CN113332865A - Composite support material for reverse osmosis membrane and preparation method thereof - Google Patents
Composite support material for reverse osmosis membrane and preparation method thereof Download PDFInfo
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- CN113332865A CN113332865A CN202110429381.5A CN202110429381A CN113332865A CN 113332865 A CN113332865 A CN 113332865A CN 202110429381 A CN202110429381 A CN 202110429381A CN 113332865 A CN113332865 A CN 113332865A
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- China
- Prior art keywords
- methyl acrylate
- reverse osmosis
- acrylate copolymer
- woven fabric
- osmosis membrane
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- 239000012528 membrane Substances 0.000 title claims abstract description 80
- 238000001223 reverse osmosis Methods 0.000 title claims abstract description 77
- 239000000463 material Substances 0.000 title claims abstract description 72
- 239000002131 composite material Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 229920006225 ethylene-methyl acrylate Polymers 0.000 claims abstract description 80
- 239000000835 fiber Substances 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 52
- 229920000728 polyester Polymers 0.000 claims abstract description 47
- 239000004744 fabric Substances 0.000 claims abstract description 39
- 239000004750 melt-blown nonwoven Substances 0.000 claims abstract description 39
- 239000004745 nonwoven fabric Substances 0.000 claims abstract description 39
- 230000008569 process Effects 0.000 claims abstract description 30
- 238000007731 hot pressing Methods 0.000 claims abstract description 25
- 239000011148 porous material Substances 0.000 claims abstract description 25
- 238000009987 spinning Methods 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 238000002844 melting Methods 0.000 claims description 23
- 230000008018 melting Effects 0.000 claims description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 17
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000007664 blowing Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000002105 nanoparticle Substances 0.000 claims description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- 239000005977 Ethylene Substances 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 4
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 2
- HGVPOWOAHALJHA-UHFFFAOYSA-N ethene;methyl prop-2-enoate Chemical class C=C.COC(=O)C=C HGVPOWOAHALJHA-UHFFFAOYSA-N 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 abstract description 12
- 238000005260 corrosion Methods 0.000 abstract description 12
- 239000000047 product Substances 0.000 abstract description 12
- 238000010612 desalination reaction Methods 0.000 abstract description 8
- 230000004907 flux Effects 0.000 abstract description 7
- 239000012466 permeate Substances 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 230000006872 improvement Effects 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 238000000605 extraction Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004537 pulping Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- PEKLJSZEUFVLKO-UHFFFAOYSA-N chloro-bis(2-methoxyphenyl)phosphane Chemical compound COC1=CC=CC=C1P(Cl)C1=CC=CC=C1OC PEKLJSZEUFVLKO-UHFFFAOYSA-N 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- -1 silane modified silicon dioxide Chemical class 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 229920001410 Microfiber Polymers 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- KAVKNHPXAMTURG-UHFFFAOYSA-N n-(4-bromonaphthalen-1-yl)acetamide Chemical compound C1=CC=C2C(NC(=O)C)=CC=C(Br)C2=C1 KAVKNHPXAMTURG-UHFFFAOYSA-N 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
- B32B5/022—Non-woven fabric
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
- B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
- B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/08—Melt spinning methods
- D01D5/098—Melt spinning methods with simultaneous stretching
- D01D5/0985—Melt spinning methods with simultaneous stretching by means of a flowing gas (e.g. melt-blowing)
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4282—Addition polymers
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/54—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
- D04H1/56—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving in association with fibre formation, e.g. immediately following extrusion of staple fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/24—Mechanical properties, e.g. strength
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
- B32B37/1207—Heat-activated adhesive
- B32B2037/1215—Hot-melt adhesive
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/02—Synthetic macromolecular fibres
- B32B2262/0246—Acrylic resin fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/02—Synthetic macromolecular fibres
- B32B2262/0276—Polyester fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Fluid Mechanics (AREA)
- Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention provides a preparation method of a composite support material for a reverse osmosis membrane. The invention adopts a paper making method to prepare the polyester non-woven fabric, and carries out melt-blown spinning on the ethylene-methyl acrylate copolymer or the modified ethylene-methyl acrylate copolymer to prepare the melt-blown non-woven fabric; and overlapping the melt-blown non-woven fabric on the upper surface of the polyester non-woven fabric, and performing hot pressing treatment to prepare the composite supporting material for the reverse osmosis membrane. Through the mode, the bonding fibers in the polyester non-woven fabric can permeate into the melt-blown non-woven fabric by utilizing the hot pressing process, the bonding strength between the polyester non-woven fabric and the melt-blown non-woven fabric layer is effectively improved, and the pore structure of the polyester non-woven fabric and the melt-blown non-woven fabric layer is further optimized, so that the support material with small average pore size, high porosity, high mechanical strength and good corrosion resistance is formed, the production of a reverse osmosis membrane product with high flux, high desalination rate and long service life is facilitated, and the practical application value is higher.
Description
Technical Field
The invention relates to the technical field of reverse osmosis membrane supporting materials, in particular to a composite supporting material for a reverse osmosis membrane and a preparation method thereof.
Background
Reverse osmosis is a membrane separation operation that uses a pressure differential as a driving force to separate a solvent from a solution. The reverse osmosis membrane is used as a core element of a reverse osmosis technology, is an artificial semipermeable membrane with certain characteristics and made of a simulated biological semipermeable membrane, has the advantages of good separation performance, thin thickness, high pressure resistance and the like, is widely applied to the fields of seawater desalination, wastewater treatment, concentration and separation and the like, is massively applied to the industries such as electric power, food and beverage, pharmacy, chemistry, petroleum and the like, and creates huge social and economic benefits.
With the development of reverse osmosis membrane preparation technology, reverse osmosis membranes are gradually developed into reverse osmosis composite membranes from traditional homogeneous membranes and asymmetric reverse osmosis membranes. The support layer and the functional cortex of the reverse osmosis composite membrane can be prepared separately, the water production efficiency and the desalination performance of the reverse osmosis composite membrane are qualitatively improved compared with those of the traditional reverse osmosis membrane, and the reverse osmosis composite membrane has the advantages of high flux, high selectivity, high stability and the like, so that the reverse osmosis composite membrane is widely applied. In the reverse osmosis composite membrane, the supporting layer is used for supporting the whole reverse osmosis membrane, so that the interface reaction environment, the mechanical strength and the stability are provided for the preparation and the application of the reverse osmosis membrane, and the research on the supporting layer has important significance for improving the performance of the reverse osmosis membrane.
Patent publication No. CN109825956A provides a reverse osmosis membrane support material and a preparation method thereof. According to the method, a non-woven material prepared from thermoplastic polymer spun-bonded filaments is used as a surface layer and a bottom layer, a polymer nanofiber membrane is used as a middle layer, and the surface layer, the middle layer and the bottom layer which are sequentially arranged from top to bottom are subjected to hot pressing treatment, so that the reverse osmosis membrane supporting material which is thin in thickness, good in uniformity and capable of effectively preventing polymer membrane casting liquid from leaking is prepared. However, the eutectic point of the polymer adopted in the middle layer of the reverse osmosis membrane supporting material is slightly lower than that of the thermoplastic polymer adopted in the surface layer and the bottom layer, the layers are still relatively independent in the hot pressing process, the bonding effect is poor, the mechanical strength and the pore structure distribution of the supporting material are influenced, and the application of the reverse osmosis membrane based on the supporting material is further restricted.
In view of the above, there is a need for an improved composite support material for reverse osmosis membranes and a method for preparing the same, which solves the above problems.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the present invention is directed to a composite support material for reverse osmosis membranes and a method for preparing the same. The polyester non-woven fabric prepared by a papermaking method and the melt-blown non-woven fabric formed by melt-blowing the ethylene-methyl acrylate copolymer are overlapped and integrated through hot-pressing treatment, so that the reverse osmosis membrane composite supporting material with high mechanical strength, good corrosion resistance, small average pore diameter and high porosity is formed by utilizing the synergistic effect between the polyester non-woven fabric and the melt-blown non-woven fabric, and the reverse osmosis membrane composite supporting material is beneficial to producing reverse osmosis membrane products with high flux, high desalination rate and long service life.
In order to achieve the above object, the present invention provides a method for preparing a composite support material for a reverse osmosis membrane, comprising the steps of:
s1, preparing polyester non-woven fabric by adopting a papermaking method;
s2, carrying out melt-blown spinning on the ethylene-methyl acrylate copolymer or the modified ethylene-methyl acrylate copolymer to obtain melt-blown non-woven fabric;
s3, overlapping the melt-blown non-woven fabric obtained in the step S2 on the upper surface of the polyester non-woven fabric obtained in the step S1, and carrying out hot pressing treatment to obtain the composite supporting material for the reverse osmosis membrane.
As a further improvement of the present invention, in step S1, the preparation of the polyester nonwoven fabric by the papermaking method specifically comprises the following steps:
mixing a predetermined amount of polyester fibers and bonding fibers with water, and then pulping to obtain fiber slurry; and fully diluting the fiber slurry into fiber suspension, making the fiber suspension into a net by using paper, and drying to obtain the polyester non-woven fabric.
As a further improvement of the present invention, in step S1, the mass fraction of the polyester fibers in the polyester nonwoven fabric is 60% to 70%, and the mass fraction of the binder fibers is 30% to 40%; the process bonding temperature of the bonding fiber is 180-200 ℃.
As a further improvement of the present invention, in step S2, the melting point of the ethylene-methyl acrylate copolymer or modified ethylene-methyl acrylate copolymer is higher than the process bonding temperature of the binding fiber.
As a further improvement of the present invention, in step S2, the melt-blown spinning process specifically includes the following steps:
adding the ethylene-methyl acrylate copolymer or the modified ethylene-methyl acrylate copolymer into a screw extruder, heating and melting the ethylene-methyl acrylate copolymer or the modified ethylene-methyl acrylate copolymer, spraying the ethylene-methyl acrylate copolymer or the modified ethylene-methyl acrylate copolymer from spinneret orifices on a melt-blowing die head, and performing air draft to form superfine fibers; and depositing the superfine fibers on the surface of a receiving device, and cooling to obtain the melt-blown non-woven fabric.
In a further improvement of the invention, in step S2, the temperature of the heating and melting is 250-290 ℃; the temperature of the air flow is 260-300 ℃, and the drafting rate is 100-200 m/s; the distance between the receiving device and the spinneret orifice is 5-15 cm; the average diameter of the superfine fibers is 0.5-1.0 mu m.
In a further improvement of the present invention, in step S3, the temperature of the hot pressing treatment is 180 to 200 ℃.
As a further improvement of the invention, in step S2, the melting point of the modified ethylene-methyl acrylate copolymer is 220-250 ℃, the tensile strength is 16-20 MPa, and the elongation at break is 600-800%.
As a further improvement of the present invention, in step S2, the preparation of the modified ethylene-methyl acrylate copolymer comprises the steps of:
s21, preparing a nickel complex catalyst;
s22, copolymerizing ethylene and methyl acrylate under the action of the nickel complex catalyst obtained in the step S21 to obtain an ethylene-methyl acrylate copolymer;
s23, melting and blending the ethylene-methyl acrylate copolymer obtained in the step S22, vinyl trimethoxy silane and di-tert-butyl peroxide, and drying to obtain a mixture A; dispersing the silicon dioxide nano particles in a solvent, adding vinyl trimethoxy silane and ammonium persulfate, and fully reacting to obtain a mixture B; and then the mixture A and the mixture B are melted and blended with sodium dodecyl benzene sulfonate, the product is placed in water for full reaction, and the modified ethylene-methyl acrylate copolymer is obtained after the product is taken out and dried.
In order to achieve the purpose, the invention also provides a composite supporting material for the reverse osmosis membrane, and the supporting material is prepared according to any one of the technical schemes.
As a further improvement of the invention, the thickness of the composite supporting material for the reverse osmosis membrane is 93-97 mu m, and the gram weight is 79-82 g/m2The average pore diameter is 7-15 mu m, the porosity is 20-35%, the tensile strength is 7-10 KN/m, and the elongation at break is 13-19%.
The invention has the beneficial effects that:
(1) the invention relates to a composite support material for a reverse osmosis membrane, which is prepared simply, conveniently and efficiently by superposing a polyester non-woven fabric prepared by a papermaking method and a melt-blown non-woven fabric formed by melt-blowing an ethylene-methyl acrylate copolymer and integrating the polyester non-woven fabric and the melt-blown non-woven fabric through hot-pressing treatment. Based on the method provided by the invention, the prepared reverse osmosis membrane composite supporting material has smaller average pore diameter, higher porosity, higher mechanical strength and better corrosion resistance by utilizing the synergistic effect between the polyester non-woven fabric and the melt-blown non-woven fabric, is beneficial to producing reverse osmosis membrane products with large flux, high desalination rate and long service life, and has higher practical application value.
(2) The invention adds the bonding fiber in the process of preparing the polyester non-woven fabric, selects the ethylene-methyl acrylate copolymer or the modified ethylene-methyl acrylate copolymer with higher melting point as the raw material of the melt-blown non-woven fabric, can utilize the melting point difference between the bonding fiber and the ethylene-methyl acrylate copolymer in the hot pressing process, ensures the integrity of the pore structure of the melt-blown non-woven fabric, leads the bonding fiber in the polyester non-woven fabric to be melted and then to permeate into the melt-blown non-woven fabric, not only can effectively improve the bonding strength between the polyester non-woven fabric and the melt-blown non-woven fabric layer and improve the mechanical strength of the prepared support material, but also can solve the problem that the melt-blown non-woven fabric is not suitable for the hot pressing process in the prior art, leads the melt-blown non-woven fabric and the polyester non-woven fabric to play a synergistic effect after the hot pressing integration, further reduces the average pore diameter of the support material, the filtration performance of the support material is improved. Meanwhile, the parameters of the melt-blown process are regulated, so that the melt-blown non-woven fabric has higher porosity and smaller pore diameter by utilizing the generated superfine fibers, and forms a gradient effect with the pore structure of the polyester non-woven fabric; on the basis, the gradient effect of pores can be further strengthened by combining with the regulation and control of the hot pressing process, and meanwhile, the mechanical property and the filtering property of the porous support material are improved, so that the support material with small average pore diameter, high porosity and high mechanical strength is obtained, and is conveniently applied to the reverse osmosis membrane to improve the flux and the desalination rate of the reverse osmosis membrane.
(3) The invention can obtain the modified ethylene-methyl acrylate copolymer by further carrying out silane grafting on the prepared ethylene-methyl acrylate copolymer and then crosslinking the ethylene-methyl acrylate copolymer with silane modified silicon dioxide nano particles, thereby effectively improving the mechanical property and the corrosion resistance of the ethylene-methyl acrylate copolymer, enabling the ethylene-methyl acrylate copolymer to have higher melting point which meets the requirement of a hot pressing process, further enabling the ethylene-methyl acrylate copolymer to form superfine fibers with certain strength in the melt-blowing process, forming melt-blown non-woven fabrics with small pore diameter and high porosity, and keeping higher stability in the hot pressing process so as to ensure that a pore structure formed by the ethylene-methyl acrylate copolymer is not damaged. On the basis, the melt-blown non-woven fabric formed by the modified ethylene-methyl acrylate copolymer and the polyester non-woven fabric are integrated through hot pressing, so that the mechanical property of the prepared support material can be further improved, the support material has better corrosion resistance, is not easy to damage in a long-term use process, and the service life of the support material is effectively prolonged, so that the requirements of practical application are met.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in detail below with reference to specific embodiments.
In addition, it is also to be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention provides a preparation method of a composite support material for a reverse osmosis membrane, which comprises the following steps:
s1, preparing polyester non-woven fabric by adopting a papermaking method;
s2, carrying out melt-blown spinning on the ethylene-methyl acrylate copolymer or the modified ethylene-methyl acrylate copolymer to obtain melt-blown non-woven fabric;
s3, overlapping the melt-blown non-woven fabric obtained in the step S2 on the upper surface of the polyester non-woven fabric obtained in the step S1, and carrying out hot pressing treatment to obtain the composite supporting material for the reverse osmosis membrane.
In step S1, the preparation of the polyester nonwoven fabric by the papermaking method specifically includes the steps of:
mixing a predetermined amount of polyester fibers and bonding fibers with water, and then pulping to obtain fiber slurry; and fully diluting the fiber slurry into fiber suspension, making the fiber suspension into a net by using paper, and drying to obtain the polyester non-woven fabric.
The polyester non-woven fabric comprises 60-70% by mass of polyester fibers and 30-40% by mass of bonding fibers; the process bonding temperature of the bonding fiber is 180-200 ℃.
In step S2, the melt-blown spinning process specifically includes the following steps:
adding the ethylene-methyl acrylate copolymer or the modified ethylene-methyl acrylate copolymer into a screw extruder, heating and melting the ethylene-methyl acrylate copolymer or the modified ethylene-methyl acrylate copolymer, spraying the ethylene-methyl acrylate copolymer or the modified ethylene-methyl acrylate copolymer from spinneret orifices on a melt-blowing die head, and performing air draft to form superfine fibers; and depositing the superfine fibers on the surface of a receiving device, and cooling to obtain the melt-blown non-woven fabric.
The ethylene methyl acrylate copolymer or modified ethylene methyl acrylate copolymer has a melting point above the process bonding temperature of the binding fiber.
The heating and melting temperature is 250-290 ℃; the temperature of the air flow is 260-300 ℃, and the drafting rate is 100-200 m/s; the distance between the receiving device and the spinneret orifice is 5-15 cm; the average diameter of the superfine fibers is 0.5-1.0 mu m.
The melting point of the modified ethylene-methyl acrylate copolymer is 220-250 ℃, the tensile strength is 16-20 MPa, and the elongation at break is 600-800%.
The preparation of the modified ethylene-methyl acrylate copolymer comprises the following steps:
s21, preparing a nickel complex catalyst;
s22, copolymerizing ethylene and methyl acrylate under the action of the nickel complex catalyst obtained in the step S21 to obtain an ethylene-methyl acrylate copolymer;
s23, melting and blending the ethylene-methyl acrylate copolymer obtained in the step S22, vinyl trimethoxy silane and di-tert-butyl peroxide, and drying to obtain a mixture A; dispersing the silicon dioxide nano particles in a solvent, adding vinyl trimethoxy silane and ammonium persulfate, and fully reacting to obtain a mixture B; and then the mixture A and the mixture B are melted and blended with sodium dodecyl benzene sulfonate, the product is placed in water for full reaction, and the modified ethylene-methyl acrylate copolymer is obtained after the product is taken out and dried.
In step S3, the temperature of the hot pressing treatment is 180-200 ℃.
The invention also provides a composite supporting material for the reverse osmosis membrane, which is prepared according to the technical scheme.
The composite supporting material for the reverse osmosis membrane is 93-97 mu m in thickness and 79-82 g/m in gram weight2The average pore diameter is 7-15 mu m, the porosity is 20-35%, the tensile strength is 7-10 KN/m, and the elongation at break is 13-19%.
The composite supporting material for reverse osmosis membrane and the preparation method thereof according to the present invention will be described with reference to specific examples.
Example 1
The embodiment provides a preparation method of a composite support material for a reverse osmosis membrane, which comprises the following steps:
s1 preparation of polyester non-woven fabric by papermaking method
Mixing polyester fibers and bonding fibers according to a mass ratio of 65:35, placing the mixture into a pulping machine, and adding water for pulping to obtain fiber pulp; and adding water into the fiber slurry, uniformly stirring, fully diluting the fiber slurry into fiber suspension, making the fiber suspension into a net by a paper making machine, and drying at 80 ℃ to obtain the polyester non-woven fabric. Wherein the process bonding temperature of the bonding fiber is 180-200 ℃.
S2 preparation of melt-blown non-woven fabric
Selecting ethylene-methyl acrylate copolymer with the melting point of 220 ℃, adding the ethylene-methyl acrylate copolymer into a screw extruder, heating and melting at 270 ℃, then spraying out from a spinneret orifice on a melt-blowing die head, and drawing by hot air flow at 280 ℃ at the speed of 150m/s to form superfine fibers; and depositing the superfine fibers on the surface of a receiving device which is 10cm away from the spinneret orifice, and cooling to obtain the melt-blown non-woven fabric. Wherein the average diameter of the ultrafine fibers is 0.8 μm.
S3 preparation of composite support material for reverse osmosis membrane
And (4) superposing the melt-blown non-woven fabric obtained in the step (S2) on the upper surface of the polyester non-woven fabric obtained in the step (S1), and performing hot pressing treatment at 190 ℃ to obtain the composite supporting material for the reverse osmosis membrane.
The composite support material for reverse osmosis membrane prepared in this example was tested to have a thickness of 96 μm and a grammage of 80.1g/m2The average pore diameter was 14.8 μm, the porosity was 28.4%, the tensile strength was 8.1KN/m, and the elongation at break was 14.8%. Therefore, the composite support material for the reverse osmosis membrane prepared by the embodiment has smaller average pore diameter, higher porosity and higher mechanical strength, and can meet the requirements of practical application.
Example 2
This example provides a preparation method of a composite support material for a reverse osmosis membrane, which is different from example 1 in that an ethylene-methyl acrylate copolymer is modified, and melt-blown spinning is performed using the modified ethylene-methyl acrylate copolymer as a raw material, and the remaining steps are the same as example 1, and are not repeated herein.
Wherein, the preparation of the modified ethylene-methyl acrylate copolymer comprises the following steps:
s21 preparation of nickel complex catalyst
Dissolving aniline in dichloromethane, adding trimethyl phosphite and iodine in a molar ratio of 5:2:1, fully stirring for reaction for 10 hours, adding hydrochloric acid (12mol/L), and sequentially adding sodium bicarbonate solution and sodium chloride solution for extraction to obtain an extraction product; and (2) spin-drying the extraction product, dissolving the extraction product in tetrahydrofuran, dropwise adding n-butyllithium at 0 ℃, fully reacting for 2 hours, then adding chlorobis (2-methoxyphenyl) phosphine, controlling the molar ratio of the extraction product to the n-butyllithium to the chlorobis (2-methoxyphenyl) phosphine to be 1:1:1, fully reacting for 10 hours, and then extracting, concentrating and recrystallizing the obtained organic phase to obtain the ligand.
Mixing methallyl nickel chloride dimer, sodium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate and the ligand according to a molar ratio of 1:2:2, dissolving in dichloromethane, fully stirring for reaction for 10 hours, and filtering, evaporating and recrystallizing to obtain the nickel complex catalyst.
S22 preparation of ethylene-methyl acrylate copolymer
And respectively dissolving methyl acrylate and the nickel complex catalyst in toluene to obtain a methyl acrylate solution with the concentration of 0.05mol/L and a catalyst solution with the concentration of 0.05 mmol/L. And then vacuumizing the reaction kettle, sequentially adding the catalyst solution and the methyl acrylate solution into the reaction kettle in an ethylene atmosphere, controlling the temperature in the reaction kettle to be 90 ℃, continuously introducing ethylene gas to ensure that the pressure in the reaction kettle is 1MPa, fully reacting for 5 hours, adding ethanol to terminate the reaction, and filtering, washing and drying to obtain the ethylene-methyl acrylate copolymer.
The activity of the nickel complex catalyst prepared in this example was tested to be 3.6X 104g/(mol. h), the molecular weight of the ethylene-methyl acrylate copolymer obtained was 4.3X 104Wherein the mass fraction of methyl acrylate is 20.63%.
S23 preparation of modified ethylene-methyl acrylate copolymer
And (3) mixing the ethylene-methyl acrylate copolymer obtained in the step (S22), vinyl trimethoxy silane and di-tert-butyl peroxide according to the mass ratio of 100:2:0.1, and then carrying out melt blending, granulation and drying to obtain a mixture A.
Dispersing the silicon dioxide nano particles in ethanol, adding vinyl trimethoxy silane and ammonium persulfate (the mass ratio of the silicon dioxide nano particles to the vinyl trimethoxy silane to the ammonium persulfate is controlled to be 100:50:0.1), fully reacting for 5 hours at 80 ℃, and performing suction filtration, washing and drying to obtain a mixture B.
And mixing the mixture A, the mixture B and sodium dodecyl benzene sulfonate according to the mass ratio of 100:3:0.1, performing melt blending, performing extrusion molding, placing in water at the temperature of 80 ℃ for sufficient reaction for 2 hours, and drying to obtain the modified ethylene-methyl acrylate copolymer.
In order to examine the mechanical properties and corrosion resistance of the modified ethylene-methyl acrylate copolymer prepared in this example, the tensile strength, elongation at break and corrosion potential were measured. Wherein the tensile strength and elongation at break are tested according to GB/T1040.3-2006; in the corrosion potential test, a stainless steel electrode coated with the modified ethylene-methyl acrylate copolymer is used as a working electrode, a saturated calomel electrode is used as a reference electrode, a platinum electrode is used as an auxiliary electrode, a NaCl solution with the mass fraction of 3% is used as an electrolyte, and scanning is carried out at the scanning speed of 10mV/s within the scanning voltage range of-1.0-0.5V.
Tests prove that the modified ethylene-methyl acrylate copolymer prepared by the embodiment has the melting point of 240 ℃, the tensile strength of 19.2MPa, the elongation at break of 758% and the corrosion potential of-0.093V, and has higher melting point, excellent mechanical property and better corrosion resistance.
The composite support material for reverse osmosis membrane prepared in this example was tested to have a thickness of 96.2 μm and a grammage of 80.1g/m2The average pore diameter was 13.8 μm, the porosity was 30.8%, the tensile strength was 8.8KN/m, and the elongation at break was 17%. Compared with the embodiment 1, the composite supporting material for the reverse osmosis membrane prepared by the embodiment has smaller pore diameter, higher porosity and better mechanical property, and shows that the modification of the ethylene-methyl acrylate copolymer is beneficial to improving the pore structure and the mechanical property of the supporting material, and has higher application value.
Examples 3 to 12 and comparative examples 1 to 4
Examples 3 to 12 and comparative examples 1 to 4 respectively provide a preparation method of a composite support material for a reverse osmosis membrane, compared with example 2, examples 3 to 12 and comparative examples 1 to 2 are different in that process parameters of a preparation process are adjusted, comparative examples 3 to 4 are different in that a used raw material is adjusted, wherein in comparative example 3, a bonding fiber is not used in preparation of a polyester non-woven fabric, in comparative example 4, a raw material for preparing a melt-blown non-woven fabric in step S2 is replaced by a modified ethylene-methyl acrylate copolymer to form a polyester master batch, and other steps are the same as those in example 2, and are not described again. The corresponding process parameters of examples 3-12 and comparative examples 1-2 are shown in Table 1.
TABLE 1 Process parameters for examples 3-12 and comparative examples 1-2
The performance of the composite support materials for a reverse osmosis membrane prepared in examples 3 to 12 and comparative examples 1 to 4 was tested, and the results are shown in table 2.
TABLE 2 Performance parameters for examples 3-12 and comparative examples 1-4
As can be seen from tables 1 and 2: when the composite supporting material for the reverse osmosis membrane is prepared, the performance of the prepared supporting material can be regulated and controlled by adjusting corresponding process parameters. As can be seen from the test data of the examples 1 to 12, the performance of the prepared support material is not greatly influenced by adjusting the process parameters within a certain range, the thickness of the support material prepared in each example is 93 to 97 mu m, and the gram weight of the support material is 79 to 82g/m2The average pore diameter is 7-15 mu m, the porosity is 20-35%, the tensile strength is 7-10 KN/m, the elongation at break is 13-19%, and all performance parameters can meet the requirements of practical application. In addition, the large-scale adjustment of the melt-blown spinning and hot-pressing process parameters in the comparative examples 1-2 and the replacement of the raw materials in the comparative examples 3-4 have great influence on the performance of the prepared support material, so that the porosity of the support material is greatly reduced, and the filtering performance of the prepared reverse osmosis membrane is further influenced.
Therefore, the bonding fiber is added in the process of preparing the polyester non-woven fabric, the ethylene-methyl acrylate copolymer or the modified ethylene-methyl acrylate copolymer with higher melting point is selected as the raw material of the melt-blown non-woven fabric, and the melt-blown non-woven fabric is integrated by utilizing a hot pressing treatment mode, and the melt-blown process and the hot pressing process are regulated and controlled, so that the prepared reverse osmosis membrane composite supporting material has smaller average pore size, higher porosity, higher mechanical strength and better corrosion resistance, and is applied to the reverse osmosis membrane so as to improve the flux and the desalination rate of the reverse osmosis membrane.
In conclusion, the invention provides a preparation method of a composite supporting material for a reverse osmosis membrane. The invention adopts a paper making method to prepare the polyester non-woven fabric, and carries out melt-blown spinning on the ethylene-methyl acrylate copolymer or the modified ethylene-methyl acrylate copolymer to prepare the melt-blown non-woven fabric; and overlapping the melt-blown non-woven fabric on the upper surface of the polyester non-woven fabric, and performing hot pressing treatment to prepare the composite supporting material for the reverse osmosis membrane. Through the mode, the bonding fibers in the polyester non-woven fabric can permeate into the melt-blown non-woven fabric by utilizing the hot pressing process, the bonding strength between the polyester non-woven fabric and the melt-blown non-woven fabric layer is effectively improved, and the pore structure of the polyester non-woven fabric and the melt-blown non-woven fabric layer is further optimized, so that the support material with small average pore size, high porosity, high mechanical strength and good corrosion resistance is formed, the production of a reverse osmosis membrane product with high flux, high desalination rate and long service life is facilitated, and the practical application value is higher.
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the spirit and scope of the present invention.
Claims (10)
1. The preparation method of the composite supporting material for the reverse osmosis membrane is characterized by comprising the following steps of:
s1, preparing polyester non-woven fabric by adopting a papermaking method;
s2, carrying out melt-blown spinning on the ethylene-methyl acrylate copolymer or the modified ethylene-methyl acrylate copolymer to obtain melt-blown non-woven fabric;
s3, overlapping the melt-blown non-woven fabric obtained in the step S2 on the upper surface of the polyester non-woven fabric obtained in the step S1, and carrying out hot pressing treatment to obtain the composite supporting material for the reverse osmosis membrane.
2. The method for preparing a composite support material for a reverse osmosis membrane according to claim 1, characterized in that: in step S1, the polyester nonwoven fabric includes polyester fibers and binder fibers; the polyester fiber accounts for 60-70% by mass, and the bonding fiber accounts for 30-40% by mass; the process bonding temperature of the bonding fiber is 180-200 ℃.
3. The method for preparing a composite support material for a reverse osmosis membrane according to claim 2, characterized in that: in step S2, the ethylene methyl acrylate copolymer or modified ethylene methyl acrylate copolymer has a melting point above the process bonding temperature of the binding fiber.
4. The method for preparing a composite support material for a reverse osmosis membrane according to claim 1, characterized in that: in step S2, the melt-blown spinning process specifically includes the following steps:
adding the ethylene-methyl acrylate copolymer or the modified ethylene-methyl acrylate copolymer into a screw extruder, heating and melting the ethylene-methyl acrylate copolymer or the modified ethylene-methyl acrylate copolymer, spraying the ethylene-methyl acrylate copolymer or the modified ethylene-methyl acrylate copolymer from spinneret orifices on a melt-blowing die head, and performing air draft to form superfine fibers; and depositing the superfine fibers on the surface of a receiving device, and cooling to obtain the melt-blown non-woven fabric.
5. The method for preparing a composite support material for a reverse osmosis membrane according to claim 4, wherein: in step S2, the heating and melting temperature is 250-290 ℃; the temperature of the air flow is 260-300 ℃, and the drafting rate is 100-200 m/s; the distance between the receiving device and the spinneret orifice is 5-15 cm; the average diameter of the superfine fibers is 0.5-1.0 mu m.
6. The method for producing a composite support material for a reverse osmosis membrane according to any one of claims 1 to 5, wherein: in step S3, the temperature of the hot pressing treatment is 180-200 ℃.
7. The method for preparing a composite support material for a reverse osmosis membrane according to claim 1, characterized in that: in step S2, the modified ethylene-methyl acrylate copolymer has a melting point of 220-250 ℃, a tensile strength of 16-20 MPa, and an elongation at break of 600-800%.
8. The method for producing a composite support material for a reverse osmosis membrane according to any one of claims 1 to 7, wherein: in step S2, the preparation of the modified ethylene-methyl acrylate copolymer includes the steps of:
s21, preparing a nickel complex catalyst;
s22, copolymerizing ethylene and methyl acrylate under the action of the nickel complex catalyst obtained in the step S21 to obtain an ethylene-methyl acrylate copolymer;
s23, melting and blending the ethylene-methyl acrylate copolymer obtained in the step S22, vinyl trimethoxy silane and di-tert-butyl peroxide, and drying to obtain a mixture A; dispersing the silicon dioxide nano particles in a solvent, adding vinyl trimethoxy silane and ammonium persulfate, and fully reacting to obtain a mixture B; and then the mixture A and the mixture B are melted and blended with sodium dodecyl benzene sulfonate, the product is placed in water for full reaction, and the modified ethylene-methyl acrylate copolymer is obtained after the product is taken out and dried.
9. A composite support material for a reverse osmosis membrane, characterized in that: the composite supporting material for the reverse osmosis membrane is prepared by the preparation method of any one of claims 1 to 8.
10. The composite support material for a reverse osmosis membrane according to claim 9, wherein: the composite supporting material for the reverse osmosis membrane is 93-97 mu m in thickness and 79-82 g/m in gram weight2The average pore diameter is 7-15 mu m, the porosity is 20-35%, the tensile strength is 7-10 KN/m, and the elongation at break is 13-19%.
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Denomination of invention: Composite support materials and preparation methods for reverse osmosis membranes Effective date of registration: 20231201 Granted publication date: 20220624 Pledgee: Anqing Millennium Tower Financing Guarantee Co.,Ltd. Pledgor: Anhui Qinglan New Material Technology Co.,Ltd. Registration number: Y2023980068789 |