Amphiphilic molecular sieve containing hydrophilic group on the outside and lipophilic group on the inside and production method threof

Patent metadata

Field	Value
Publication number	US-10759667-B2
Application number	US-201816029215-A
Country	US
Kind code	B2
Filing date	Jul 6, 2018
Priority date	Jan 3, 2018
Publication date	Sep 1, 2020
Grant date	Sep 1, 2020

Abstract

The present invention provides an amphiphilic molecular sieve containing a hydrophilic group on the outside and a lipophilic group on the inside and a production method thereof. The production method comprises: dispersing the ZSM-5 spherical nano-molecular sieve into toluene, adding thereto an organosilane containing a hydrophilic group and reacting at 40-80° C. for 2-16 h, to obtain a molecular sieve containing a hydrophilic group; placing the molecular sieve containing a hydrophilic group in an aqueous solution of sodium hydroxide and reacting at 50-90° C. for 10-50 min, to obtain a molecular sieve containing a hydrophilic group on the outside; dispersing the molecular sieve containing a hydrophilic group on the outside into toluene, adding thereto an organosilane containing a lipophilic group and reacting at 40-80° C. for 2-12 h, to obtain the amphiphilic molecular sieve containing a hydrophilic group on the outside and a lipophilic group on the inside. The present invention also provides an amphiphilic molecular sieve obtained by the above production method, which contains a hydrophilic group on the outside and a lipophilic group on the inside.

First claim

The invention claimed is:

1. A method of producing an amphiphilic molecular sieve containing a hydrophilic group on the outside and a lipophilic group on the inside, comprising:
a) producing a ZSM-5 spherical nano-molecular sieve with a diameter of 50-200 nm;
b) dispersing the ZSM-5 spherical nano-molecular sieve into toluene, adding thereto an organosilane containing a hydrophilic group and reacting at 40-80° C. for 2-16 h, followed by centrifugation, washing and drying, to obtain a molecular sieve containing a hydrophilic group; wherein the amount of substance of the toluene is 40-80 times that of the ZSM-5 spherical nano-molecular sieve, and the amount of substance of the organosilane containing a hydrophilic group is 4-8 times that of the ZSM-5 spherical nano-molecular sieve;
c) placing the molecular sieve containing a hydrophilic group in an aqueous solution of sodium hydroxide and reacting at 50-90° C. for 10-50 min, followed by centrifugation, washing and drying, to obtain a molecular sieve containing a hydrophilic group on the outside; and
d) dispersing the molecular sieve containing a hydrophilic group on the outside into toluene, adding thereto an organosilane containing a lipophilic group and reacting at 40-80° C. for 2-12 h, followed by centrifugation, washing and drying, to obtain the amphiphilic molecular sieve containing a hydrophilic group on the outside and a lipophilic group on the inside; wherein the amount of substance of the toluene is 40-80 times that of the molecular sieve containing a hydrophilic group on the outside, and the amount of substance of the organosilane containing a lipophilic group is 4-8 times that of the molecular sieve containing a hydrophilic group on the outside.

2. The method according to claim 1 , wherein the organosilane containing a hydrophilic group has a structural formula as shown below:
(R 1 O) a —Si—R 4-a or X—Si—R 4-a

wherein R 1 is —CH 3 , —C 2 H 5 or H;
R is —NH 2 , COOH, —CN or —SH;
X is halogen; and
a is 1, 2 or 3.

3. The method according to claim 1 , wherein the organosilane containing a hydrophilic group is 3-aminopropyltriethoxysilane, 2-cyanoethyltriethoxysilane or 3-mercaptopropylmethyltriethoxysilane.

4. The method according to claim 1 , wherein in c), the concentration of the aqueous solution of sodium hydroxide is 0.1-4 mol/L.

5. The method according to claim 1 , wherein in c), when the concentration of the aqueous solution of sodium hydroxide is less than 0.5 mol/L, and the alkali etching time is less than 30 min, the obtained amphophilic molecular sieve containing a hydrophilic group on the outside and a lipophilic group on the inside has a hollow structure;
when the concentration of the aqueous solution of sodium hydroxide is more than 0.5 mol/L, and the alkali etching time is more than 30 min, the obtained amphophilic molecular sieve containing a hydrophilic group on the outside and a lipophilic group on the inside has a half-shell structure.

6. The method according to claim 1 , wherein in c), the rotate speed of the centrifugation is 5000-10000 rpm, and the duration of the centrifugation is 5-8 min.

7. The method according to claim 1 , wherein in c), the washing is performed 1-2 times with ethanol.

8. The method according to claim 1 , wherein in c), the drying is performed at 50-80° C. for 5-12 h.

9. The method according to claim 1 , wherein the organosilane containing a lipophilic group has a structural formula as shown below:
(R′ 1 O) b —Si—R′ 4-b or Y—Si—R′ 4-b

Wherein R′ 1 is —CH 3 , —C 2 H 5 or H;
R′ is a benzene ring, linear alkane or cycloalkane;
Y is halogen;
b is 1, 2 or 3.

10. The method according to claim 1 , wherein the organosilane containing a lipophilic group is methyltriethoxysilane, cetyltrimethoxysilane, n-octyltrichlorosilane, or cyclohexylmethyldimethoxysilane.

11. The method according to claim 1 , wherein in b) and d), the rotate speed of the centrifugation is 5000-10000 rpm, and the duration of the centrifugation is 5-8 min.

12. The method according to claim 1 , wherein in b) and d), the washing is washing with toluene followed by washing with trichloromethane.

13. The method according to claim 1 , wherein in b) and d), the temperature of the drying is 50-80° C., and the duration of the drying is 5-12 h.

Assignees

• Petrochina Co Ltd

Inventors

• Luo Jianhui
• Zhang Zongtao
• Peng Baoliang
• Wang Runwei
• He Lipeng
• Wang Pingmei
• Ding Bin
• Wang Ying
• Geng Xiangfei

Classifications

• B01J2229/40

  Special temperature treatment, i.e. other than just for template removal · CPC title

• C01P2002/72

  by d-values or two theta-values, e.g. as X-ray diagram · CPC title

• B01J20/28019

  Spherical, ellipsoidal or cylindrical · CPC title

• C01P2006/16

  Pore diameter · CPC title

• C01B39/026 Primary

  After-treatment · CPC title