CN114984782B - Anti-pollution polyamide reverse osmosis membrane with high flux and high desalination rate and preparation method thereof - Google Patents
Anti-pollution polyamide reverse osmosis membrane with high flux and high desalination rate and preparation method thereof Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 75
- 238000001223 reverse osmosis Methods 0.000 title claims abstract description 66
- 239000004952 Polyamide Substances 0.000 title claims abstract description 55
- 229920002647 polyamide Polymers 0.000 title claims abstract description 55
- 230000004907 flux Effects 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000010612 desalination reaction Methods 0.000 title claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 27
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 27
- 150000003839 salts Chemical class 0.000 claims abstract description 15
- 239000000243 solution Substances 0.000 claims description 57
- 239000012071 phase Substances 0.000 claims description 28
- 239000007864 aqueous solution Substances 0.000 claims description 19
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 18
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 10
- 239000008346 aqueous phase Substances 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 229920002492 poly(sulfone) Polymers 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 7
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 6
- 239000004760 aramid Substances 0.000 claims description 6
- 229920003235 aromatic polyamide Polymers 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical group ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 claims description 5
- 239000002798 polar solvent Substances 0.000 claims description 5
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 4
- 150000001266 acyl halides Chemical class 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- 238000007605 air drying Methods 0.000 claims description 3
- -1 alicyclic amine Chemical class 0.000 claims description 3
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 3
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 claims description 2
- 150000004982 aromatic amines Chemical class 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- SSJXIUAHEKJCMH-UHFFFAOYSA-N cyclohexane-1,2-diamine Chemical compound NC1CCCCC1N SSJXIUAHEKJCMH-UHFFFAOYSA-N 0.000 claims description 2
- GEQHKFFSPGPGLN-UHFFFAOYSA-N cyclohexane-1,3-diamine Chemical compound NC1CCCC(N)C1 GEQHKFFSPGPGLN-UHFFFAOYSA-N 0.000 claims description 2
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical group [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- GHAIYFTVRRTBNG-UHFFFAOYSA-N piperazin-1-ylmethanamine Chemical compound NCN1CCNCC1 GHAIYFTVRRTBNG-UHFFFAOYSA-N 0.000 claims description 2
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 8
- 239000002131 composite material Substances 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 230000007717 exclusion Effects 0.000 abstract description 2
- 230000002209 hydrophobic effect Effects 0.000 abstract description 2
- 229920002521 macromolecule Polymers 0.000 abstract description 2
- 230000007935 neutral effect Effects 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 16
- 210000004379 membrane Anatomy 0.000 description 15
- 238000012360 testing method Methods 0.000 description 14
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 239000012487 rinsing solution Substances 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- CNPVJWYWYZMPDS-UHFFFAOYSA-N 2-methyldecane Chemical group CCCCCCCCC(C)C CNPVJWYWYZMPDS-UHFFFAOYSA-N 0.000 description 2
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 2
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 210000002469 basement membrane Anatomy 0.000 description 2
- 229940098773 bovine serum albumin Drugs 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000009438 liyan Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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
- B01D71/56—Polyamides, e.g. polyester-amides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—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
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/30—Cross-linking
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/38—Graft polymerization
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/46—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/50—Control of the membrane preparation process
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention provides a preparation method of an anti-pollution polyamide reverse osmosis membrane with high flux and high salt rejection rate, which adopts double-end amino polyethylene glycol to react with carboxyl on the surface of a polyamide layer so as to improve the salt rejection rate of the composite polyamide reverse osmosis membrane, and meanwhile, the flux is not basically lost, and the polyethylene glycol is an electrically neutral water-soluble long-chain polymer, has flexible and flexible molecular chains, and can prevent hydrophobic substances and macromolecules from being adsorbed through the volume exclusion effect and the unique compatibility with water molecules so as to improve the anti-pollution performance of the composite polyamide reverse osmosis membrane.
Description
Technical Field
The invention belongs to the technical field of reverse osmosis membranes, and particularly relates to an anti-pollution polyamide reverse osmosis membrane with high flux and high desalination rate and a preparation method thereof.
Background
Reverse osmosis is an advanced and energy efficient separation technology today. The principle is to separate the solute from the solvent in solution by selective interception by means of a semi-permeable membrane that allows only water to permeate but not other substances, under the action of a pressure higher than the osmotic pressure of the solution. By utilizing the separation characteristic of the reverse osmosis membrane, impurities such as dissolved salt, colloid, organic matters, bacteria, microorganisms and the like in water can be effectively removed. Has the advantages of low energy consumption, no pollution, advanced process, simple and convenient operation and maintenance, and the like. The reverse osmosis membrane is the core of reverse osmosis technology, and the research and application of the reverse osmosis membrane are always the most popular research direction in the field of reverse osmosis technology.
Chinese patent CN 109847597A provides a method for preparing a high flux high desalination reverse osmosis membrane, which can increase the flux of the reverse osmosis membrane by adding one or a mixture of any of chloroform, dichloroethane, trichloroethane, chloroform, tetrahydrofuran and ethyl acetate in an oil phase reaction solution, on the premise of keeping the desalination rate of the reverse osmosis membrane unchanged, but it does not mention the improvement of the anti-pollution capability.
Xun et al (Xurong, liyan, guo fieng, etc.. PA/PEG cross-linked copolymerized reverse osmosis membrane preparation and fouling resistance [ J ] chemical engineering progress, 2021, 40 (12): 8.) polyethylene glycol (PEG) is introduced in the interface polymerization reaction process of trimesoyl chloride (TMC) and m-phenylenediamine (MPD) to prepare a Polyamide (PA)/PEG reverse osmosis composite membrane, so that the fouling resistance is greatly improved, but the method cannot simultaneously improve the flux and desalination rate of the reverse osmosis membrane.
Disclosure of Invention
In view of this, the present invention provides an anti-pollution polyamide reverse osmosis membrane with high flux and high salt rejection and a preparation method thereof, wherein the reverse osmosis membrane prepared by the method has greatly improved salt rejection and improved anti-pollution capability.
The invention provides a preparation method of an anti-pollution polyamide reverse osmosis membrane with high flux and high salt rejection rate, which comprises the following steps:
coating a water phase solution on the polysulfone supporting layer, then coating an oil phase solution, and drying to obtain the nascent state aromatic polyamide reverse osmosis membrane;
the aqueous phase solution comprises 0.5 to 5 percent of polyfunctional amine, 0.05 to 2 percent of surfactant, 3 to 10 percent of polar solvent and the balance of water; the multifunctional amine is selected from one or more of aromatic amine, aliphatic amine and alicyclic amine;
the pH value of the aqueous phase solution is 7 to 9; the pH value is preferably adjusted by using a sodium hydroxide solution.
The multifunctional amine is selected from one or more of m-phenylenediamine, ethylenediamine, propylenediamine, butylenediamine, hexylenediamine, N- (2-hydroxyethyl) ethylenediamine, 1, 2-diaminocyclohexane, 1, 3-diaminocyclohexane, 1, 4-diaminocyclohexane, diethylenetriamine, m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, pyromellitic triamine, piperazine and 4-aminomethylpiperazine;
the surfactant is selected from sodium dodecyl benzene sulfonate or sodium lauryl sulfate;
the polar solvent is selected from dimethyl sulfoxide and/or N-methyl pyrrolidone. The invention uses polar solvent with higher concentration to carry out interfacial polymerization reaction in water phase to form a nascent polyamide reverse osmosis membrane with higher flux;
the oil phase solution comprises 0.05 to 0.3 percent of polyfunctional acyl halide, and the balance is oil phase solvent; the oil phase solvent is selected from one or more of C4-C12 aliphatic hydrocarbon, cycloaliphatic hydrocarbon and aromatic hydrocarbon, and is preferably isoparaffin solvent oil; in a specific embodiment, the oil phase solvent is Isopar G.
After the polysulfone supporting layer is coated with the water phase solution, the redundant solution on the surface is removed, and then the polysulfone membrane absorbed with the water phase solution passes through a closed space with a heat supply and air exhaust system. In the invention, the aqueous phase solution is coated, then the aqueous phase solution is volatilized at the temperature of 20 to 30 ℃ and the relative humidity of 40 to 80 percent until the water content is 28 to 31 percent, and then the oil phase solution is coated.
After the oil phase solution is coated, the polyamide reverse osmosis membrane is dried in an oven at the temperature of 60-80 ℃, water on the surface of the membrane and a solvent of the oil phase solution volatilize in the drying process, and simultaneously unreacted monomers can further react, so that the desalination rate of the polyamide reverse osmosis membrane can be improved. The drying time is generally 1 to 3min, the drying is carried out until no oil printing exists on the surface of the film, and the temperature of the surface of the film is generally controlled to be 25 to 40 ℃.
Rinsing the nascent state aromatic polyamide reverse osmosis membrane, soaking in the grafted treatment solution, and air-drying to obtain the anti-pollution polyamide reverse osmosis membrane with high flux and high desalination rate.
In the present invention, the rinsing specifically includes:
and rinsing the nascent state aromatic polyamide reverse osmosis membrane by deionized water, an isopropanol aqueous solution, a citric acid aqueous solution, deionized water and a glycerol aqueous solution in sequence.
In the present invention, the mass concentration of the isopropyl alcohol (IPA) aqueous solution is 5 to 25%, preferably 10 to 20%; the invention adopts IPA solution with higher concentration to rinse and then remove residual reactant, and can further improve the flux of the nascent polyamide reverse osmosis membrane through the swelling action;
the concentration of the citric acid aqueous solution is 1 to 5 percent, preferably 1 to 2 percent;
the concentration of the aqueous glycerol solution is 0.5 to 10%, preferably 5 to 9%.
The invention adopts the treatment solution after grafting for soaking, and mainly aims to fully wash away unreacted residues and other impurities. In the invention, the post-grafting treatment fluid is of the molecular formula H 2 NCH 2 CH 2 （CH 2 CH 2 O） n CH 2 CH 2 NH 2 The molecular weight of the aqueous solution of amino-terminated polyethylene glycol is 400 to 5000; the mass fraction is 0.01 to 0.08 percent, and the mass fraction is preferably 0.01 to 0.05 percent. The molecular weight of the amino-terminated polyethylene glycol is 400 to 2000. In a specific embodiment, the amino-terminated polyethylene glycol is amino-terminated polyethylene glycol with a molecular weight of 400, amino-terminated polyethylene glycol with a molecular weight of 1000, amino-terminated polyethylene glycol with a molecular weight of 2000, or amino-terminated polyethylene glycol with a molecular weight of 400. According to the invention, the polyethylene glycol with double amino groups is used as a cross-linking agent to improve the cross-linking degree of the polyamide layer on the surface of the reverse osmosis membrane, so that the anti-pollution capability of the reverse osmosis membrane is further improved, and the anti-pollution polyamide reverse osmosis membrane with high flux and high desalination rate is obtained.
In the present invention, the polyfunctional acyl halide is trimesoyl chloride.
The present invention is preferably blow dried with dry air until the film surface is free of visible moisture.
The performance of the reverse osmosis membrane is tested by adopting the following test method:
and (3) filtering a 1500ppm sodium chloride aqueous solution at 1.03MPa, 25 ℃ and the membrane surface flow rate of 1.1GPM/min, flushing for 30min, and testing to obtain the initial flux and the desalination rate of the polyamide reverse osmosis membrane with high flux, high desalination rate and pollution resistance.
And under the same operation condition, the test aqueous solution is changed into a mixed solution of an electronegative lauryl sodium sulfate solution (50 g/L), electropositive lauryl trimethyl ammonium bromide (50 g/L) and electroneutral bovine serum albumin (100 g/L) for dissolving and washing for 30min, the flux of the anti-pollution polyamide reverse osmosis membrane with high flux and high desalination rate after pollution is obtained through testing, all test results are shown in table 2, pressure is relieved after pollution testing is finished, the polluted membrane is cleaned by using deionized water as a feeding solution, then 1500ppm of sodium chloride aqueous solution is filtered for 30min at 1.03MPa and 25 ℃ at the membrane surface flow rate of 1.1GPM/min, and the flux and the desalination rate of the polyamide reverse osmosis membrane with high flux and high desalination rate and anti-pollution after pollution treatment are obtained through testing.
The invention provides a preparation method of an anti-pollution polyamide reverse osmosis membrane with high flux and high salt rejection rate, which adopts double-end amino polyethylene glycol to react with carboxyl on the surface of a polyamide layer so as to improve the salt rejection rate of the composite polyamide reverse osmosis membrane, and meanwhile, the flux is not basically lost, and the polyethylene glycol is an electrically neutral water-soluble long-chain polymer, has flexible and flexible molecular chains, and can prevent hydrophobic substances and macromolecules from being adsorbed through the volume exclusion effect and the unique compatibility with water molecules so as to improve the anti-pollution performance of the composite polyamide reverse osmosis membrane.
Detailed Description
To further illustrate the present invention, the following examples are provided to describe in detail the anti-fouling polyamide reverse osmosis membrane with high flux and high salt rejection and the preparation method thereof, but they should not be construed as limiting the scope of the present invention.
Comparative example:
the production method of the anti-pollution polyamide reverse osmosis membrane with high flux and high desalination rate comprises the following steps:
1. preparing an aqueous phase liquid: 25g of m-phenylenediamine, 1g of sodium dodecyl sulfate and 80g of N-methylpyrrolidone are added and dissolved in 894g of water, the pH value is adjusted to 8.5-9 by adopting sodium hydroxide, and the mixture is uniformly stirred to obtain an aqueous phase solution.
2. Preparing an oil phase solution: 2.5G of trimesoyl chloride was dissolved in 997.5G of Isopar G, and stirred uniformly to obtain an oil phase solution.
3. Firstly, coating a water phase solution on a polysulfone support layer, removing the redundant solution on the surface, then leading the polysulfone basement membrane adsorbed with the water phase solution to pass through a closed space with a heat supply and air exhaust system, controlling the internal temperature to be 20-30 ℃ and the relative humidity to be 40-80%, and further volatilizing the water on the membrane surface. And then coating an oil phase solution on the surface of the polyamide reverse osmosis membrane, removing a part of the oil phase solution on the surface, and then drying in an oven at the temperature of 60-80 ℃ to form a polyamide ultrathin separation layer, thereby obtaining the nascent polyamide reverse osmosis membrane.
4. And (3) filtering a 1500ppm sodium chloride aqueous solution at 1.03MPa, 25 ℃ and the membrane surface flow rate of 1.1GPM/min, flushing for 30min, and testing to obtain the initial flux and the desalination rate of the polyamide reverse osmosis membrane with high flux, high desalination rate and pollution resistance, wherein all test results are shown in Table 1. And under the same operation condition, the test aqueous solution is changed into a mixed solution of an electronegative lauryl sodium sulfate solution (50 g/L), electropositive lauryl trimethyl ammonium bromide (50 g/L) and electroneutral bovine serum albumin (100 g/L) for dissolving and washing for 30min, the flux of the anti-pollution polyamide reverse osmosis membrane with high flux and high desalination rate after pollution is obtained through testing, all test results are shown in table 2, pressure is relieved after the pollution test is finished, the polluted membrane is cleaned by using deionized water as a feeding solution, then 1500ppm of sodium chloride aqueous solution is filtered for 30min at 1.03MPa and 25 ℃ at the membrane surface flow rate of 1.1GPM/min, the flux and the desalination rate of the polyamide reverse osmosis membrane after pollution treatment and cleaning are obtained through testing, and all test results are shown in table 2.
Example 1
The production method of the anti-pollution polyamide reverse osmosis membrane with high flux and high desalination rate comprises the following steps:
1. the same as the comparative example.
2. The same as the comparative example.
3. Preparation of rinsing liquid 1: 1200g IPA was dissolved in 8800g water to give rinse 1;
4. preparation of rinsing liquid 2: dissolving 200g of citric acid in 9800g of water to obtain a rinsing solution 2;
5. preparation of rinsing liquid 3: dissolving 800g of glycerol in 9200g of water to obtain a rinsing liquid 3;
6. preparation of a graft post-treatment solution: 1g of double-end amino polyethylene glycol with the molecular weight of 400 is dissolved in 9999g of water to obtain a grafted post-treatment solution;
7. firstly, coating a water phase solution on a polysulfone support layer, removing the redundant solution on the surface, then leading the polysulfone basement membrane adsorbed with the water phase solution to pass through a closed space with a heat supply and air exhaust system, controlling the internal temperature to be 20-30 ℃ and the relative humidity to be 40-80%, and further volatilizing the water on the membrane surface. And then coating an oil phase solution on the surface of the polyamide ultra-thin separation layer, removing a part of the oil phase solution on the surface of the polyamide ultra-thin separation layer, drying the polyamide ultra-thin separation layer in a drying oven at 60-80 ℃ to form a nascent polyamide reverse osmosis membrane, soaking and rinsing the nascent polyamide reverse osmosis membrane by using deionized water, a rinsing solution 1, a rinsing solution 2, deionized water and a rinsing solution 3 in sequence, soaking and rinsing the nascent polyamide reverse osmosis membrane, then soaking and grafting a post-treatment solution, and air-drying the solution to obtain the anti-pollution polyamide reverse osmosis membrane with high flux and high desalination rate.
8. The same as the comparative example.
Example 2:
the production method of the anti-pollution polyamide reverse osmosis membrane with high flux and high salt rejection rate comprises the following steps:
1. the same as the comparative example.
2. The same as the comparative example.
3. The same as example 1;
4. the same as example 1;
5. the same as example 1;
6. preparation of a grafting post-treatment solution: 1g of double-end amino polyethylene glycol with the molecular weight of 1000 is dissolved in 9999g of water to obtain a grafted post-treatment solution;
7. the same as in example 1.
8. The same as the comparative example.
Example 3:
the production method of the anti-pollution polyamide reverse osmosis membrane with high flux and high desalination rate comprises the following steps:
1. the same as the comparative example.
2. The same as the comparative example.
3. The same as example 1;
4. the same as example 1;
5. the same as example 1;
6. preparation of a graft post-treatment solution: 1g of double-end amino polyethylene glycol with molecular weight of 2000 is dissolved in 9999g of water to obtain a grafted post-treatment solution;
7. the same as in example 1.
8. The same as the comparative example.
Example 4:
the production method of the anti-pollution polyamide reverse osmosis membrane with high flux and high desalination rate comprises the following steps:
1. the same as the comparative example.
2. The same as the comparative example.
3. The same as example 1;
4. the same as example 1;
5. the same as example 1;
6. preparation of a graft post-treatment solution: selecting 3g of double-end amino polyethylene glycol with molecular weight of 400 to be dissolved in 9997g of water to obtain a grafted post-treatment solution;
7. the same as in example 1.
8. The same as the comparative example.
Example 5:
the production method of the anti-pollution polyamide reverse osmosis membrane with high flux and high desalination rate comprises the following steps:
1. the same as the comparative example.
2. The same as the comparative example.
3. The same as example 1;
4. the same as example 1;
5. the same as example 1;
6. preparation of a graft post-treatment solution: selecting 6g of double-end amino polyethylene glycol with molecular weight of 400 to be dissolved in 9994g of water to obtain a grafting post-treatment solution;
7. the same as in example 1.
8. The same as the comparative example.
TABLE 1 initial flux and salt rejection of polyamide composite reverse osmosis membranes
TABLE 2 flux of polyamide composite reverse osmosis membrane after fouling
Post-contamination flux decay rate = (1-post-contamination flux/initial flux) × 100%; post-wash flux recovery = (post-wash flux/initial flux) × 100%.
From the above examples, it can be seen that in the method provided by the present invention, the polyamide separation layer is formed and then subjected to a crosslinking reaction with the amino group-terminated polyethylene glycol, such that the degree of crosslinking of the polyamide separation layer can be increased, and the salt rejection of the polyamide reverse osmosis membrane can be increased. The experimental results show that: the method provided by the invention can improve the flux of the obtained polyamide reverse osmosis membrane by 12%; (2) the salt rejection is improved by 0.7-1.5%; and (3) the flux recovery rate of the membrane after pollution cleaning can reach 90-92%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (5)
1. A preparation method of an anti-pollution polyamide reverse osmosis membrane with high flux and high salt rejection rate comprises the following steps:
coating a water phase solution on a polysulfone support layer, volatilizing at 20-30 ℃ and relative humidity of 40-80% until the water mass content is 28-31%, coating an oil phase solution, and drying to obtain a nascent-state aromatic polyamide reverse osmosis membrane;
the aqueous phase solution comprises 0.5 to 5 percent of polyfunctional amine, 0.05 to 2 percent of surfactant, 3 to 10 percent of polar solvent and the balance of water; the multifunctional amine is selected from one or more of aromatic amine, aliphatic amine and alicyclic amine; the pH value of the aqueous phase solution is 7 to 9;
the oil phase solution comprises 0.05 to 0.3 percent of polyfunctional acyl halide, and the balance is oil phase solvent; the oil phase solvent is selected from one of C4-C12 aliphatic hydrocarbon, cycloaliphatic hydrocarbon and aromatic hydrocarbon;
rinsing the nascent state aromatic polyamide reverse osmosis membrane, soaking in the grafted treatment solution, and air-drying to obtain the anti-pollution polyamide reverse osmosis membrane with high flux and high desalination rate;
the grafting post-treatment solution has a molecular formula H 2 NCH 2 CH 2 （CH 2 CH 2 O） n CH 2 CH 2 NH 2 An aqueous solution of amino-terminated polyethylene glycol having a molecular weight of 400 to 2000; the mass fraction is 0.01 to 0.05 percent;
the rinsing specifically comprises:
rinsing the nascent state aromatic polyamide reverse osmosis membrane by deionized water, an isopropanol aqueous solution, a citric acid aqueous solution, deionized water and a glycerol aqueous solution in sequence;
the mass concentration of the isopropanol aqueous solution is 5 to 25 percent;
the concentration of the citric acid aqueous solution is 1 to 5 percent;
the concentration of the glycerol aqueous solution is 0.5 to 10 percent.
2. The method according to claim 1, wherein the polyfunctional amine is selected from one or more of m-phenylenediamine, ethylenediamine, propylenediamine, butylenediamine, hexylenediamine, N- (2-hydroxyethyl) ethylenediamine, 1, 2-diaminocyclohexane, 1, 3-diaminocyclohexane, 1, 4-diaminocyclohexane, diethylenetriamine, m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, sym-benzenetriamine, piperazine, and 4-aminomethylpiperazine;
the surfactant is selected from sodium dodecyl benzene sulfonate or sodium lauryl sulfate;
the polar solvent is selected from dimethyl sulfoxide and/or N-methyl pyrrolidone.
3. The method of claim 1, wherein the polyfunctional acyl halide is trimesoyl chloride.
4. The method according to claim 1, wherein the amino-terminated polyethylene glycol is specifically an amino-terminated polyethylene glycol having a molecular weight of 1000, an amino-terminated polyethylene glycol having a molecular weight of 2000, or an amino-terminated polyethylene glycol having a molecular weight of 400.
5. An anti-pollution polyamide reverse osmosis membrane with high flux and high salt rejection rate, which is prepared by the preparation method of any one of claims 1 to 4.
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| CN115738768A (en) * | 2022-12-19 | 2023-03-07 | 湖南沁森高科新材料有限公司 | Polyamide reverse osmosis membrane with high salt rejection rate and preparation method thereof |
| CN115869779A (en) * | 2023-03-02 | 2023-03-31 | 湖南沁森高科新材料有限公司 | Efficient bacteriostatic anti-pollution reverse osmosis membrane and preparation method thereof |
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| CN102824855A (en) * | 2011-06-17 | 2012-12-19 | 中国科学院大连化学物理研究所 | Surface modification method of polyamide reverse-osmosis composite membrane |
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