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纪镁铃 ，刘国柱，王莅 * ，张香文 天津大学 化工学院 化学工艺

b. a. c. b- 轴取向 HZSM-5 分子筛涂层的合成 及其催化裂解正十二烷性能研究. 纪镁铃 ，刘国柱，王莅 * ，张香文 天津大学 化工学院 化学工艺. * Email: wlytj @tju.edu.cn. b- 轴取向 HZSM-5 催化涂层. Zeolites. Zeolite membranes/coatings. Preferred-oriented MFI membranes. anisotropic pore structure. Excellent. Separation membranes.

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纪镁铃 ，刘国柱，王莅 * ，张香文 天津大学 化工学院 化学工艺

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  1. b a c b-轴取向HZSM-5分子筛涂层的合成 及其催化裂解正十二烷性能研究 纪镁铃，刘国柱，王莅*，张香文 天津大学 化工学院 化学工艺 *Email: wlytj @tju.edu.cn

  2. b-轴取向 HZSM-5 催化涂层 Zeolites Zeolite membranes/coatings Preferred-oriented MFI membranes anisotropic pore structure Excellent Separation membranes Faster diffusion pathway Catalysts Chemical sensors Low-k dielectrics • Our work • b-oriented HZSM-5 • catalytic coaitngs Adsorbents Corrosion protection coatings Ion exchangers Zeolite film for catalysis ······ 1

  3. b-轴取向 HZSM-5 催化涂层（单层） Rough surface 1. dip coating with TiO2 sols OH OH OH OH OH OH OH OH TiO2 layer Stainless steel tube 2. in-situ growth b-oriented ZSM-5 zeolite coating • Positive effects of TiO2 interlayer: • provide a smooth surface • provide high density of Ti-OH groups • promote the attraction forces between the substrate and the zeolite crystals 2 Meiling Ji, Guozhu Liu, Chen Chen, Li Wang, Xiangwen Zhang, Micropor Mesopor Mater,2012, 155:117-.123

  4. b-轴取向 HZSM-5 催化涂层（单层） b-oriented HZSM-5 coating on SST 3 µm 10 µm Fig.1 SEM images of b-HZSM-5 monolayer. Fig.2 XRD pattern of b-HZSM-5 monolayer. 3

  5. 怎么样得到b-取向HZSM-5 涂层（多层）? Method 1: Direct secondary growth 3 µm 3 µm 10 µm 10 µm Fig.3 SEM images of a&b-HZSM-5 bi-layer. Fig.4 XRD pattern of a&b-HZSM-5 bi-layer. 4

  6. 怎么样得到b-取向HZSM-5 涂层（多层）? Solution 2: With TiO2 modification TiO2 ZSM-5 TiO2 1 μm 5 μm Fig.5 SEM images of b@b-HZSM-5 bi-layer. Fig.6 XRD pattern of b@b-HZSM-5 bi-layer. 5

  7. 分子筛催化涂层表征 Table 1.Si/Al ratio, zeolite thickness and mass loading of the zeolite film. TiO2 6

  8. 分子筛催化涂层反应活性 —正十二烷催化裂解反应 conversion 反应装置示意图 ≈ 45% improvement Catalytic cracking of n-dodecane over prepared oriented HZSM-5 films as a function of stream time. (pressure=4 MPa, LHSV=637 h-1, temperature=550 ºC). 7

  9. 分子筛催化涂层渗透性能 permeation 渗透装置示意图 Permeance of N2 gas through the porous stainless steel support and the zeolite coatings. 8

  10. 分子筛催化涂层积碳分析 The total amount of coke and the penetration depth of the carbonaceous deposit. a Estimated from the XPS profiles; b Calculated from the intergral areas of the TPO profiles. 9

  11. 有效扩散因子η的估算 L reactant Stainless steel Zeolite coating Z dZ 10

  12. 讨论：分子筛取向对反应活性的影响 b a coke n-dodecane coke n-dodecane c b&b-HZSM-5 b-HZSM-5 a&b-HZSM-5 11

  13. 小结 • 提出一种合成b-轴HZSM-5 催化涂层（多层）的制备方法。 • TiO2中间层是合成b-轴HZSM-5 催化涂层（多层）的关键之一。 • b-轴取向ZSM-5孔道有利于提高涂层扩散性能和催化反应活性。 12

  14. Q&A Thank you for your time! 纪镁铃，刘国柱，王莅*，张香文 天津大学 化工学院 化学工艺 *Email: wlytj @tju.edu.cn

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