CN108905625B - Reverse osmosis membrane and preparation method and application thereof - Google Patents
Reverse osmosis membrane and preparation method and application thereof Download PDFInfo
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- CN108905625B CN108905625B CN201810805115.6A CN201810805115A CN108905625B CN 108905625 B CN108905625 B CN 108905625B CN 201810805115 A CN201810805115 A CN 201810805115A CN 108905625 B CN108905625 B CN 108905625B
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- 239000012528 membrane Substances 0.000 title claims abstract description 85
- 238000001223 reverse osmosis Methods 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011259 mixed solution Substances 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 10
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 9
- 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 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 9
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 9
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 9
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 9
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 8
- 238000005266 casting Methods 0.000 claims description 8
- 239000002086 nanomaterial Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004695 Polyether sulfone Substances 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical group 0.000 claims description 4
- 125000001072 heteroaryl group Chemical group 0.000 claims description 4
- 238000007731 hot pressing Methods 0.000 claims description 4
- -1 hydroxy, propyl Chemical group 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000001624 naphthyl group Chemical group 0.000 claims description 4
- 229920006393 polyether sulfone Polymers 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 2
- XJQZRVQRVPICGK-UHFFFAOYSA-N 3-[dimethoxy(prop-2-enoxy)silyl]propan-1-amine Chemical compound C(=C)CO[Si](OC)(OC)CCCN XJQZRVQRVPICGK-UHFFFAOYSA-N 0.000 claims description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 150000002431 hydrogen Chemical group 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 125000004076 pyridyl group Chemical group 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 125000001544 thienyl group Chemical group 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Chemical group 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 abstract description 5
- 230000035699 permeability Effects 0.000 abstract description 3
- 238000007598 dipping method Methods 0.000 abstract 2
- 239000002105 nanoparticle Substances 0.000 description 6
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000004907 flux Effects 0.000 description 4
- 239000005489 Bromoxynil Substances 0.000 description 2
- UNAQSRLBVVDYGP-UHFFFAOYSA-N hex-5-enenitrile Chemical compound C=CCCCC#N UNAQSRLBVVDYGP-UHFFFAOYSA-N 0.000 description 2
- 229940098779 methanesulfonic acid Drugs 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000001728 nano-filtration Methods 0.000 description 2
- YJMNOKOLADGBKA-UHFFFAOYSA-N naphthalene-1-carbonitrile Chemical compound C1=CC=C2C(C#N)=CC=CC2=C1 YJMNOKOLADGBKA-UHFFFAOYSA-N 0.000 description 2
- AZKDTTQQTKDXLH-UHFFFAOYSA-N naphthalene-2-carbonitrile Chemical compound C1=CC=CC2=CC(C#N)=CC=C21 AZKDTTQQTKDXLH-UHFFFAOYSA-N 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- NHWQMJMIYICNBP-UHFFFAOYSA-N 2-chlorobenzonitrile Chemical compound ClC1=CC=CC=C1C#N NHWQMJMIYICNBP-UHFFFAOYSA-N 0.000 description 1
- YXDXXGXWFJCXEB-UHFFFAOYSA-N 2-furonitrile Chemical compound N#CC1=CC=CO1 YXDXXGXWFJCXEB-UHFFFAOYSA-N 0.000 description 1
- OQRMWUNUKVUHQO-UHFFFAOYSA-N 2-naphthalen-1-ylacetonitrile Chemical compound C1=CC=C2C(CC#N)=CC=CC2=C1 OQRMWUNUKVUHQO-UHFFFAOYSA-N 0.000 description 1
- LPCWDVLDJVZIHA-UHFFFAOYSA-N 2-naphthalen-2-ylacetonitrile Chemical compound C1=CC=CC2=CC(CC#N)=CC=C21 LPCWDVLDJVZIHA-UHFFFAOYSA-N 0.000 description 1
- UPMXNNIRAGDFEH-UHFFFAOYSA-N 3,5-dibromo-4-hydroxybenzonitrile Chemical compound OC1=C(Br)C=C(C#N)C=C1Br UPMXNNIRAGDFEH-UHFFFAOYSA-N 0.000 description 1
- WWPPXDOOKMWVDN-UHFFFAOYSA-N 3-amino-3,4-dihydro-1h-1,5-naphthyridin-2-one Chemical compound C1=CC=C2NC(=O)C(N)CC2=N1 WWPPXDOOKMWVDN-UHFFFAOYSA-N 0.000 description 1
- WBUOVKBZJOIOAE-UHFFFAOYSA-N 3-chlorobenzonitrile Chemical compound ClC1=CC=CC(C#N)=C1 WBUOVKBZJOIOAE-UHFFFAOYSA-N 0.000 description 1
- AEKVBBNGWBBYLL-UHFFFAOYSA-N 4-fluorobenzonitrile Chemical compound FC1=CC=C(C#N)C=C1 AEKVBBNGWBBYLL-UHFFFAOYSA-N 0.000 description 1
- VCZNNAKNUVJVGX-UHFFFAOYSA-N 4-methylbenzonitrile Chemical compound CC1=CC=C(C#N)C=C1 VCZNNAKNUVJVGX-UHFFFAOYSA-N 0.000 description 1
- MMNWSHJJPDXKCH-UHFFFAOYSA-N 9,10-dioxoanthracene-2-sulfonic acid Chemical compound C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 MMNWSHJJPDXKCH-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PLUBXMRUUVWRLT-UHFFFAOYSA-N Ethyl methanesulfonate Chemical compound CCOS(C)(=O)=O PLUBXMRUUVWRLT-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- OBESRABRARNZJB-UHFFFAOYSA-N aminomethanesulfonic acid Chemical compound NCS(O)(=O)=O OBESRABRARNZJB-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 1
- XDRMBCMMABGNMM-UHFFFAOYSA-N ethyl benzenesulfonate Chemical compound CCOS(=O)(=O)C1=CC=CC=C1 XDRMBCMMABGNMM-UHFFFAOYSA-N 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- SDAXRHHPNYTELL-UHFFFAOYSA-N heptanenitrile Chemical compound CCCCCCC#N SDAXRHHPNYTELL-UHFFFAOYSA-N 0.000 description 1
- AILKHAQXUAOOFU-UHFFFAOYSA-N hexanenitrile Chemical compound CCCCCC#N AILKHAQXUAOOFU-UHFFFAOYSA-N 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 1
- QHDRKFYEGYYIIK-UHFFFAOYSA-N isovaleronitrile Chemical compound CC(C)CC#N QHDRKFYEGYYIIK-UHFFFAOYSA-N 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- CZXGXYBOQYQXQD-UHFFFAOYSA-N methyl benzenesulfonate Chemical compound COS(=O)(=O)C1=CC=CC=C1 CZXGXYBOQYQXQD-UHFFFAOYSA-N 0.000 description 1
- MBXNQZHITVCSLJ-UHFFFAOYSA-N methyl fluorosulfonate Chemical compound COS(F)(=O)=O MBXNQZHITVCSLJ-UHFFFAOYSA-N 0.000 description 1
- MBABOKRGFJTBAE-UHFFFAOYSA-N methyl methanesulfonate Chemical compound COS(C)(=O)=O MBABOKRGFJTBAE-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- KVBGVZZKJNLNJU-UHFFFAOYSA-N naphthalene-2-sulfonic acid Chemical compound C1=CC=CC2=CC(S(=O)(=O)O)=CC=C21 KVBGVZZKJNLNJU-UHFFFAOYSA-N 0.000 description 1
- PLZZPPHAMDJOSR-UHFFFAOYSA-N nonanenitrile Chemical compound CCCCCCCCC#N PLZZPPHAMDJOSR-UHFFFAOYSA-N 0.000 description 1
- YSIMAPNUZAVQER-UHFFFAOYSA-N octanenitrile Chemical compound CCCCCCCC#N YSIMAPNUZAVQER-UHFFFAOYSA-N 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- PTWLOSARXIJRRJ-UHFFFAOYSA-N pyridin-1-ium-4-sulfonate Chemical compound OS(=O)(=O)C1=CC=NC=C1 PTWLOSARXIJRRJ-UHFFFAOYSA-N 0.000 description 1
- SXVRECLPTCOMIA-UHFFFAOYSA-N quinoline-8-sulfonic acid Chemical compound C1=CN=C2C(S(=O)(=O)O)=CC=CC2=C1 SXVRECLPTCOMIA-UHFFFAOYSA-N 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- RHSBIGNQEIPSCT-UHFFFAOYSA-N stearonitrile Chemical compound CCCCCCCCCCCCCCCCCC#N RHSBIGNQEIPSCT-UHFFFAOYSA-N 0.000 description 1
- BSXLLFUSNQCWJP-UHFFFAOYSA-N thiophene-2-sulfonic acid Chemical compound OS(=O)(=O)C1=CC=CS1 BSXLLFUSNQCWJP-UHFFFAOYSA-N 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 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
- B01D67/0002—Organic membrane manufacture
-
- 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
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
-
- 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
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
A preparation method of a reverse osmosis membrane comprises the steps of dipping a reverse osmosis membrane base membrane in a mixed solution, repeatedly drying and dipping to obtain a dried membrane, washing for 2-3 times by using deionized water, and drying to obtain the reverse osmosis membrane. The reverse osmosis membrane has the characteristics of easy preparation and operation, high water permeability, high salt retardation rate and long service life.
Description
Technical Field
The invention relates to a reverse osmosis membrane and a preparation method and application thereof.
Background
The reverse osmosis membrane is an artificial semipermeable membrane with certain characteristics and is made by simulating a biological semipermeable membrane, and is a core component of a reverse osmosis technology. The principle of reverse osmosis is that under the action of the osmotic pressure higher than that of the solution, other substances are separated from water based on the fact that the substances cannot permeate a semipermeable membrane. The reverse osmosis membrane has a very small membrane pore size, and thus can effectively remove dissolved salts, colloids, microorganisms, organic substances, and the like in water. The system has the advantages of good water quality, low energy consumption, no pollution, simple process, simple and convenient operation and the like.
The reverse osmosis membrane is a core element for realizing reverse osmosis and is an artificial semipermeable membrane with certain characteristics and made by simulating a biological semipermeable membrane. Generally made of high molecular materials. Such as cellulose acetate films, aromatic polyhydrazide films, aromatic polyamide films. The diameter of the surface micropores is generally between 0.5 and 10nm, and the size of the permeability is related to the chemical structure of the membrane. Some polymer materials have good salt repellency, but the water permeation rate is not good. Some polymer materials have more hydrophilic groups in their chemical structures, so that the permeation rate of water is relatively fast. A satisfactory reverse osmosis membrane should therefore have a suitable permeate or salt rejection.
Disclosure of Invention
The invention adopts the following technical scheme:
a method for preparing a reverse osmosis membrane, comprising the steps of:
mixing N, N-dimethylformamide, polyvinylpyrrolidone, trimesoyl chloride and cyclohexane, stirring at room temperature for 5-10h, heating to 40-60 ℃, and reacting for 5-10h to obtain a mixed solution for later use;
soaking a reverse osmosis membrane base membrane in the mixed solution, keeping the mixed solution for 20-30min, taking out the membrane, drying the membrane in vacuum, soaking the membrane in the mixed solution again after drying, and repeating the step for 2-3 times to obtain a dried membrane;
and step three, placing the dried membrane in deionized water at 50 ℃, washing for 2-3 times, and finally drying in an oven at 80 ℃ for 30-60min to obtain the reverse osmosis membrane.
In the step one, the N, N-dimethylformamide, the polyvinylpyrrolidone, the trimesoyl chloride and the cyclohexane are mixed according to the mass ratio of 1-5:3-4:1-2: 10-15.
And in the step one, mixing the N, N-dimethylformamide, the polyvinylpyrrolidone, the trimesoyl chloride and the cyclohexane according to the mass ratio of 4:3.5:1.5: 15.
A reverse osmosis membrane characterized in that it is prepared as described above.
An ultrafiltration membrane characterized by comprising at least one reverse osmosis membrane as hereinbefore described.
Nanofiltration membrane, characterized in that it comprises at least one layer of reverse osmosis membrane as described above.
Use of a reverse osmosis membrane as hereinbefore described in water treatment and chemical separation.
Has the advantages that:
the reverse osmosis membrane has the characteristics of easy preparation and operation, high water permeability, high salt retardation rate and long service life; the nano material has good dispersibility, gives the film the advantages of high flux and low pollution, does not need an additional pore-forming agent, is environment-friendly, and can be widely applied to the fields of water treatment and chemical separation.
Detailed Description
The invention will be further illustrated with reference to the following specific examples.
A method for preparing a reverse osmosis membrane, comprising the steps of:
mixing N, N-dimethylformamide, polyvinylpyrrolidone, trimesoyl chloride and cyclohexane, stirring at room temperature for 5-10h, heating to 40-60 ℃, and reacting for 5-10h to obtain a mixed solution for later use;
soaking a reverse osmosis membrane base membrane in the mixed solution, keeping the mixed solution for 20-30min, taking out the membrane, drying the membrane in vacuum, soaking the membrane in the mixed solution again after drying, and repeating the step for 2-3 times to obtain a dried membrane;
and step three, placing the dried membrane in deionized water at 50 ℃, washing for 2-3 times, and finally drying in an oven at 80 ℃ for 30-60min to obtain the reverse osmosis membrane.
In the step one, the N, N-dimethylformamide, the polyvinylpyrrolidone, the trimesoyl chloride and the cyclohexane are mixed according to the mass ratio of 1-5:3-4:1-2: 10-15.
And in the step one, mixing the N, N-dimethylformamide, the polyvinylpyrrolidone, the trimesoyl chloride and the cyclohexane according to the mass ratio of 4:3.5:1.5: 15.
A reverse osmosis membrane characterized in that it is prepared as described above.
An ultrafiltration membrane characterized by comprising at least one reverse osmosis membrane as hereinbefore described.
Nanofiltration membrane, characterized in that it comprises at least one layer of reverse osmosis membrane as described above.
Use of a reverse osmosis membrane as hereinbefore described in water treatment and chemical separation.
The preparation of the reverse osmosis membrane base membrane in the second step of the invention comprises the following steps:
step A, preparation of surface modified nano material
a. Placing the nano titanium dioxide in deionized water, and magnetically stirring for 15-30h to prepare suspension with the mass percentage concentration of 5-10% for later use;
b. mixing m-phenylenediamine, acetic acid, a silane coupling agent, N-methylpyrrolidone, a first compound and deionized water according to the mass ratio of 2-5:1-2:0.5-2:2-4:5-8:30-60, and stirring for 3-6h to prepare a first solution for later use;
the silane coupling agent is prepared by mixing aminopropyltrimethoxysilane and vinyl aminopropyltrimethoxysilane in a mass ratio of 1-2: 2-3;
the structural formula of the first compound is shown in the formula (1)
Wherein R1 is selected from benzene ring, methyl, ethyl, hydroxy, propyl, ester group, amino, aryl, aralkyl, heteroaryl, vinyl, thienyl, naphthyl, pyridyl, halogen;
r2 is selected from hydrogen, halogen, methyl, ethyl;
c. mixing the suspension prepared in the step a and the first solution prepared in the step b, placing the mixture in an oil bath at the temperature of 80-150 ℃, stirring for 30-60min, cooling to room temperature, introducing nitrogen, standing for 10-30min, adding the first mixed solution and a catalyst, heating to 60-70 ℃, refluxing for 4-6h, filtering a reaction product in vacuum, washing for 3-6 times by using ethanol, and drying in vacuum to obtain a surface-modified nano material for later use;
the first mixed solution consists of vinyl pyrrolidone and sodium acetate in a mass ratio of 1-5: 2-4;
the catalyst is PtxCoyA chemical catalyst, wherein x/y = 1.5-2;
the mass ratio of the suspension prepared in the step a, the first solution prepared in the step b, the first mixed solution and the catalyst is 2-3:5-8:1-2: 0.2-0.5;
step B, preparation of reverse osmosis membrane base membrane
Placing the polymer solution and the surface modified nano material prepared in the step A into a container, stirring for 20-60min, stopping stirring to obtain a casting solution, standing, casting the casting solution on glass to form a film after the casting solution is completely bubble-free, heating to 50-90 ℃, vacuum-drying for 10-20 h, lifting and hot-pressing the dried film, wherein the hot-pressing temperature is 100-150 ℃, and the pressure is 3-9 Mpa; cutting the hot-pressed membrane and stretching to obtain a reverse osmosis membrane base membrane;
the polymer solution is prepared by mixing polyether sulfone, polyether sulfone ketone and a second compound according to the mass ratio of 1-4:2-5: 1-2;
the structural formula of the second compound is shown in formula (2)
Wherein R3 is selected from alkyl, aryl, aralkyl, heteroaryl, hydrocarbyl, naphthyl;
the stretching in the step B is longitudinal stretching at the temperature of 100-120 ℃, and then natural cooling to room temperature; heating to 130-140 ℃ and transversely stretching at the stretching speed of 2-4m/s and the stretching ratio of 10-20 times; placing the stretched film at 150 ℃ for heat setting for 10-60 minutes to obtain a reverse osmosis membrane base film;
the first compound in the present invention may be selected from: methanesulfonic acid, 1-naphthalenesulfonic acid, 2-naphthalenesulfonic acid, benzenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, 1-propanesulfonic acid, 4-borabenzenesulfonic acid, methyl fluorosulfonate, ethyl methanesulfonate, aminomethanesulfonic acid, 1-anthraquinone sulfonic acid, 2-anthraquinone sulfonic acid, vinylsulfonic acid, thiophene-2-sulfonic acid, quinoline-8-sulfonic acid, methyl benzenesulfonate, ethyl benzenesulfonate, p-toluenesulfonic acid, pyridine-4-sulfonic acid, methyl methanesulfonate, and the like.
The second compound in the present invention may be selected from: hexanenitrile, nonanenitrile, octanenitrile, octadecanenitrile, decanedionitrile, n-heptanenitrile, isobutyronitrile, p-tolunitrile, bromoxynil, 3-chlorobenzonitrile, o-chlorobenzonitrile, 5-hexenenitrile, 2-naphthaleneacetonitrile, 2-furancarbonitrile, isovaleronitrile, o-iodoxynil, 2-bromoxynil, p-fluorobenzonitrile, 1-naphthaleneacetonitrile, 2-naphthalenecarbonitrile, 1-naphthalenecarbonitrile, and the like.
The reverse osmosis membrane of the invention is researched:
1. step A, preparation of surface modified nano material, adding PtxCoyAn alloy catalyst is creatively adopted, x/y =1.5-2, and research shows that the first compound and the silane coupling agent are combined to form a branch on the surface of the nanoparticle in the presence of a first mixed solution after the catalyst is added, a reticular molecular bond is formed between the first compound and the silane coupling agent, the branch is firmly arranged on the surface of the nanoparticle, and the branch ratio after the catalyst is added exceeds 25-40% of that without the catalyst; thereby improving the bonding property between the polymer matrixStability of a high reverse osmosis membrane;
2. the first compound is added in the modification of the nanoparticles, and the first compound and the silane coupling agent are combined to be capable of being on the surface of the branched nanoparticles; the self-made polymer solution is adopted in the base membrane of the reverse osmosis membrane, the second compound is added in the polymer solution, the second compound can enter between the first compound and the silane coupling agent to form a reticular molecular bond to be consolidated to form a more stable reticular compound, and the nano particles and the polymer matrix form a molecular bond to be combined together, so that the bonding strength of an interface is enhanced, and the chlorine resistance of the reverse osmosis membrane is effectively improved through the later heat treatment on the base membrane; the addition of the second compound enables an additional nano-scale channel to be provided between the nano-particles and the polymer interface, so that the water flux of the reverse osmosis membrane is effectively improved; at room temperature, the operating pressure is 0.5Mpa, 2g/L MgSO4The flux of the aqueous solution is tested to reach 38.2L/(m 2. n), and the retention rate is 97.6 percent
3. Research shows that after the NaCl solution is soaked in 1000ppm NaClO water solution for 10 hours, the NaCl interception rate is still as high as 96.4-99.6%, preferably 99.1%; the water flux reaches 1.87-2.13M3/M2D, preferably 1.99M3/M2.d。
It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Claims (5)
1. A method for preparing a reverse osmosis membrane, comprising the steps of:
mixing N, N-dimethylformamide, polyvinylpyrrolidone, trimesoyl chloride and cyclohexane, stirring at room temperature for 5-10h, heating to 40-60 ℃, and reacting for 5-10h to obtain a mixed solution for later use;
soaking a reverse osmosis membrane base membrane in the mixed solution, keeping the mixed solution for 20-30min, taking out the membrane, drying the membrane in vacuum, soaking the membrane in the mixed solution again after drying, and repeating the step for 2-3 times to obtain a dried membrane;
thirdly, placing the dried membrane in deionized water at 50 ℃, washing for 2-3 times, and finally drying in a drying oven at 80 ℃ for 30-60min to obtain the reverse osmosis membrane;
the preparation of the reverse osmosis membrane base membrane in the step two comprises the following steps:
step A, preparation of surface modified nano material
a. Placing the nano titanium dioxide in deionized water, and magnetically stirring for 15-30h to prepare suspension with the mass percentage concentration of 5-10% for later use;
b. mixing m-phenylenediamine, acetic acid, a silane coupling agent, N-methylpyrrolidone, a first compound and deionized water according to the mass ratio of 2-5:1-2:0.5-2:2-4:5-8:30-60, and stirring for 3-6h to prepare a first solution for later use;
the silane coupling agent is prepared by mixing aminopropyltrimethoxysilane and vinyl aminopropyltrimethoxysilane in a mass ratio of 1-2: 2-3;
the structural formula of the first compound is shown in the formula (1)
Wherein R1 is selected from benzene ring, methyl, ethyl, hydroxy, propyl, ester group, amino, aralkyl, heteroaryl, vinyl, thienyl, naphthyl, pyridyl, halogen;
r2 is selected from hydrogen, halogen, methyl, ethyl;
c. mixing the suspension prepared in the step a and the first solution prepared in the step b, placing the mixture in an oil bath at the temperature of 80-150 ℃, stirring for 30-60min, cooling to room temperature, introducing nitrogen, standing for 10-30min, adding the first mixed solution and a catalyst, heating to 60-70 ℃, refluxing for 4-6h, filtering a reaction product in vacuum, washing for 3-6 times by using ethanol, and drying in vacuum to obtain a surface-modified nano material for later use;
the first mixed solution consists of vinyl pyrrolidone and sodium acetate in a mass ratio of 1-5: 2-4;
the catalyst is PtxCoyAn alloy catalyst, wherein x/y is 1.5-2;
the mass ratio of the suspension prepared in the step a, the first solution prepared in the step b, the first mixed solution and the catalyst is 2-3:5-8:1-2: 0.2-0.5;
step B, preparation of reverse osmosis membrane base membrane
Placing the polymer solution and the surface modified nano material prepared in the step A into a container, stirring for 20-60min, stopping stirring to obtain a casting solution, standing, casting the casting solution on glass to form a film after the casting solution is completely bubble-free, heating to 50-90 ℃, vacuum-drying for 10-20 h, lifting and hot-pressing the dried film, wherein the hot-pressing temperature is 100-150 ℃, and the pressure is 3-9 Mpa; cutting the hot-pressed membrane and stretching to obtain a reverse osmosis membrane base membrane;
the polymer solution is prepared by mixing polyether sulfone, polyether sulfone ketone and a second compound according to the mass ratio of 1-4:2-5: 1-2;
the structural formula of the second compound is shown in formula (2)
Wherein R3 is selected from alkyl, aryl, aralkyl, heteroaryl, naphthyl.
2. The method of preparing a reverse osmosis membrane according to claim 1, wherein in step one, the N, N-dimethylformamide, the polyvinylpyrrolidone, the trimesoyl chloride and the cyclohexane are mixed in a mass ratio of 1-5:3-4:1-2: 10-15.
3. The method of claim 2, wherein in step one the N, N-dimethylformamide, polyvinylpyrrolidone, trimesoyl chloride and cyclohexane are combined in a mass ratio of 4:3.5:1.5: 15.
4. A reverse osmosis membrane characterized in that it is prepared by the process of any one of claims 1 to 3.
5. Use of the reverse osmosis membrane of claim 4 in water treatment and chemical separation.
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