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Hydrothermal synthesis of ZSM-5 membranes. Outline content 1.1. In situ growth 2.2. Secondary growth 3.3. Work plan.

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Presentation on theme: "Hydrothermal synthesis of ZSM-5 membranes. Outline content 1.1. In situ growth 2.2. Secondary growth 3.3. Work plan."— Presentation transcript:

1 Hydrothermal synthesis of ZSM-5 membranes

2 Outline content 1.1. In situ growth 2.2. Secondary growth 3.3. Work plan

3 1.1. In situ growth

4 crystallization conditions Time & Temperature 165 ℃, 4 h 165 ℃, 12 h 165 ℃, 24 h 185 ℃, 4 h 185 ℃, 24 h

5 165 ℃, 12 h substrate 165 ℃, 24 h

6 Concentration Crystallization Time nucleation crystal growth C1C1 t1t1 t3t3 24 h t2t2 t4t4

7 020 surface roughness

8 2.2. Secondary growth

9 Random orientation Thickness ~1.8μm 101 200/020 332/051 151/303 133 Reproducity of secondary growth Random orientation good intergrowth

10 0.36TPAOH:1TEOS:58H 2 O:4EtOH aging Crystallization 98 ℃, 48 h Centrifugation 10000 r/min for 10 min The amount of seed can be easily controlled. The obtained seed can be stored in a desiccator for later use. weighing Ultrasonication 15 min Preparation of seed

11 Impact of seed concentration

12 Random orientation seed obtained after centrifugation 5 mg/mL in EtOH 25SiO 2 : 9TPAOH : 1450H 2 O: 100EtOH 100 ℃ , 48 h A gel layer formedDiscrete zeolite particles PH = 12.49PH = 6.16 Seed coated

13 Effect of Al It facilitate the formation of the gel layer on the support. It retard zeolitization in this gel layer. JH Koegler, H Bekkum, et al., Zeolites,1997,19(4): 262-269. Re Lai, Yushan Yan, George R. Gavalas, Micropor Mesopor Mater, 2000,37(1-2):9-19

14 good stable unstable agglomerate Si/Al Zeta potential(mv) Adv. Funct. Mater. 2008, 18, 952–958 Figure1. Zeta potential vs. PH for zeolite silicalite-1 crystals in aqueous suspension.

15 100% ( 101 ) 21.9% ( 051 ) 56.8% ( 051 ) 59.0% ( 051 ) PDF : #44-0003 ZSM-5:Al 2 O 3 54SiO 2 0mg/mL 2mg/mL 5mg/mL CPO(101)/(051) = ? Concentration ( mg/mL ) CPO I: intensity of ( 101 ) and ( 051 ) P: PDF#44-0003 S: 0mg/mL 、 2mg/mL 、 5mg/mL 0 20.0373 50.6288

16 I:intensity of a peak P:powder reference S:film sample Characteristic planes and growing axis for MFI type zeolite Plane(Miller index)Growing axis Reference (501)a-axis[1] (051)b-axis[2] [(200)+(020)][a+b]-axis[1] (002)c-axis[2,3,4] (101) Oblique c-axis [3] (133) Oblique c-axis [1,2,4] [1] Microporous and Mesoporous Materials, 1999. 28(1): 185-194 [2] Journal of Materials Chemistry, 1998, 8(10): 2217-2221. [3]Microporous and Mesoporous Materials, 2009,123(1-3):113-112 [4]Microporous and Mesoporous Materials, 2008, 115(1-2): 113-122. I:intensity of a peak P:powder reference S:film sample Fig.1. Typical shape of MFI-typ zeolite crystals CPO definition

17 100% ( 101 ) 21.9% ( 051 ) 56.8% ( 051 ) 59.0% ( 051 ) PDF : #44-0003 ZSM-5:Al 2 O 3 54SiO 2 0mg/mL 2mg/mL 5mg/mL CPO(101)/(051) = ? Concentration ( mg/mL ) CPO I: intensity of ( 101 ) and ( 051 ) P: PDF#44-0003 S: 0mg/mL 、 2mg/mL 、 5mg/mL 0 20.0373 50.6288

18 3.3. Work plan

19 1 Sub-layer SiO 2 、 TiO 2 ZrO 2 、 Al 2 O 3 2 Cationic polymer layer 3 Characterization AFM XRD(pole figure 、 GID) Zeta potential measurement +++++++

20 Q&A Thanks for your time !


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