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

Patent metadata

Field	Value
Publication number	US-10647586-B2
Application number	US-201816029170-A
Country	US
Kind code	B2
Filing date	Jul 6, 2018
Priority date	Jan 3, 2018
Publication date	May 12, 2020
Grant date	May 12, 2020

Abstract

The present invention provides an amphiphilic molecular sieve containing a lipophilic group on the outside and a hydrophilic group on the inside and a production method thereof. The production method comprises: dispersing the nano-ZSM-5 molecular sieve into toluene, adding an organosilane containing a lipophilic group and reacting at 60-100° C. for 4-16 h, to obtain a molecular sieve containing a lipophilic group; placing the molecular sieve containing a lipophilic group in a mixed solution of sodium hydroxide solution and ethanol and reacting at 60-95° C. for 20-60 min, to obtain a molecular sieve containing a lipophilic group on the outside; dispersing the molecular sieve containing a lipophilic group on the outside into toluene, adding an organosilane containing a hydrophilic group and reacting at 60-100° C. for 4-16 h, to obtain the amphiphilic molecular sieve containing a lipophilic group on the outside and a hydrophilic group on the inside. The present invention also provides a molecular sieve obtained by the above production method, which does not destroy the characteristics of the original molecular sieve and has hydrophilic and lipophilic amphiphilic properties.

First claim

The invention claimed is:

1. A method of producing an amphiphilic molecular sieve containing a lipophilic group on the outside and a hydrophilic group on the inside, comprising:
a) producing a nano-ZSM-5 molecular sieve with a diameter of 50-200 nm;
b) dispersing the nano-ZSM-5 molecular sieve into toluene, adding an organosilane containing a lipophilic group and reacting at 60-100° C. for 4-16 h, followed by centrifugation, washing and drying, to obtain a molecular sieve containing a lipophilic group; wherein the amount of substance of the toluene is 60-100 times that of the nano-ZSM-5 molecular sieve, and the amount of substance of the organosilane containing a lipophilic group is 6-10 times that of the nano-ZSM-5 molecular sieve;
c) placing the molecular sieve containing a lipophilic group in a mixed solution of sodium hydroxide solution and ethanol and reacting at 60-95° C. for 20-60 min, followed by centrifugation, washing and drying, to obtain a molecular sieve containing a lipophilic group on the outside; and
d) dispersing the molecular sieve containing a lipophilic group on the outside into toluene, adding an organosilane containing a hydrophilic group and reacting at 60-100° C. for 4-16 h, followed by centrifugation, washing and drying, to obtain the amphiphilic molecular sieve containing a lipophilic group on the outside and a hydrophilic group on the inside; wherein the amount of substance of the toluene is 60-100 times that of the molecular sieve containing a lipophilic group on the outside, and the amount of substance of the organosilane containing a hydrophilic group is 6-10 times that of the molecular sieve containing a lipophilic group on the outside.

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

wherein R is a benzene ring, linear alkane or cycloalkane;
X is halogen, siloxane or silanol; and
a is 1, 2 or 3.

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

4. The method according to claim 1 , wherein in c), the concentration of the sodium hydroxide solution is 0.5-6 mol/L.

5. The method according to claim 1 , wherein in c), the concentration of ethanol is 99%.

6. The method according to claim 1 , wherein in c), the volume ratio of the sodium hydroxide solution to ethanol in the mixed solution of the sodium hydroxide solution and ethanol is 1:0.1 to 1:10.

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

8. The method according to claim 1 , wherein in c), the rotate speed of the centrifugation is 6000-12000 rpm, and the duration of the centrifugation is 6-10 min.

9. The method according to claim 1 , wherein in c), the washing is performed 5-8 times with a mixed solution of clean water and ethanol.

10. The method according to claim 1 , wherein in c), the drying is performed at 60-100° C. for 8-18 h.

11. The method according to claim 1 , wherein the organosilane containing a hydrophilic group has a structural formula as shown below:
Y—Si—R′ 4-b

wherein R′ is —NH 2 , COOH, —CN or —SH;
Y is halogen, siloxane or silanol; and
b is 1, 2 or 3.

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

13. 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.

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

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

16. An amphiphilic molecular sieve containing a lipophilic group on the outside and a hydrophilic group on the inside, produced by the method according to claim 1 .

17. The amphiphilic molecular sieve according to claim 16 , wherein the amphiphilic molecular sieve has a diameter of 50-200 nm, and has a half-shell structure, with a lipophilic group on the outside and a hydrophilic group on the inside.

Assignees

• Petrochina Co Ltd

Inventors

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

Classifications

• C01B39/38 Primary

  Type ZSM-5 · CPC title

• C01P2004/03

  obtained by SEM · CPC title

• C01P2006/90

  Other properties not specified above · CPC title

• B01J29/40

  of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively · CPC title

• B01J20/22

  comprising organic material · CPC title