CN108043252B - High-performance reverse osmosis composite membrane and preparation method thereof - Google Patents
High-performance reverse osmosis composite membrane and preparation method thereof Download PDFInfo
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- CN108043252B CN108043252B CN201711249761.0A CN201711249761A CN108043252B CN 108043252 B CN108043252 B CN 108043252B CN 201711249761 A CN201711249761 A CN 201711249761A CN 108043252 B CN108043252 B CN 108043252B
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- reverse osmosis
- composite membrane
- polyvinyl alcohol
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- solution
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- 238000001223 reverse osmosis Methods 0.000 title claims abstract description 39
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000243 solution Substances 0.000 claims description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 36
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 30
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 30
- 150000001263 acyl chlorides Chemical class 0.000 claims description 23
- 239000008346 aqueous phase Substances 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 21
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- 229920002647 polyamide Polymers 0.000 claims description 17
- 238000011033 desalting Methods 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 15
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
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- 239000000178 monomer Substances 0.000 claims description 14
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- 229920001577 copolymer Polymers 0.000 claims description 13
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000012074 organic phase Substances 0.000 claims description 12
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- 239000000126 substance Substances 0.000 claims description 11
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 claims description 10
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- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 9
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
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- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 4
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- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 4
- 239000004745 nonwoven fabric Substances 0.000 claims description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 4
- 239000002352 surface water Substances 0.000 claims description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004471 Glycine Substances 0.000 claims description 3
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims description 3
- QIVBCDIJIAJPQS-VIFPVBQESA-N L-tryptophane Chemical compound C1=CC=C2C(C[C@H](N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-VIFPVBQESA-N 0.000 claims description 3
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004472 Lysine Substances 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- QIVBCDIJIAJPQS-UHFFFAOYSA-N Tryptophan Natural products C1=CC=C2C(CC(N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-UHFFFAOYSA-N 0.000 claims description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 3
- 235000013922 glutamic acid Nutrition 0.000 claims description 3
- 239000004220 glutamic acid Substances 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 238000012695 Interfacial polymerization Methods 0.000 claims description 2
- ONIBWKKTOPOVIA-BYPYZUCNSA-N L-Proline Chemical compound OC(=O)[C@@H]1CCCN1 ONIBWKKTOPOVIA-BYPYZUCNSA-N 0.000 claims description 2
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims description 2
- AGPKZVBTJJNPAG-WHFBIAKZSA-N L-isoleucine Chemical compound CC[C@H](C)[C@H](N)C(O)=O AGPKZVBTJJNPAG-WHFBIAKZSA-N 0.000 claims description 2
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- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 claims description 2
- COLNVLDHVKWLRT-QMMMGPOBSA-N L-phenylalanine Chemical compound OC(=O)[C@@H](N)CC1=CC=CC=C1 COLNVLDHVKWLRT-QMMMGPOBSA-N 0.000 claims description 2
- AYFVYJQAPQTCCC-GBXIJSLDSA-N L-threonine Chemical compound C[C@@H](O)[C@H](N)C(O)=O AYFVYJQAPQTCCC-GBXIJSLDSA-N 0.000 claims description 2
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- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 claims description 2
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- 239000004473 Threonine Substances 0.000 claims description 2
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- AGPKZVBTJJNPAG-UHFFFAOYSA-N isoleucine Natural products CCC(C)C(N)C(O)=O AGPKZVBTJJNPAG-UHFFFAOYSA-N 0.000 claims description 2
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- 239000000203 mixture Substances 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 claims description 2
- 229920002492 poly(sulfone) Polymers 0.000 claims description 2
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 claims description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
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- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 claims description 2
- 238000000108 ultra-filtration Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 abstract description 21
- 230000004907 flux Effects 0.000 abstract description 17
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 150000003839 salts Chemical class 0.000 description 17
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 238000000034 method Methods 0.000 description 6
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 4
- 229940098773 bovine serum albumin Drugs 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
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- 238000002156 mixing Methods 0.000 description 3
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 2
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
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- LAXBNTIAOJWAOP-UHFFFAOYSA-N 2-chlorobiphenyl Chemical class ClC1=CC=CC=C1C1=CC=CC=C1 LAXBNTIAOJWAOP-UHFFFAOYSA-N 0.000 description 1
- QQSURLJQEUZMQU-UHFFFAOYSA-N 3-(4-ethenyl-2h-pyridin-1-yl)propane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCN1CC=C(C=C)C=C1 QQSURLJQEUZMQU-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000012696 Interfacial polycondensation Methods 0.000 description 1
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- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
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- 230000000052 comparative effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
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- 230000035699 permeability Effects 0.000 description 1
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Classifications
-
- 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
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/78—Graft polymers
-
- 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
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
Abstract
The invention relates to the technical field of reverse osmosis membrane modification, in particular to a high-performance reverse osmosis composite membrane and a preparation method thereof. The prepared reverse osmosis composite membrane can still keep stable high flux and rejection rate after long-time continuous filtration, and simultaneously has firm membrane structure and excellent pollution resistance.
Description
Technical Field
The invention relates to the technical field of reverse osmosis membrane modification, in particular to a high-performance reverse osmosis composite membrane and a preparation method thereof.
Background
Today, with the growing social population and the development of industrialization, the pollution and shortage of water resources become a problem which is more and more regarded by the public. In order to solve the pollution and shortage of water resources, the technology of reverse osmosis membrane water treatment is produced at present.
The reverse osmosis membrane water treatment technology is a method for separating, extracting, purifying and concentrating component solutes and solvents in a solution according to different selective permeabilities of materials. However, in current practice, the most significant problem is membrane fouling, which results in irreversible flux loss due to fouling of the membrane pore size. Frequent cleaning of the membrane module by chemical or physical means not only increases the treatment cost but also reduces the separation efficiency of the reverse osmosis membrane.
In the prior art, for a reverse osmosis composite membrane, trimesoyl chloride is generally adopted as an organic phase monomer, and o-phenylenediamine or m-phenylenediamine of a water phase monomer is subjected to reaction to obtain a polyamide desalting layer. However, the structure between the polyamide desalting layer and the porous supporting layer is not compact enough, and the polyamide desalting layer is easy to fall off in the using process and has short service life.
For example, CN102553460B discloses a method for preparing a contamination-resistant low-pressure reverse osmosis membrane, which comprises preparing a polyamide membrane by interfacial polycondensation of an organic phase monomer of trimesoyl chloride or polychlorinated biphenylyl chloride and an aqueous phase monomer of o-phenylenediamine or m-phenylenediamine, and then coating and cross-linking a layer of polyvinyl alcohol grafted zwitterionic polymer membrane on the surface of the polyamide membrane. The technical scheme has the defects that zwitterions in the polyvinyl alcohol grafted zwitterionic polymer are N, N-dimethyl N- (2-methyl acrylamide oxyethyl) N- (2-sulfoethyl) ammonium or N- (3-sulfopropyl) 4-vinylpyridine, and the zwitterions are complex in chemical structure, difficult to synthesize and difficult to obtain.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a technical scheme of a high-performance reverse osmosis composite membrane and a preparation method thereof.
A high-performance reverse osmosis composite membrane consists of a non-woven fabric layer, a porous supporting layer and a polyamide desalting layer, wherein the porous supporting layer is a polysulfone ultrafiltration membrane layer on the surface of the non-woven fabric layer; the polyamide desalting layer is prepared by placing a porous support layer in an aqueous phase solution containing an aqueous phase monomer, and carrying out interfacial polymerization reaction in an organic phase monomer solution, wherein the aqueous phase solution is doped with a polyvinyl alcohol grafted zwitterionic copolymer.
The water phase monomer is m-phenylenediamine.
The synthetic method of the polyvinyl alcohol grafted zwitterionic copolymer comprises the following steps: adding 1-40% by mass of zwitterionic monomer alpha-amino acid into 100ml of 10% polyvinyl alcohol aqueous solution, adding 0.05mol of DCC (dicyclohexylcarbodiimide) as an oxidation-reduction catalyst under the protection of nitrogen, reacting for 1-12h at the temperature of 40 ℃, precipitating and washing a product by using methanol, and drying the obtained solid for 1-24h at the temperature of 60 ℃ in an oven to obtain the polyvinyl alcohol grafted zwitterionic copolymer.
The alpha-amino acid is one or more of alanine, leucine, isoleucine, proline, phenylalanine, glycine, tyrosine, tryptophan, serine, threonine, glutamic acid, lysine and methionine.
The organic phase monomer is polybasic acyl chloride.
The chemical structure of the polybasic acyl chloride is shown as the formula (I):
in the formula (I), R1、R2、R3Are respectively as
One or more of:
the preparation method of the polyacyl chloride comprises the following steps: placing 0.15-0.30mol of trichloromethyl carbonate and 0.15-0.30mol of 1,3,5 benzene compound containing hydroxyl or carboxyl in a four-necked bottle, adding 150ml of organic solvent, and stirring until the mixture is dissolved; dripping 1-5g of catalyst into the reaction system through a constant-pressure separating funnel, and reacting for 1-30h at the temperature of 0-20 ℃; after the reaction is finished, distilling the reactant to remove low boiling point substances; adding 50-100ml of DMF and 50-100ml of n-hexane into the obtained reactant for extraction to remove oligomers generated in the reaction and partial impurities which cannot be removed by distillation, and finally carrying out reduced pressure distillation and column chromatography purification to obtain the poly-acyl chloride; wherein the chemical structure of the 1,3,5 benzene compound containing hydroxyl or carboxyl is shown as (II):
in the formula (II), R4、R5、R6Are respectively as
One or more of (a).
The organic solvent is one or more of chlorobenzene, dichloromethane, chloroform, dichloroethane, Tetrahydrofuran (THF), n-hexane, ethyl acetate, ethylcyclohexane, petroleum ether, diethyl ether, ethanol, isopropanol, propylene oxide, acetone, methyl isobutyl ketone and the like; the catalyst is one or more of N, N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), triethylamine, methylamine, ethylamine, dimethylamine, diethylamine, 2-methylpyridine, 3-methylpyridine, pyridine, imidazole, sodium methoxide, potassium ethoxide, potassium tert-butoxide and butyl lithium.
A preparation method of a high-performance reverse osmosis composite membrane comprises the following steps:
(1) preparation of aqueous phase solution: dissolving a polyvinyl alcohol grafted zwitterionic polymer and m-phenylenediamine in pure water, adding triethylamine and camphorsulfonic acid as acid receiving agents, and adding sodium dodecyl sulfate to improve the wettability of an aqueous phase solution on a base membrane; in the finally obtained aqueous phase solution, the mass concentrations of the polyvinyl alcohol grafted zwitterionic polymer and the m-phenylenediamine are respectively 1-10% and 1-10%, the mass concentration of the triethylamine is 1-2%, the mass concentration of the camphorsulfonic acid is 2.5-7.5%, and the mass solubility of the sodium dodecyl sulfate is 0.1-0.2%;
(2) and (3) treating a porous support layer: soaking the porous support layer in 1% sodium hydroxide water solution for 30-90min, washing with ultrapure water, air drying, soaking in water phase solution, treating for 5-300s, taking out, removing water drops on the surface, soaking in organic phase solution, and treating for 5-300s to form polyamide desalting layer; taking out, placing in a drying oven at 60-140 deg.C, and heat treating for 1-60 min; preferably, the pore size of the surface of the porous support layer is 10-100 nm.
The organic solution is prepared by the following steps: dissolving polybasic acyl chloride in an organic solvent, wherein the mass concentration of the polybasic acyl chloride is 0.05-3%; the organic solvent is one or more of dichloromethane, n-hexane, n-heptane, n-octane, n-nonane, cyclohexane, ethyl acetate, ethylcyclohexane, naphtha, diethyl ether, ethanol, isopropanol, propylene oxide, acetone, and methyl isobutyl ketone.
Compared with the prior art, the invention has the following advantages:
1. the reverse osmosis composite membrane prepared by the invention has stable performance, and is obtained by detection tests, as shown in table 1:
TABLE 1
2. In the invention, the polyvinyl alcohol grafted zwitterionic copolymer adopts alpha-amino acid as a raw material, wherein the alpha-amino acid has the advantages of simple structure, low price, easy obtainment and the like, so that the membrane cost is lower.
3. In addition, in the invention, the polybasic acyl chloride is prepared by a triphosgene method, and a carbon chain or an ether bond is introduced between an acyl chloride group and a benzene ring, so that the polyamide desalting layer has stronger hydrophobicity, the polyamide desalting layer and the porous supporting layer are more tightly combined, the connection strength of the polyamide desalting layer and the porous supporting layer is improved, and the falling probability of the desalting layer is reduced.
Detailed Description
The technical solution of the present invention is further explained and illustrated below with reference to specific examples and experimental examples to facilitate the full understanding of the present invention for those skilled in the art, but the explanation and illustration are not further limitations of the technical solution of the present invention, and the technical solutions of the modifications of the present invention, which are made by simple numerical replacement and routine adjustment based on the technical solution of the present invention, are within the protection scope of the present invention.
Example 1
Preparation of polyvinyl alcohol graft zwitterionic copolymer: adding tryptophan accounting for 1% of the mass fraction into 100ml of 10% polyvinyl alcohol aqueous solution, adding 0.05mol of DCC (dicyclohexylcarbodiimide) serving as an oxidation-reduction catalyst under the protection of nitrogen, reacting for 1h at the temperature of 40 ℃, precipitating and washing a product by using methanol, and drying the obtained solid for 1h at the temperature of 60 ℃ in an oven to obtain the polyvinyl alcohol grafted zwitterionic copolymer.
Preparing polybasic acyl chloride: mixing 0.15mol of trichloromethyl carbonate and 0.15mol of trichloromethyl carbonate
Put into a four-necked flask, 150ml of ether is added and stirred until dissolved. 1g of sodium methoxide was added dropwise to the reaction system through a constant pressure separatory funnel, and the reaction was carried out at 0 ℃ for 1 hour. After the reaction is finished, distilling the reactant to remove low boiling point substances; adding 50ml of DMF and 50ml of n-hexane into the obtained reactant for extraction to remove oligomers generated in the reaction and partial impurities which cannot be removed by distillation, and finally carrying out reduced pressure distillation and column chromatography purification to obtain the polybasic acyl chloride.
Preparing an organic solution: dissolving polybasic acyl chloride in an organic solvent, wherein the mass concentration of the polybasic acyl chloride is 0.05%, and the organic solvent is cyclohexane.
The preparation method of the reverse osmosis composite membrane comprises the following steps:
(1) preparation of aqueous phase solution: dissolving a polyvinyl alcohol grafted zwitterionic polymer and m-phenylenediamine in pure water, adding triethylamine and camphorsulfonic acid as acid receiving agents, and adding sodium dodecyl sulfate to improve the wettability of an aqueous phase solution on a base membrane; in the finally obtained aqueous phase solution, the mass concentrations of the polyvinyl alcohol grafted zwitterionic polymer and the m-phenylenediamine are respectively 1 percent and 1 percent, the mass concentration of the triethylamine is 1 percent, the mass concentration of the camphorsulfonic acid is 2.5 percent, and the mass solubility of the sodium dodecyl sulfate is 0.1 percent;
(2) and (3) treating a porous support layer: soaking the porous support layer in 1% sodium hydroxide water solution for 30 times, washing with ultrapure water, air drying, soaking in water phase solution, treating for 5s, taking out, removing surface water drops, soaking in organic phase solution, and treating for 5s to form a polyamide desalting layer; taking out, placing in a 60 deg.C oven, and heat treating for 1min to obtain high performance reverse osmosis composite membrane.
The prepared reverse osmosis composite membrane is continuously filtered for 1h, 24h, 48h, 72h and 96h respectively under the operation pressure of 80psi by using a mixed aqueous solution of 2000ppm NaCl and 1000ppm bovine serum albumin as a test solution, the pH value is 7.3, and the performance of the reverse osmosis composite membrane is tested. After 1h of filtration, the water flux was 33.1 L.m-2·h-1The salt rejection rate is 99.3%; after 24h of filtration, the water flux was 32.6 L.m-2·h-1The salt rejection rate is 99.6%; after 48h of filtration, the water flux was 32.0 L.m-2·h-1The salt rejection rate is 99.6%; after 72 hours of filtration, the water flux was 31.2 L.m-2·h-1The salt rejection rate is 99.7%; after 96h of filtration, the water flux was 30.1 L.m-2·h-1The salt rejection was 99.7%.
Example 2
Preparation of polyvinyl alcohol graft zwitterionic copolymer: adding 20 mass percent of glutamic acid into 100ml of 10 percent polyvinyl alcohol aqueous solution, adding 0.05mol of DCC (dicyclohexylcarbodiimide) as an oxidation-reduction catalyst under the protection of nitrogen, reacting for 6h at the temperature of 40 ℃, precipitating and washing a product by using methanol, and drying the obtained solid for 12h at the temperature of 60 ℃ in an oven to obtain the polyvinyl alcohol grafted zwitterionic copolymer.
Preparing polybasic acyl chloride: mixing 0.23mol of trichloromethyl carbonate and 0.23mol of trichloromethyl carbonate
Put into a four-necked flask, 150ml of acetone is added and stirred until dissolved. 3g of diethylamine is dripped into the reaction system through a constant pressure separating funnel, and the reaction is carried out for 15h under the condition of 10 ℃. After the reaction is finished, distilling the reactant to remove low boiling point substances; 75ml of DMF and 75ml of n-hexane were added to the resultant reaction mixture to conduct extraction to remove oligomers formed in the reaction and to remove the oligomers which were not removed by distillationRemoving part of impurities, and finally performing reduced pressure distillation and column chromatography purification to obtain the polyacyl chloride.
Preparing an organic solution: dissolving polybasic acyl chloride in an organic solvent, wherein the mass concentration of the polybasic acyl chloride is 2%, and the organic solvent is naphtha.
The preparation method of the reverse osmosis composite membrane comprises the following steps:
(1) preparation of aqueous phase solution: dissolving a polyvinyl alcohol grafted zwitterionic polymer and m-phenylenediamine in pure water, adding triethylamine and camphorsulfonic acid as acid receiving agents, and adding sodium dodecyl sulfate to improve the wettability of an aqueous phase solution on a base membrane; in the finally obtained aqueous phase solution, the mass concentrations of the polyvinyl alcohol grafted zwitterionic polymer and the m-phenylenediamine are respectively 5 percent and 5 percent, the mass concentration of the triethylamine is 1.5 percent, the mass concentration of the camphorsulfonic acid is 5 percent, and the mass solubility of the sodium dodecyl sulfate is 0.15 percent;
(2) and (3) treating a porous support layer: soaking the porous support layer in 1% sodium hydroxide water solution for 60min, washing with ultrapure water, air drying, soaking in water phase solution, treating for 150s, taking out, removing surface water drops, soaking in organic phase solution, and treating for 150s to form a polyamide desalting layer; taking out, placing in a baking oven at 100 ℃, and carrying out heat treatment for 30min to obtain the high-performance reverse osmosis composite membrane.
The prepared reverse osmosis composite membrane is continuously filtered for 1h, 24h, 48h, 72h and 96h respectively under the operation pressure of 80psi by using a mixed aqueous solution of 2000ppm NaCl and 1000ppm bovine serum albumin as a test solution, the pH value is 7.5, and the performance of the reverse osmosis composite membrane is tested. After 1h of filtration, the water flux was 33.1 L.m-2·h-1The salt rejection rate is 99.3%; after 24h of filtration, the water flux was 33.0 L.m-2·h-1The salt rejection rate is 99.6%; after 48h of filtration, the water flux was 32.4 L.m-2·h-1The salt rejection rate is 99.7%; after 72 hours of filtration, the water flux was 31.5 L.m-2·h-1The salt rejection rate is 99.8%; after 96h of filtration, the water flux was 30.2 L.m-2·h-1The salt rejection was 99.8%.
Example 3
Preparation of polyvinyl alcohol graft zwitterionic copolymer: adding 24 mass percent of glycine and 16 mass percent of lysine into 100ml of 10 percent polyvinyl alcohol aqueous solution, adding 0.05mol of DCC (dicyclohexylcarbodiimide) as an oxidation-reduction catalyst under the protection of nitrogen, reacting for 12 hours at the temperature of 40 ℃, precipitating and washing a product by using methanol, and drying the obtained solid for 24 hours at the temperature of 60 ℃ in an oven to obtain the polyvinyl alcohol grafted zwitterionic copolymer.
Preparing polybasic acyl chloride: mixing 0.3mol of trichloromethyl carbonate and 0.3mol of trichloromethyl carbonate
Put into a four-necked flask, 50ml of isopropanol and 100ml of dichloroethane are added and stirred until dissolved. 5g of 3-methylpyridine is dropwise added into the reaction system through a constant-pressure separating funnel, and the reaction is carried out for 30 hours at the temperature of 20 ℃. After the reaction is finished, distilling the reactant to remove low boiling point substances; adding 100ml of DMF and 100ml of n-hexane into the obtained reactant for extraction to remove oligomers generated in the reaction and partial impurities which cannot be removed by distillation, and finally carrying out reduced pressure distillation and column chromatography purification to obtain the polybasic acyl chloride.
Preparing an organic solution: dissolving polybasic acyl chloride in an organic solvent, wherein the mass concentration of the polybasic acyl chloride is 3%, and the organic solvent comprises 20% of dichloromethane and 77% of propylene oxide.
The preparation method of the reverse osmosis composite membrane comprises the following steps:
(1) preparation of aqueous phase solution: dissolving a polyvinyl alcohol grafted zwitterionic polymer and m-phenylenediamine in pure water, adding triethylamine and camphorsulfonic acid as acid receiving agents, and adding sodium dodecyl sulfate to improve the wettability of an aqueous phase solution on a base membrane; in the finally obtained aqueous phase solution, the mass concentrations of the polyvinyl alcohol grafted zwitterionic polymer and the m-phenylenediamine are respectively 10 percent and 10 percent, the mass concentration of the triethylamine is 2 percent, the mass concentration of the camphorsulfonic acid is 7.5 percent, and the mass solubility of the sodium dodecyl sulfate is 0.2 percent;
(2) and (3) treating a porous support layer: soaking the porous support layer in 1% sodium hydroxide water solution for 90min, washing with ultrapure water, air drying, soaking in water phase solution, treating for 300s, taking out, removing surface water drops, soaking in organic phase solution, and treating for 300s to form polyamide desalting layer; taking out, placing in a drying oven at 140 ℃, and carrying out heat treatment for 60min to obtain the high-performance reverse osmosis composite membrane.
The prepared reverse osmosis composite membrane is continuously filtered for 1h, 24h, 48h, 72h and 96h respectively under the operation pressure of 80psi by using a mixed aqueous solution of 2000ppm NaCl and 1000ppm bovine serum albumin as a test solution, the pH value is 7.4, and the performance of the reverse osmosis composite membrane is tested. After 1h of filtration, the water flux was 33.0 L.m-2·h-1The salt rejection rate is 99.3%; after 24h of filtration, the water flux was 32.7 L.m-2·h-1The salt rejection rate is 99.5%; after 48h of filtration, the water flux was 32.0 L.m-2·h-1The salt rejection rate is 99.6%; after 72h of filtration, the water flux was 31.1 L.m-2·h-1The salt rejection rate is 99.7%; after 96h of filtration, the water flux was 29.8 L.m-2·h-1The salt rejection was 99.7%.
Test example: comparative experimental study
Test group a: a reverse osmosis composite membrane prepared according to the method disclosed in patent CN 102553460B.
Test group B: the reverse osmosis composite membrane prepared by the method of the invention.
The reverse osmosis composite membrane prepared in the test group was subjected to 10 filtration tests under conditions of a pH of 7.1 and an operating pressure of 80psi using a mixed aqueous solution of 2000ppm NaCl and 1000ppm bovine serum albumin as a test solution. The single filtration time is 48h, the water capacity and the salt rejection rate after the filtration time of each time are recorded, and the reverse osmosis composite membrane after each filtration is subjected to back flush regeneration, wherein the regeneration time is 1 h. The results are shown in Table 2.
TABLE 2
As can be seen from the above table, the reverse osmosis composite membranes of test group a began to have a tendency of a steep increase in water flow and a decrease in salt rejection rate in the 8 th to 10 th filtration tests, while the change of test group B was not very significant. From this, it can be judged that the structural joint strength of the reverse osmosis composite membranes of test group B is tighter.
Claims (6)
1. A high-performance reverse osmosis composite membrane consists of a non-woven fabric layer, a porous supporting layer and a polyamide desalting layer, wherein the porous supporting layer is a polysulfone ultrafiltration membrane layer on the surface of the non-woven fabric layer; the polyamide desalting layer is formed by placing a porous supporting layer in an aqueous phase solution containing an aqueous phase monomer and carrying out interfacial polymerization reaction in an organic phase monomer solution, and is characterized in that a polyvinyl alcohol grafted zwitterionic copolymer is doped in the aqueous phase solution; the water phase monomer is m-phenylenediamine; the organic phase monomer is polybasic acyl chloride;
the synthetic method of the polyvinyl alcohol grafted zwitterionic copolymer comprises the following steps: adding 1-40% by mass of zwitterionic monomer alpha-amino acid into 100ml of 10% polyvinyl alcohol aqueous solution, adding 0.05mol of dicyclohexylcarbodiimide serving as an oxidation-reduction catalyst under the protection of nitrogen, reacting for 1-12h at the temperature of 40 ℃, precipitating and washing a product by using methanol, and drying the obtained solid for 1-24h at the temperature of 60 ℃ in an oven to obtain the polyvinyl alcohol grafted zwitterionic copolymer.
2. The high performance composite reverse osmosis membrane of claim 1, wherein the α -amino acid is one or more of alanine, leucine, isoleucine, proline, phenylalanine, glycine, tyrosine, tryptophan, serine, threonine, glutamic acid, lysine, and methionine.
3. The high performance reverse osmosis composite membrane of claim 1, wherein the chemical structure of the poly-acyl chloride is represented by formula (I):
in the formula (I), R1, R2 and R3 are respectively-CH2-、
-O-、-CH2-O-、
One or more of:
4. the high performance reverse osmosis composite membrane according to claim 1 or 3, wherein the preparation method of the polyacyl chloride comprises: placing 0.15-0.30mol of trichloromethyl carbonate and 0.15-0.30mol of 1,3,5 benzene compound containing hydroxyl or carboxyl in a four-necked bottle, adding 150ml of organic solvent, and stirring until the mixture is dissolved; dripping 1-5g of catalyst into the reaction system through a constant-pressure separating funnel, and reacting for 1-30h at the temperature of 0-20 ℃; after the reaction is finished, distilling the reactant to remove low boiling point substances; adding 50-100ml of DMF and 50-100ml of n-hexane into the obtained reactant for extraction to remove oligomers generated in the reaction and partial impurities which cannot be removed by distillation, and finally carrying out reduced pressure distillation and column chromatography purification to obtain the poly-acyl chloride; wherein the chemical structure of the 1,3,5 benzene compound containing hydroxyl or carboxyl is shown as (II):
in the formula (II), R4, R5 and R6 are respectively-CH2COOH、
-OH、
-CH2OH、
One or more of (a).
5. The composite membrane of claim 4, wherein the organic solvent is one or more of chlorobenzene, dichloromethane, chloroform, dichloroethane, tetrahydrofuran, n-hexane, ethyl acetate, ethylcyclohexane, petroleum ether, diethyl ether, ethanol, isopropanol, propylene oxide, acetone, methyl isobutyl ketone, etc.; the catalyst is one or more of N, N-dimethylformamide, N-dimethylacetamide, triethylamine, methylamine, ethylamine, dimethylamine, diethylamine, 2-methylpyridine, 3-methylpyridine, pyridine, imidazole, sodium methoxide, potassium ethoxide, potassium tert-butoxide and butyl lithium.
6. A preparation method of a high-performance reverse osmosis composite membrane is characterized by comprising the following steps:
(1) preparation of aqueous phase solution: dissolving a polyvinyl alcohol grafted zwitterionic polymer and m-phenylenediamine in pure water, adding triethylamine and camphorsulfonic acid as acid receiving agents, and adding sodium dodecyl sulfate to improve the wettability of an aqueous phase solution on a base membrane; in the finally obtained aqueous phase solution, the mass concentrations of the polyvinyl alcohol grafted zwitterionic polymer and the m-phenylenediamine are respectively 1-10% and 1-10%, the mass concentration of the triethylamine is 1-2%, the mass concentration of the camphorsulfonic acid is 2.5-7.5%, and the mass solubility of the sodium dodecyl sulfate is 0.1-0.2%;
(2) and (3) treating a porous support layer: soaking the porous support layer in 1% sodium hydroxide water solution for 30-90min, washing with ultrapure water, air drying, soaking in water phase solution, treating for 5-300s, taking out, removing surface water drops, soaking in organic phase solution, treating for 5-300s, and forming polyamide desalting layer; taking out, placing in a drying oven at 60-140 deg.C, and heat treating for 1-60 min; the pore size of the surface of the porous support layer is 10-100 nm;
the organic phase solution is prepared by the following steps: dissolving polybasic acyl chloride in an organic solvent, wherein the mass concentration of the polybasic acyl chloride is 0.05-3%; the organic solvent is one or more of dichloromethane, n-hexane, n-heptane, n-octane, n-nonane, cyclohexane, ethyl acetate, ethylcyclohexane, naphtha, diethyl ether, ethanol, isopropanol, propylene oxide, acetone, and methyl isobutyl ketone.
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