WO2013085343A1 - 은 나노 와이어층을 포함하는 역삼투막 및 그 제조 방법 - Google Patents
은 나노 와이어층을 포함하는 역삼투막 및 그 제조 방법 Download PDFInfo
- Publication number
- WO2013085343A1 WO2013085343A1 PCT/KR2012/010639 KR2012010639W WO2013085343A1 WO 2013085343 A1 WO2013085343 A1 WO 2013085343A1 KR 2012010639 W KR2012010639 W KR 2012010639W WO 2013085343 A1 WO2013085343 A1 WO 2013085343A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- reverse osmosis
- osmosis membrane
- membrane
- silver nanowire
- nanowire layer
- Prior art date
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- 239000012528 membrane Substances 0.000 title claims abstract description 97
- 238000001223 reverse osmosis Methods 0.000 title claims abstract description 72
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000002042 Silver nanowire Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title abstract 2
- 229920002647 polyamide Polymers 0.000 claims abstract description 42
- 239000004952 Polyamide Substances 0.000 claims abstract description 41
- 239000000243 solution Substances 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 24
- -1 polypropylene Polymers 0.000 claims description 22
- 150000003839 salts Chemical class 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 150000001412 amines Chemical class 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 10
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 8
- 239000000460 chlorine Substances 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- 238000012695 Interfacial polymerization Methods 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 7
- 229920002492 poly(sulfone) Polymers 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- 150000001266 acyl halides Chemical class 0.000 claims description 6
- ZWUBBMDHSZDNTA-UHFFFAOYSA-N 4-Chloro-meta-phenylenediamine Chemical compound NC1=CC=C(Cl)C(N)=C1 ZWUBBMDHSZDNTA-UHFFFAOYSA-N 0.000 claims description 5
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 5
- 239000004745 nonwoven fabric Substances 0.000 claims description 5
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 claims description 4
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims description 4
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 3
- 229940044174 4-phenylenediamine Drugs 0.000 claims description 3
- 229910019093 NaOCl Inorganic materials 0.000 claims description 3
- 239000005018 casein Substances 0.000 claims description 3
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 claims description 3
- 235000021240 caseins Nutrition 0.000 claims description 3
- 230000029142 excretion Effects 0.000 claims description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 3
- 239000002033 PVDF binder Substances 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 2
- 239000004695 Polyether sulfone Substances 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920006393 polyether sulfone Polymers 0.000 claims description 2
- 229920002530 polyetherether ketone Polymers 0.000 claims description 2
- 229920001601 polyetherimide Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 229920000306 polymethylpentene Polymers 0.000 claims description 2
- 239000011116 polymethylpentene Substances 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- 239000004697 Polyetherimide Substances 0.000 claims 1
- 238000002347 injection Methods 0.000 claims 1
- 239000007924 injection Substances 0.000 claims 1
- 239000010410 layer Substances 0.000 description 34
- 230000000052 comparative effect Effects 0.000 description 8
- 239000012466 permeate Substances 0.000 description 8
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000004332 silver Substances 0.000 description 6
- 229910052709 silver Inorganic materials 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000002070 nanowire Substances 0.000 description 3
- 230000003204 osmotic effect Effects 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XAXXXFOWCPSWLO-UHFFFAOYSA-N 3-n-chlorobenzene-1,3-diamine Chemical compound NC1=CC=CC(NCl)=C1 XAXXXFOWCPSWLO-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 241001136249 Agriotes lineatus Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920001284 acidic polysaccharide Polymers 0.000 description 1
- 150000004805 acidic polysaccharides Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- JSYBAZQQYCNZJE-UHFFFAOYSA-N benzene-1,2,4-triamine Chemical compound NC1=CC=C(N)C(N)=C1 JSYBAZQQYCNZJE-UHFFFAOYSA-N 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/025—Reverse osmosis; Hyperfiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
- B01D69/107—Organic support material
- B01D69/1071—Woven, non-woven or net mesh
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/1213—Laminated layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/1216—Three or more layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
- B01D69/1251—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction by interfacial polymerisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/14—Dynamic membranes
- B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/022—Metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/12—Specific ratios of components used
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/40—Details relating to membrane preparation in-situ membrane formation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/04—Characteristic thickness
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/20—Specific permeability or cut-off range
Definitions
- the present invention relates to a reverse osmosis membrane and a method for producing the same, and more particularly, to a reverse osmosis membrane comprising a silver nanowire layer between a support and a polyamide membrane, and a method for producing the same.
- Osmotic phenomenon is the movement of a solvent through a membrane from a solution having a low solute concentration to a high solution between two solutions separated by a semi-permeable membrane. Is called osmotic pressure. However, applying an external pressure higher than osmotic pressure causes the solvent to move toward a solution with a low concentration of solute. This phenomenon is called reverse osmosis. Using the reverse osmosis principle, a pressure gradient can be used as a driving force to separate various salts or organic substances through the semipermeable membrane.
- Reverse osmosis membrane by reverse osmosis such a phenomenon (hereinafter, referred to as a reverse osmosis membrane) is used to separate the material at the molecular level, and supplies the home and building, industrial water to remove the brine or saltwater fish, iseo salt.
- a reverse osmosis membrane includes polyamide reverse osmosis membranes, and polyamide reverse osmosis membranes are manufactured by forming a polyamide active layer on a microporous layer support, and more specifically, a polysulfone layer on a nonwoven fabric.
- microporous support which is microporous
- the support is immersed in an aqueous solution of m-Phenylene Diamine (mPD) to form an mPD layer, which is in turn immersed in an organic solvent of triMesoyl Chloride (TMC) to contact the mPD layer with TMC
- TMC triMesoyl Chloride
- the silver nanoparticles have a particle shape (spherical or square) having a smaller surface area than silver nanowires, for example, in the case of a reverse osmosis membrane, the silver nanoparticles are not exposed or expressed outside the polyamide membrane. There was a problem that was difficult to get the inherent effect.
- the present invention is to solve the above problems, to provide a reverse osmosis membrane excellent in salt removal rate, permeate flow rate chlorine resistance and fouling resistance and a method of manufacturing the same.
- a reverse osmosis membrane comprising a polyamide membrane.
- the present invention comprises the steps of coating a porous support with an aqueous amine solution containing silver nanowires to form a silver nanowire layer; And contacting an aliphatic hydrocarbon-based organic solution including an acyl halide on the silver nanowire layer to form a polyamide membrane.
- the amine aqueous solution preferably contains the silver nanowires in an amount of 0.001% by weight to 0.5% by weight.
- the reverse osmosis membrane of the present invention contains silver nanowires having antibacterial performance and is excellent in fouling resistance and chlorine resistance.
- the reverse osmosis membrane of the present invention has improved surface characteristics of the polyamide membrane by the silver nanowire layer, and thus exhibits superior performance in comparison with the conventional reverse osmosis membrane in terms of salt removal rate and permeate flow rate.
- the reverse osmosis membrane of the present invention is manufactured by adding silver nanowires to the amine aqueous solution, the conventional reverse osmosis membrane manufacturing equipment can be used as it is, and the manufacturing process is simple, and a thin reverse osmosis membrane can be realized. have.
- 1 is a view showing the structure of the reverse osmosis membrane of the present invention.
- 2 is a SEM photograph of the surface of the polyamide film of Example 7 of the present invention.
- . 3 is a SEM photograph of the surface of the polyamide film of Comparative Example 7 of the present invention.
- FIG. 1 schematically shows the structure of the reverse osmosis membrane of the present invention.
- the reverse osmosis membrane 1 of the present invention has a structure in which a silver nanowire layer 20 and a polyamide membrane 30 are sequentially stacked on a porous support 10.
- the porous support 10 may be a coating layer 14 of a polymeric material formed on the nonwoven fabric 12, the polymer material, for example, polysulfone, polyether sulfone, polycarbonate, polyethylene Oxides, polyimides, polyetherimides, polyetheretherketones, polypropylene, polymethylpentene, polymethylchloride, polyvinylidene fluoride and the like can be used, but are not necessarily limited thereto. Especially among these, a pulley sulfone is preferable.
- the silver nanowire layer 20 may be formed on the porous support 10, and may be formed by immersing the porous support 10 in a solution containing silver nanowires.
- the thickness of the silver nanowire layer may be about 1 to 50% of the thickness of the polyamide membrane, for example, about 1 to 30% or 30 to 50%. Most preferably about 1% to 5%. More specifically, considering that the thickness of the polyamide membrane in the reverse osmosis membrane is about several hundred nanometers, preferably about 150 ⁇ 200nm, the thickness of the silver nanowire layer is about O.lnm to 100nm, preferably 2nm ' to It is preferable to form about 10 nm.
- the silver nanowires content in the solution containing the silver nanowires is about 0.0 wt% to 0.5 wt%, more preferably about 0.05 to 0.15 wt% It is desirable. This is because when the content of the silver nanowire is in the above range, excellent fouling resistance can be obtained without disturbing the polyamide interfacial polymerization.
- the nanowire is used in the same sense as the wire structure having a size of a unit of nanometer, which is generally used in the art. That is, the silver nanowire has a relatively large surface area compared to the silver nanoparticle form, a length is also considerably longer than the silver nanoparticle form, and the direction thereof is random.
- the silver nanowire layer is formed at the lowermost part of the polyamide film, due to the characteristics of the wire structure, the silver nanowire is exposed or expressed to the upper surface layer of the polyamide film to exhibit the effect according to the present invention.
- the "reverse osmosis membrane is a porous support 10 of the present invention because the laminated nanowire layer 20, and a polyamide film 30 are sequentially, for example, of the lower film is a polyamide of the nanowire layer Silver nanowires can increase the surface roughness. Therefore, the permeation flow rate can be improved by increasing the surface area.
- the polyamide film 30 may be formed by interfacial polymerization of an amine compound and an acyl halide compound.
- the amine compound is not limited thereto, for example, m-phenylenediamine, P-phenylenediamine, 1 36-benzenetriamine, 4- It may be at least one selected from the group consisting of chloro-1,3-phenylenediamine, 6-chloro-1,3-phenylenediamine, 3-chloro 1,4-phenylene diamine, and combinations thereof.
- M phenylenediamine, P-phenylenediamine, 1,3,6-benzenetriamine, 4-chloro-1,3-phenylenediamine, 6-chloro-1,3-phenylenediamine, 3- Chloro-1,4-phenylene diamine, or a combination thereof.
- the acyl halide compound may be, but is not limited to, at least one selected from the group consisting of trimezoyl chloride, isophthaloyl chloride and terephthaloyl chloride. That is, it may be trimezoyl chloride, isophthaloyl chloride, terephthaloyl chloride, or a combination thereof.
- Method for producing a reverse osmosis membrane of the present invention (1) coating a porous support with an aqueous amine solution containing silver nanowires to form a silver nanowire layer and (2) an aliphatic hydrocarbon-based containing acyl halide on the silver nanowire layer Contacting the organic solution to form a polyamide film.
- the porous support is coated with an aqueous amine solution containing silver nanowires.
- the coating is then carried out in a variety of ways well known in the art, for example immersion, It may be made by spraying, coating, or the like, but is preferably carried out through an immersion method.
- the immersion time is preferably enough to penetrate the solution into the pores inside the polysulfone porous support, for example, may be 10 minutes or less, and 30 seconds to Most preferably, it is about 2 minutes.
- the amine aqueous solution is contained in an amount of 2 to 5% by weight.
- the aqueous amine solution preferably contains silver nanowires in an amount of 0.001 weight ⁇ 3 ⁇ 4 to 0.5 increase 3 ⁇ 4, preferably 0.05 to 0.15 weight%, most preferably 0.06 to 0.08 weight>.
- the amine aqueous solution may further include a polar compound, an additive, etc. to assist the interfacial polymerization of the amine compound and the acyl halide within a range that does not impair the physical properties of the reverse osmosis membrane.
- the excess amine aqueous solution is removed from the surface of the support and dried to form a silver nanowire layer.
- the formed silver nano The wireworm contains silver nanowires and amine compounds.
- the silver nanowire layer is contacted with an aliphatic hydrocarbon-based organic solution containing acyl halide.
- the amine compound coated on the surface and the acyl halide compound react to produce polyamide by interfacial polymerization, which is adsorbed to form a polyamide film.
- the silver nanowires exist only in the aqueous amine solution below the interface, when the polyamide polymerization is completed, the silver nanowires are positioned only between the lowermost part of the polyamide membrane and the uppermost part of the porous support.
- the silver nanowires may be safely used even under high-pressure
- the silver nanowires since the silver nanowires may be embedded in some or all of the silver nanowire layers, or due to the high aspect ratio of the silver nanowires, the silver nanowires may be embedded in some or all of the polyamide film. The possibility of eluting to the outside of the polyamide membrane is remarkably low. Therefore, it can be free from problems such as environmental pollution.
- the aliphatic hydrocarbon-based organic solution including the acyl halide preferably contains 0.1 to 0.5% by weight of an acyl halide compound such as trimezoyl chloride, isophthaloyl chloride and ' terephthaloyl chloride.
- an acyl halide compound such as trimezoyl chloride, isophthaloyl chloride and ' terephthaloyl chloride.
- the organic solvent it is preferable to use a solvent that does not participate in the interfacial polymerization reaction, does not form a chemical bond with the acyl halide compound, and does not damage the porous support layer.
- IsoPar Exxon
- IS0L-C SK Chem
- ISOL-GCSK Chem ISOL-GCSK Chem
- the drying is preferably performed for about 2 to 10 minutes at 40 to 80 ° C.
- the washing is not particularly limited, for example, it can be washed in a basic aqueous solution.
- Basic aqueous solution that can be used is not particularly limited, for example, sodium carbonate aqueous solution can be used, specifically,
- the reverse osmosis membrane of the present invention prepared by the above method is because the silver nanowire layer is formed between the porous support and the polyamide membrane, it has excellent pollution resistance and chlorine resistance by the intrinsic properties of silver.
- the silver nanowire layer is formed between the porous support and the polyamide membrane as shown in the present invention, it was confirmed that the surface properties of the polyamide membrane is improved by the silver nanowire layer, The initial salt removal rate and initial permeate flow rate characteristics were also excellent.
- the reverse osmosis membrane of the present invention has an initial salt excretion rate of 90% or more, more preferably 94% or more, most preferably 98% or more, and an initial permeation flux of 40 gallon / ft 2 -day or more, more preferably. 42 gal lon / ft 2 -day, most preferably
- the reverse osmosis membrane of the present invention has a salt rejection rate of 90% or more, preferably 96% or more after 2 hours after the addition of casein, a contaminant, a permeation flow rate of 36 gallon / ft 2 -day or more, more preferably 40 gallon / Above ft 2 .day, it has excellent pollution resistance.
- the reverse osmosis membrane of the present invention has a salt rejection ratio of 80% or more, more preferably 90% or more after 12 hours after adding 2,000 ppm of NaOCl aqueous solution,
- the chlorine resistance is superior to 37gallon / ft 2 -day or more, more preferably 40gal lon / ft 2 -day or later.
- a reverse osmosis membrane was prepared in the same manner as in Example 1, except that the content of the silver nanowire was 0.005 wt%.
- a reverse osmosis membrane was prepared in the same manner as in Example 1, except that the content of the silver nanowire was 0.01% by weight.
- a reverse osmosis membrane was prepared in the same manner as in Example 1, except that the content of the silver nanowire was 0.05% by weight.
- Example 5 A reverse osmosis membrane was prepared in the same manner as in Example 1, except that the content of the silver nanowire was 0.05% by weight.
- a reverse osmosis membrane was prepared in the same manner as in Example 1, except that the content of the silver nanowire was 0.068 wt%.
- a reverse osmosis membrane was prepared in the same manner as in Example 1, except that the content of the silver nanowires was 0.1 wt3 ⁇ 4.
- a reverse osmosis membrane was prepared in the same manner as in Example 1, except that the content of the silver nanowire was 0.445 wt%. Comparative example
- a reverse osmosis membrane was prepared in the same manner as in Example 1, except that an aqueous solution containing 2 wt% of metaphenylenediamine was used without the silver nanowires.
- the reverse osmosis membranes prepared by 3 to 6 were prepared using 32,000ppm NaCl solution and 2,000 ⁇
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JP2014502492A JP5692885B2 (ja) | 2011-12-08 | 2012-12-07 | 銀ナノワイヤ層を含む逆浸透膜及びその製造方法 |
CN201280019831.2A CN103492051B (zh) | 2011-12-08 | 2012-12-07 | 包括银纳米线层的反渗透膜及其制备方法 |
US14/005,822 US8875906B2 (en) | 2011-12-08 | 2012-12-07 | Reverse osmosis membrane including nano-silver wire layer and fabrication method thereof |
EP12854843.5A EP2789379B1 (en) | 2011-12-08 | 2012-12-07 | Reverse osmosis membrane comprising silver nanowire layer, and preparation method thereof |
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JP2016524530A (ja) * | 2013-06-18 | 2016-08-18 | エルジー・ケム・リミテッド | 塩除去率及び透過流量特性に優れたポリアミド系逆浸透分離膜の製造方法、及び上記製造方法で製造された逆浸透分離膜 |
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EP2789379B1 (en) | 2020-02-05 |
CN103492051A (zh) | 2014-01-01 |
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US8875906B2 (en) | 2014-11-04 |
CN103492051B (zh) | 2015-07-22 |
JP5692885B2 (ja) | 2015-04-01 |
KR101407445B1 (ko) | 2014-06-17 |
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US20140299537A1 (en) | 2014-10-09 |
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