
  [19] Li Z Z, Tong K E, Shi R, et al. Reactive plasma deposition of high quality single phase CuO thin films suitable for metal oxide solar cells[J]. Journal of Alloys and Compounds, 2017, 695:3116-3123.
  [20] Chen H H, Zhang H P, Yan Y. Fabrication of porous copper/manganese binary oxides modified ZSM-5 membrane catalyst and potential application in the removal of VOCs[J]. Chemical Engineering Journal, 2014, 254(7):133-142.
  [21] Yang S X, Feng Y J, Wan J F, et al. Effect of CeO₂ addition on the structure and activity of RuO₂/γ-Al₂O₃ catalyst[J]. Applied Surface Science, 2005, 246(1):222-228.
  [22] Wang J B, Zhu W P, He X W, et al. Catalytic wet air oxidation of acetic acid over different ruthenium catalysts[J]. Catalysis Communications, 2008, 9(13):2163-2167.
  [23] Wang X Y, Kang Q, Li Q. Catalytic combustion of chlorobenzene over MnOx-CeO₂ mixed oxide catalysts[J]. Applied Catalysis B:Environmental, 2009, 86(3):166-175.
  [24] Zhang K, Lively R P, Noel J D, et al. Adsorption of water and ethanol in MFI-type zeolites[J]. Langmuir, 2012, 28(23):8664-8673.
  [25] Zhang Z Q, Atkinson J D, Jiang B Q, et al. NO oxidation by microporous zeolites:isolating the impact of pore structure to predict NO conversion[J]. Applied Catalysis B:Environmental, 2015, 163:573-583.
  [26] Bashkova S, Baker F S, Wu X X, et al. Activated carbon catalyst for selective oxidation of hydrogen sulphide:on the influence of pore structure, surface characteristics, and catalytically-active nitrogen[J]. Carbon, 2007, 45(6):1354-1363.