# US 8,770,414 B2 · Reverse osmosis membrane including ultra-hydrophilic passivation layer and method of manufacturing the same

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- Number: US 8,770,414 B2
- Document ID: US8770414B2
- Status: Granted
- Kind: B2
- Application number: 13/920,739
- Filed: 2013-06-18
- Published: 2013-10-31
- Granted: 2014-07-08
- Earliest claimed: 2011-06-17
- Assignees: LG Chem, Ltd.
- Applicants: LG Chem, Ltd.
- Inventors: Young-Ju Lee; Chong-Kyu Shin; Joung-Eun Yoo; Seung-Pyo Jeong; Phill Lee
- Web page: https://patentgrep.com/patent/US8770414B2

## CPC

- B01D 71/70: Polymers having silicon in the main chain, with or without sulfur, nitrogen, oxygen or carbon only
- B01D 67/0088: {Physical treatment with compounds, e.g. swelling, coating or impregnation}
- B01D 69/02: characterised by their properties
- B01D 69/12: Composite membranes; Ultra-thin membranes
- B05D 1/18: performed by dipping
- B01D 61/025: {Reverse osmosis; Hyperfiltration}
- B01D 71/027: {Silicium oxide}
- B01D 2323/02: Hydrophilization
- B01D 2325/36: Hydrophilic membranes
- C02F 1/441: {by reverse osmosis}
- C02F 2103/08: Seawater, e.g. for desalination
- C02F 2303/22: Eliminating or preventing deposits, scale removal, scale prevention (C02F1/042, C02F1/4602, C02F5/00 take precedence)
- Y02A 20/131: Reverse-osmosis
- B01D: SEPARATION (separating solids from solids by wet methods B03B, B03D; by pneumatic jigs or tables B03B; by other dry methods B07; magnetic or electrostatic separation of solid materials from solid materials or fluids, separation by high-voltage electric fields B03C; centrifuges, vortex apparatus B04; presses per se for squeezing-out liquid from liquid-containing material B30B9/02; treatment of water C02F, e.g. softening by ion-exchange C02F1/42; {arrangements of air intake cleaners in gas turbine plants F02C7/05} ; arrangements or mounting of filters in air-conditioning, air-humidification or ventilation F24F13/28)
- B05D: PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL (conveying articles or workpieces through baths of liquid B65G, e.g. B65G49/02)
- C02F: TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE (separation in general B01D; special arrangements on waterborne vessels of installations for treating water, waste water or sewage, e.g. for producing fresh water, B63J; adding materials to water to prevent corrosion C23F; treating radioactively-contaminated liquids G21F9/04; regeneration of reactants for recirculation into processes, see the relevant places for the processes)
- Y02A: TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE

## Abstract

A reverse osmosis separation membrane includes a porous support, a separation active layer formed on the supporting layer, and a ultra hydrophilic layer formed on the separation active layer. The ultra-hydrophilic layer includes a complex metal oxide including at least one metal element selected from the group consisting of Ti(IV), Zr(IV), Sn(IV) and Al(III), and Si, and an organic compound containing a hydrophilic group making a physical or chemical bond with Ti(IV), Zr(IV), Sn(IV) or Al(III) among the complex metal oxide. A method of manufacturing the reverse osmosis separation membrane also is provided. A reverse osmosis membrane including a single coating layer and having an improved durability, chlorine-resistance and antifouling properties may be provided.

## Claims

### Claim 1

A reverse osmosis separation membrane, comprising a porous support, a separation active layer formed on the supporting layer, and a ultra hydrophilic layer formed on the separation active layer,
the ultra-hydrophilic layer comprising a complex metal oxide including at least one metal element selected from the group consisting of Ti(IV), Zr(IV), Sn(IV) and Al (III), and Si; and an organic compound containing a hydrophilic group making a physical or chemical bond with Ti(IV), Zr(IV), Sn(IV) or Al(III) among the complex metal oxide.

### Claim 2 (depends on 1)

The reverse osmosis separation membrane of claim 1, wherein the complex metal oxide has a meso-porous structure.

### Claim 3 (depends on 1)

The reverse osmosis separation membrane of claim 1, wherein the complex metal oxide has a hollow tube type meso-porous structure.

### Claim 4 (depends on 3)

The reverse osmosis separation membrane of claim 3, wherein the hollow tube type meso-porous structure includes an organic compound containing a hydrophilic group through a physical or chemical bond.

### Claim 5 (depends on 1)

The reverse osmosis separation membrane of claim 1, wherein the ultra-hydrophilic layer includes a compound having a structure represented by following Chemical Formula 6.
in Chemical Formula 6.
M represents Ti(IV), Zr(IV), Sn(IV) or Al(III),
R6 represents hydrogen, a C1-20 alkyl group, CnH2n—OH, or CnH2n—CHCH2O (in which, n represents an integer of 1 to 20), and
R7 represents a functional group originated from an organic compound containing the hydrophilic group.

### Claim 6 (depends on 1)

The reverse osmosis separation membrane of claim 1, wherein the hydrophilic group of the organic compound containing the hydrophilic compound is at least one selected from the group consisting of a sulfonate salt, sulfuric acid, a carboxylate salt, carboxylic acid, a phosphate salt, phosphoric acid and a hydroxyl group (OH).

### Claim 7 (depends on 1)

The reverse osmosis separation membrane of claim 1, wherein the organic compound containing the hydrophilic group includes at least one functional group selected from the group consisting of a hydroxyl group (OH), an amine group and a phosphate, the functional group possibly making a physical or chemical bond with Ti(IV), Zr(IV), Sn(IV) or Al(III) among the complex metal oxide.

### Claim 8 (depends on 1)

The reverse osmosis separation membrane of claim 1, wherein the organic compound containing the hydrophilic group is a chelating agent possibly making a coordination bond with Ti(IV), Zr(IV), Sn(IV) or Al(III) among the complex metal oxide.

### Claim 9 (depends on 1)

The reverse osmosis separation membrane of claim 1, wherein the organic compound containing the hydrophilic group is at least one selected from the group consisting of disodium 1,2-dihydroxybenzene-3,5-disulfonate, sodium 1,2-dihydroxy-3-sulfonate, sodium 1,2-dihydroxy-4-sulfonate, sodium 1,2-dihydroxy-5-sulfonate, disodium 1,2-dihydroxy-4-chlorobenzene-3,5-disulfonate, disodium 1,2-dihydroxy-6-chlorobenzene-3,5-disulfonate, 1,2-dihydroxybenzene-3.5-disulfonic acid, 1,2-dihydroxy-3-sulfonic acid. 1,2-dihydroxy-4-sulfonic acid, 1,2-dihydroxy-5-sulfonic acid, 1,2-dihydroxy-4-chlorobenzene-3,5-disulfonic acid, 1,2-dihydroxy-6-chlorobenzene-3,5-disulfonic acid, disodium 1,2-dihydroxybenzene-3,5-dicarboxylate, sodium 1,2-dihydroxy-3-carboxylate, sodium 1,2-dihydroxy-4-carboxylate, sodium 1,2-dihydroxy-5-carboxylate, disodium 1,2-dihydroxy-4-chlorobenzene-3,5-dicarboxylate, disodium 1,2-dihydroxy-6-chlorobenzene-3,5-dicarboxylate, 1,2-dihydroxybenzene-3,5-dicarboxylic acid, 1,2-dihydroxy-3-carboxylic acid, 1,2-dihydroxy-4-carboxylic acid, 1,2-dihydroxy-5-carboxylic acid, 1.2-dihydroxy-4-chlorobenzene-3,5-dicarboxylic acid, 1.2-dihydroxy-6-chlorobenzene-3,5-dicarboxylic acid, disodium 1,2-dihydroxybenzene-3,5-diphosphate, sodium 1,2-dihydroxy-3-phosphate, sodium 1,2-dihydroxy-4-phosphate, sodium 1,2-dihydroxy-5-phosphate, disodium 1,2-dihydroxy-4-chlorobenzene-3,5-diphosphate, disodium 1,2-dihydroxy-6-chlorobenzene-3,5-diphosphate, 1,2-dihydroxybenzene-3,5-diphosphoric acid, 1,2-dihydroxybenzene-3-phosphoric acid, 1,2-dihydroxybenzene-4-phosphoric acid, 1,2-dihydroxybenzene-5-phosphoric acid, 1,2-dihydroxy-4-chlorobenzene-3,5-diphosphoric acid, 1,2-dihydroxy-6-chlorobenzene-3,5-diphosphoric acid, dihexadecyl phosphate, monododecyl phosphate, and nafion (tetrafluoroethylene-perfluoro-3,6-dioxa-4-methyl-7-octenesulfonic acid copolymer).

### Claim 10 (depends on 2)

The reverse osmosis separation membrane of claim 2, wherein the complex metal oxide having the meso-porous structure is prepared by a polymerization reaction of a precursor including at least one element selected from the group consisting of Si, Ti(IV), Zr(IV), Sn(IV) and Al(III) in the presence of a solvent and a surfactant.

### Claim 11 (depends on 10)

The reverse osmosis separation membrane of claim 10, wherein the solvent is at least one selected from the group consisting of ethanol, water, isopropyl alcohol, methanol and ethyl acetate.

### Claim 12 (depends on 10)

The reverse osmosis separation membrane of claim 10, wherein the surfactant is a nonionic surfactant represented by following Chemical Formula 3 or an ionic surfactant represented by following Chemical Formula 4,
EOXPOYEOX [Chemical Formula 3]
in Chemical Formula 3, x=5-40%, y=90-20%, 2x+y=100%, EO represents ethylene oxide, and PO represents propylene oxide,
(CnH2n+1)(CH3)3NX1 [Chemical Formula 4]
in Chemical Formula 4, n=12 to 18, and X1=Cl or Br.

### Claim 13 (depends on 1)

The reverse osmosis separation membrane of claim 1, wherein the ultra-hydrophilic layer further comprises a silane coupling agent.

### Claim 14 (depends on 1)

The reverse osmosis separation membrane of claim 1, wherein the ultra-hydrophilic layer further comprises a multi-functional organic material represented by following Chemical Formula 5,
R3(EO)kR4 [Chemical Formula 5]
in Chemical Formula 5, EO represents ethylene oxide, k represents an integer of 3 to 400, R3 is selected from the group consisting of OH, (meth)acrylate having C1 to C15, di(meth)acrylate having C1 to C15, tri(meth)acrylate having C1 to C15, and vinyl having C1 to C15 , and R4 is selected from the group consisting of hydrogen, (meth)acrylate having C1 to C3, and vinyl having C1 to C3.