Nanofiltration membrane with high flux for selectively removing hydrophobic endocrine disrupting chemicals and preparation method thereof

Patent metadata

Field	Value
Publication number	US-11623182-B2
Application number	US-202016908670-A
Country	US
Kind code	B2
Filing date	Jun 22, 2020
Priority date	Jun 25, 2019
Publication date	Apr 11, 2023
Grant date	Apr 11, 2023

Abstract

A nanofiltration membrane with a high flux for selectively removing hydrophobic endocrine disrupting chemicals and a preparation method thereof are provided. The method includes the following steps: immersing a porous support layer into a first solution, removing excess droplets from a surface of the support layer after taking the support layer out of the first solution, and then immersing the support layer attached with the first solution into a second solution for an interfacial polymerization reaction, followed by washing after completion of the reaction to obtain the subject nanofiltration membrane. The first solution is an aqueous solution containing a polyamine monomer and an acid binding agent, and the second solution is an organic solution containing an acid chloride monomer and a metal-organic framework.

First claim

What is claimed is:

1. A method for preparing a nanofiltration membrane with a high flux for selectively removing hydrophobic endocrine disrupting chemicals, comprising the following steps: immersing a first porous support layer into a first solution, removing excess droplets from a surface of the first porous support layer after taking the first porous support layer out of the first solution to obtain a second porous support layer, wherein the second porous support layer is provided with the first solution attached into pores of the second porous support layer, and then immersing the second porous support layer into a second solution for an interfacial polymerization reaction, followed by washing after a completion of the interfacial polymerization reaction to obtain the nanofiltration membrane, wherein the first solution is an aqueous solution containing a polyamine monomer and an acid binding agent, and the second solution is an organic solution containing an acid chloride monomer and a metal-organic framework with a metal center of aluminum, chromium or iron, the metal-organic framework with the metal center of aluminum, chromium or iron has a mass/volume percentage concentration of 0.2 wt/v % to 0.40 wt/v % in the second solution; and
wherein the acid binding agent is a mixture of triethylamine and sodium hydroxide and the acid binding agent has a total mass percentage concentration of 0.2 wt % to 1.0 wt % in the first solution.

2. The method for preparing the nanofiltration membrane according to claim 1 , wherein the metal-organic framework has a pore size ranging from 0.7 nm to 2.0 nm, and a ligand of the metal-organic framework is an organic ligand containing a carboxyl group.

3. The method for preparing the nanofiltration membrane according to claim 2 , wherein the ligand is terephthalic acid or 2-aminoterephthalic acid.

4. The method for preparing the nanofiltration membrane according to claim 1 , wherein the metal-organic framework is at least one selected from the group consisting of MIL-101(Cr), MIL-101(Al), MIL-53(Cr), and MIL-53(Al).

5. The method for preparing the nanofiltration membrane according to claim 1 , wherein the polyamine monomer is at least one selected from the group consisting of piperazine, m-phenylenediamine and p-phenylenediamine, and the polyamine monomer has a mass percentage concentration of 0.5 wt % to 2.0 wt % in the first solution.

6. The method for preparing the nanofiltration membrane according to claim 1 , wherein the triethylamine and the sodium hydroxide are present at a concentration ratio of 2 to 5.

7. The method for preparing the nanofiltration membrane according to claim 1 , wherein the acid chloride monomer is at least one selected from the group consisting of trimesoyl chloride and terephthaloyl chloride, and the acid chloride monomer has a mass percentage concentration of 0.05 wt % to 0.3 wt % in the second solution.

8. The method for preparing the nanofiltration membrane according to claim 1 , wherein the second solution is formed by dissolving the acid chloride monomer and the metal-organic framework in an organic solvent, followed by an ultrasonic blending, wherein the ultrasonic blending is performed with an ultrasonic intensity of 150 W to 500 W at a temperature of 10° C. to 40° C. for a time period of 0.5 hours to 2.0 hours.

9. The method for preparing the nanofiltration membrane according to claim 1 , wherein the washing is specifically performed by drying the nanofiltration membrane in air for 1 to 3 minutes, and then soaking the nanofiltration membrane in n-hexane for 1 to 3 minutes, followed by soaking the nanofiltration membrane in water for 1 to 3 minutes.

10. A nanofiltration membrane prepared by the method for preparing the nanofiltration membrane according to claim 1 .

11. The method for preparing the nanofiltration membrane according to claim 2 , wherein the metal-organic framework is at least one selected from the group consisting of MIL-101(Cr), MIL-101(Al), MIL-53(Cr), and MIL-53(Al).

12. The method for preparing the nanofiltration membrane according to claim 3 , wherein the metal-organic framework is at least one selected from the group consisting of MIL-101(Cr), MIL-101(Al), MIL-53(Cr), and MIL-53(Al).

13. The method for preparing the nanofiltration membrane according to claim 2 , wherein the polyamine monomer is at least one selected from the group consisting of piperazine, m-phenylenediamine and p-phenylenediamine, and the polyamine monomer has a mass percentage concentration of 0.5 wt % to 2.0 wt % in the first solution.

14. The method for preparing the nanofiltration membrane according to claim 3 , wherein the polyamine monomer is at least one selected from the group consisting of piperazine, m-phenylenediamine and p-phenylenediamine, and the polyamine monomer has a mass percentage concentration of 0.5 wt % to 2.0 wt % in the first solution.

15. The method for preparing the nanofiltration membrane according to claim 2 , wherein the triethylamine and the sodium hydroxide are present at a concentration ratio of 2 to 5.

16. The method for preparing the nanofiltration membrane according to claim 3 , wherein the triethylamine and the sodium hydroxide are present at a concentration ratio of 2 to 5.

17. The method for preparing the nanofiltration membrane according to claim 2 , wherein the acid chloride monomer is at least one selected from the group consisting of trimesoyl chloride and terephthaloyl chloride, and the acid chloride monomer has a mass percentage concentration of 0.05 wt % to 0.3 wt % in the second solution.

18. The method for preparing the nanofiltration membrane according to claim 3 , wherein the acid chloride monomer is at least one selected from the group consisting of trimesoyl chloride and terephthaloyl chloride, and the acid chloride monomer has a mass percentage concentration of 0.05 wt % to 0.3 wt % in the second solution.

19. The method for preparing the nanofiltration membrane according to claim 2 , wherein the second solution is formed by dissolving the acid chloride monomer and the metal-organic framework in an organic solvent, followed by an ultrasonic blending, wherein the ultrasonic blending is performed with an ultrasonic intensity of 150 W to 500 W at a temperature of 10° C. to 40° C. for a time period of 0.5 hours to 2.0 hours.

20. The method for preparing the nanofiltration membrane according to claim 3 , wherein the second solution is formed by dissolving the acid chloride monomer and the metal-organic framework in an organic solvent, followed by an ultrasonic blending, wherein the ultrasonic blending is performed with an ultrasonic intensity of 150 W to 500 W at a temperature of 10° C. to 40° C. for a time period of 0.5 hours to 2.0 hours.

Assignees

• Univ Tongji
• Univ Tianjin Polytechnic

Inventors

• Wang Zhiwei
• Dai Ruobin
• Zhang Hongwei
• Wang Liang
• Wang Qiaoying
• Wu Zhichao

Classifications

• B01D71/60

  Polyamines · CPC title

• B01D69/1251

  by interfacial polymerisation · CPC title

• B01D2323/40

  in-situ membrane formation · CPC title

• B01D71/06

  Organic material · CPC title

• B01D2325/36

  Hydrophilic membranes · CPC title