Semipermeable membrane and preparation method thereof

Patent metadata

Field	Value
Publication number	US-2019282967-A1
Application number	US-201916269669-A
Country	US
Kind code	A1
Filing date	Feb 7, 2019
Priority date	Feb 7, 2018
Publication date	Sep 19, 2019
Grant date	—

Abstract

Disclosed is a semipermeable membrane and its preparation method. The semipermeable membrane obtained has a Turing structure. The Turing structure is an ordered pattern composed of microstructures. The existence of the structure enables the semipermeable membrane of this invention to have both high water permeation flux and excellent salt retention performance, which breaks the flux limit value of the semipermeable membrane while ensuring high selective permeability of the membrane. It also has good anti-pollution properties. The preparation method of the invention can be easily integrated into the existing semipermeable membrane production line without further cost input which has far-reaching practical significance and commercial value.

First claim

1 - 20 . (canceled)

21 . A method for preparing a semipermeable membrane, comprising the following steps:
preparing the semipermeable membrane by an interfacial polymerization of a solution A and a solution B in the presence of a porous substrate; wherein the solution A comprises a compound a and a polar solvent, and the compound a contains amino groups and/or imino groups; the solution B comprises a compound b and a non-polar solvent, and the compound b contains acid halide groups and/or isocyanate groups; a diffusion coefficient D A of the compound a in the solution A and a diffusion coefficient D B of the compound b in the solution B satisfy the following condition: D B /D A ≥10.

22 . The method according to claim 1 , further comprises the following steps:
S1. coating a surface of the porous substrate with the solution A to form a liquid film on the surface of the porous substrate; S2. bringing the liquid film in step S1 into contact with the solution B, and forming a separation layer by the interfacial polymerization to obtain the semipermeable membrane.

23 . The method according to claim 2 , wherein in the step S1, a liquid membrane residence time is 10˜600 s; and/or, in the step S2, a reaction time of the interfacial polymerization is 10˜600 s.

24 . The method according to claim 1 , wherein the diffusion coefficient D A of the compound a in the solution A and the diffusion coefficient D B of the compound b in the solution B satisfy the following conditions: 10≤D B /D A ≤10 5 .

25 . The method according to claim 1 , wherein the compound a has a molecular formula:
R(NH x ) n, wherein 1≤x≤2, 2≤n≤3, and R comprises one or more from the group consisting of aromatic ring, alicyclic ring, aromatic heterocyclic ring, heterocyclic ring, and carbon chain; wherein the concentration the compound a in the solution A is 0.1˜5.0 (w/v) %.

26 . The method according to claim 1 , wherein the compound b is a polyisocyanate and/or a third compound containing at least two acid halide groups.

27 . The method according to claim 6 , wherein the polyisocyanate comprises one or more from the group consisting of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, 1,4-phenylene diisocyanate, isophorone diisocyanate, methylene-bis(4-cyclohexyl isocyanate), naphthalene diisocyanate, 1,4-cyclohexane diisocyanate, xylyl diisocyanate, bis(isocyanatomethyl)-cyclohexane, lysine diisocyanate, dimethyl diphenylmethane diisocyanate, methyl cyclohexyl diisocyanate, polymethylene phenyl isocyanate, and their oligomers thereof;
the third compound containing at least two acid halide groups has a molecular formula:
R(COX) n,
wherein, 2≤n≤4, and X comprises one from the group consisting of halogens, and R comprises at least one or more from the group consisting of aromatic ring, alicyclic ring, heteroaromatic ring, heterocyclic ring, and carbon chain; wherein the compound b comprises at least one or more from the group consisting of 1,3,5-benzenetricarboxylic acid chloride, 1,4-phthaloyl dichloride, 1,3-phthaloyl dichloride, 2,6-pyridine dicarboxylic acid chloride, 2,5-thiophenedicarbonyl dichloride, 2,5-furandicarbonyl dichloride, 4,4′-biphenyldicarbonyl chloride, glutaryl chloride, adipoyl chloride, heptanedioyl dichloride, suberoyl chloride, azelaoyl chloride, sebacoyl chloride, cyclohexyl-1,4-dicarbonyl chloride, and 1,3-adamantanedicarbonyl dichloride.

28 . The method according to claim 1 , wherein the polar solvent comprises at least one or more from the group consisting of water, dimethylformamide, dimethylacetamide, alcohols, ketones, and esters.

29 . The method according to claim 1 , wherein the non-polar solvent comprises at least one or more from the group consisting of C 6 -C 14 isoparaffin mixture cycloalkanes, and aromatic hydrocarbons.

30 . The method according to claim 1 , the solution A further comprises a first material which reduces the diffusion coefficient D A of the compound a in the solution A; wherein the first material comprises at least one or more from the group consisting of macromolecules and nanoparticles.

31 . The method according to claim 10 , wherein at least one of that macromolecule is capable of forming an intermolecular hydrogen bond and/or an intramolecular hydrogen bond to reduce the diffusion coefficient D A of the compound a in solution A.

32 . The method according to claim 10 , wherein the concentration of the macromolecules in the solution A is 0.01˜0.05 (w/v) %.

33 . The method according to claim 10 , wherein the nanoparticles are organic or inorganic substances, and the nanoparticles comprise at least one or more from the group consisting of surface hydroxylated nanotubes, graphene, carbon nitride; surface carboxylated nanotubes, graphene, carbon nitride, surface aminated nanotubes, graphene, and carbon nitride.

34 . The method according to claim 1 , the solution A further comprises at least one first additive from the group consisting of catalyst, surfactant, zwitterionic compound, acid, and base.

35 . The method according to claim 1 , the solution B further comprises at least one second additive from the group consisting of cosolvent, complexing agent, and phase transfer agent.

36 . A semipermeable membrane, comprising
a porous substrate, and a separation layer; wherein the separation layer has an ordered pattern of microstructure; and the microstructure comprises at least one from speckled structure, vesicle-like structure, tubular structure, spotted structure, and ring structure; and the microstructure is a three-dimensional hollow structure.

37 . The semipermeable membrane according to claim 16 , wherein the semipermeable membrane has a three-dimensional nano-scale turing structure generated in situ, and the three-dimensional nano-scale turing structure is a stationary pattern structure in which the concentration of chemical substances changes periodically according to space and the three-dimensional nano-scale turning structure is formed by system instability due to diffusion.

38 . The semipermeable membrane according to claim 16 , wherein the semipermeable membrane comprises a porous substrate and a nanoseparation layer, the three-dimensional nano-scale turing structure being located on the nanoseparation layer;
wherein the porous substrate has a surface pore diameter ranged from 2 nm to 1,000 nm, and a cutting molecular weight ranged from 2,000 to 200,000 Daltons.

39 . The semipermeable membrane according to claim 16 , wherein the semipermeable membrane is a polyamide semipermeable membrane obtained by an interfacial polymerization of a compound a and a third compound containing at least two acid halide groups; or
the semipermeable membrane is a polyurea semipermeable membrane obtained by the interfacial polymerization of a polyisocyanate and a polyamine.

40 . A membrane module, comprising a semipermeable membrane prepared by the method of claim 1 .

Assignees

• Univ Zhejiang

Inventors

• Zhang Lin
• Tan Zhe
• Chen Shengfu
• Meng Lida

Classifications

• B01D69/148

  Organic/inorganic mixed matrix membranes · CPC title

• B01D69/02

  characterised by their properties · CPC title

• B01D71/54

  Polyureas; Polyurethanes · CPC title

• B01D61/02

  Reverse osmosis; Hyperfiltration {; Nanofiltration} · CPC title

• B01D2323/40

  in-situ membrane formation · CPC title