CN116272371A - Method for preparing reverse osmosis membrane with high boric acid rejection rate by utilizing ultraviolet light modification process - Google Patents
Method for preparing reverse osmosis membrane with high boric acid rejection rate by utilizing ultraviolet light modification process Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 131
- 238000001223 reverse osmosis Methods 0.000 title claims abstract description 80
- 238000000034 method Methods 0.000 title claims abstract description 68
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000004327 boric acid Substances 0.000 title claims abstract description 48
- 230000008569 process Effects 0.000 title claims abstract description 35
- 230000004048 modification Effects 0.000 title claims abstract description 20
- 238000012986 modification Methods 0.000 title claims abstract description 20
- 239000000243 solution Substances 0.000 claims abstract description 62
- 238000012695 Interfacial polymerization Methods 0.000 claims abstract description 25
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 claims abstract description 24
- PRAMZQXXPOLCIY-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethanesulfonic acid Chemical compound CC(=C)C(=O)OCCS(O)(=O)=O PRAMZQXXPOLCIY-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000002791 soaking Methods 0.000 claims abstract description 14
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 239000003999 initiator Substances 0.000 claims abstract description 7
- 239000000654 additive Substances 0.000 claims abstract description 6
- 230000000996 additive effect Effects 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 4
- 239000002954 polymerization reaction product Substances 0.000 claims abstract description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 30
- 239000012071 phase Substances 0.000 claims description 24
- 239000008346 aqueous phase Substances 0.000 claims description 21
- 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 12
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract description 50
- 230000014759 maintenance of location Effects 0.000 abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 26
- 239000011780 sodium chloride Substances 0.000 abstract description 25
- 230000004907 flux Effects 0.000 abstract description 15
- 238000002360 preparation method Methods 0.000 abstract description 6
- 238000000926 separation method Methods 0.000 description 26
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 20
- 239000004952 Polyamide Substances 0.000 description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 18
- 229920002647 polyamide Polymers 0.000 description 18
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 8
- JXRGUPLJCCDGKG-UHFFFAOYSA-N 4-nitrobenzenesulfonyl chloride Chemical compound [O-][N+](=O)C1=CC=C(S(Cl)(=O)=O)C=C1 JXRGUPLJCCDGKG-UHFFFAOYSA-N 0.000 description 8
- 229940018564 m-phenylenediamine Drugs 0.000 description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 6
- 229910052796 boron Inorganic materials 0.000 description 6
- MIOPJNTWMNEORI-UHFFFAOYSA-N camphorsulfonic acid Chemical compound C1CC2(CS(O)(=O)=O)C(=O)CC1C2(C)C MIOPJNTWMNEORI-UHFFFAOYSA-N 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 239000013535 sea water Substances 0.000 description 5
- 125000000542 sulfonic acid group Chemical group 0.000 description 5
- 238000010612 desalination reaction Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000008961 swelling Effects 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
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- 230000037048 polymerization activity Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- GYSCBCSGKXNZRH-UHFFFAOYSA-N 1-benzothiophene-2-carboxamide Chemical compound C1=CC=C2SC(C(=O)N)=CC2=C1 GYSCBCSGKXNZRH-UHFFFAOYSA-N 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N Decanoic acid Natural products CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000009878 intermolecular interaction Effects 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- 241000208818 Helianthus Species 0.000 description 1
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- 230000001276 controlling effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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Classifications
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- 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
- 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
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
-
- 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
-
- 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
- B01D2323/00—Details relating to membrane preparation
- B01D2323/34—Use of radiation
- B01D2323/345—UV-treatment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/108—Boron compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/08—Seawater, e.g. for desalination
-
- 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
Abstract
The invention relates to a method for preparing a reverse osmosis membrane with high boric acid rejection rate by an ultraviolet light modification process, which comprises the steps of immersing a support membraneWetting in an aqueous solution containing a 2-sulfoethyl methacrylate additive and an ultraviolet initiator; soaking the film in the oil phase solution for interfacial polymerization reaction, and placing the film under an ultraviolet lamp for irradiation in the process; rinsing the film surface with a solution containing n-hexyl methacrylate, and then applying ultraviolet light irradiation; and (3) placing the membrane in a temperature of 70-90 ℃ for heat treatment to prepare a reverse osmosis membrane containing 2-sulfoethyl methacrylate ultraviolet polymerization reaction products and n-hexyl methacrylate chemical grafting. H of reverse osmosis membrane prepared by the method 3 BO 3 The retention rate is improved from 83.82% to 92.47%, and the NaCl retention rate is improved from 98.89% to 99.19%. The preparation method is simple and efficient, is easy to implement, and can greatly improve the boric acid retention rate of the prepared membrane on the premise of ensuring the water flux.
Description
Technical Field
The invention relates to a method for preparing a reverse osmosis membrane with high boric acid rejection rate by utilizing an ultraviolet light modification process, which combines an ultraviolet reinforced interfacial polymerization process and an ultraviolet irradiation modification process, respectively optimizes the main body part and the surface area of a reverse osmosis membrane separation layer in a targeted manner, improves the boric acid rejection performance of the reverse osmosis membrane, and belongs to the field of preparation of composite reverse osmosis membranes.
Background
The reverse osmosis membrane technology has wide application in the fields of sea water desalination, wastewater/sewage treatment, food processing, drinking water purification and the like because of the characteristics of stability, high efficiency, mild operation conditions and easy integrated amplification. Among them, sea water desalination is the most common application field of reverse osmosis membrane technology. In general, brine cannot be directly used in human production and life, and brine which cannot be directly utilized is required to be changed into fresh water which can be directly utilized by means of proper desalination means. In recent years, a large number of researchers have been working on improving the water permeability coefficient and sodium chloride rejection of reverse osmosis membranes. In the membrane method sea water desalination technology taking a reverse osmosis membrane as a core, in order to ensure that the water quality of desalinated produced water meets the regulation of the upper limit of the boron element content in drinking water and the water quality requirement of partial crop irrigation water in China and other countries, the reverse osmosis membrane needs to remove more than about 90% of boron element in sea water. Therefore, the preparation of the reverse osmosis membrane with high salt rejection rate and high boric acid rejection rate has important significance. In seawater, the boron element is mainly boric acid (H) 3 BO 3 ) In the form of H, however 3 BO 3 The weak hydrolytic capacity and small molecular size are difficult for the common reverse osmosis membrane to realize H through electrostatic repulsive effect and steric hindrance effect 3 BO 3 This prevents further popularization and application of reverse osmosis membrane technology.
At present, common methods for improving the boric acid retention rate of a reverse osmosis membrane can be divided into two types. Firstly, strengthening the compactness of the reverse osmosis membrane, thereby enhancing the trans-membrane mass transfer resistance of boric acid molecules; and secondly, reasonably regulating and controlling the interaction between boric acid molecules and the reverse osmosis membrane. Both can promote the H of the reverse osmosis membrane to a certain extent 3 BO 3 The interception performance is realized, so that the combination of the two methods is expected to effectively improve the H of the reverse osmosis membrane 3 BO 3 Retention properties. Research has found that ideal high H 3 BO 3 The main body of the interception reverse osmosis membrane has a compact structure and also has H 3 BO 3 Has strong interaction to slow down H 3 BO 3 Speed of transfer within the film. At the same time ideal high H 3 BO 3 The interception reverse osmosis membrane has nonpolar or weak polar surface to reduce H containing polar group on membrane surface and raw material liquid 3 BO 3 Is prevented from H 3 BO 3 Enriching on the membrane surface. Li et al utilized a "swelling-intercalation-contraction" strategy to intercalate 4-nitrobenzenesulfonyl chloride (NBS) containing sulfonic acid groups into the Polyamide (PA) separation layer of a reverse osmosis membrane. Firstly pouring an ethanol solution dissolved with NBS on the surface of a reverse osmosis membrane, wherein the ethanol has stronger affinity to PA materials, so that the reverse osmosis membrane PA separation layer can be swelled, the size of a PA chain gap in the separation layer is increased, the ethanol is gradually volatilized after the NBS enters the swelled separation layer, PA chains shrink, and finally the NBS is fixed in the membrane separation layer. The embedding of NBS reduces the size of PA chain gaps within the membrane separation layer. In addition, sulfonic acid groups within the membrane are able to inhibit H through strong intermolecular interactions 3 BO 3 Fast diffusion within the membrane. Under the action of the two factors, after NBS is embedded into the PA separation layer of the reverse osmosis membrane, H of the reverse osmosis membrane 3 BO 3 The rejection rate was from 82.12% is improved to 93.10%, and NaCl rejection rate is improved from 99.20% to 99.57%. (Li y., wang s., song x., zhou y., shen h., cao x., zhang p., gao c., high boron removal polyamide reverse osmosis membranes by swelling induced embedding of a sulfonyl molecular plug, journal of Membrane Science J],2020,597:117716.). However, NBS having a rigid benzene ring structure tends to block the water transfer passage in the inner portion of the membrane, so that the water flux of the reverse osmosis membrane is from 33.8L.m -2 ·h -1 Down to 16.9 L.m -2 ·h -1 (the raw material liquid is 32000mg/L sodium chloride and 5mg/L boric acid in water, and the test pressure is 5.5 MPa). Li et al prepared a reverse osmosis membrane with high H by embedding a non-polar alkyl chain-containing decanoic acid molecule into the PA separation layer of the membrane using a strategy similar to "swelling-embedding-shrinking 3 BO 3 Reverse osmosis membranes of retention properties. After nonpolar sunflower acid molecules are embedded into the reverse osmosis membrane, the polarity of the membrane surface is obviously reduced, and the compactness of the separation layer is improved, so that the H of the reverse osmosis membrane is improved 3 BO 3 Rejection (Li Yunhao, li Aiai, yang, yu Junjie, wang Kaizhen, zhou Yong, high-grade , swelling of embedded fatty acid molecules to prepare high-boron-removal reverse osmosis membranes, chemical report [ J)],2020,71:1343-1351+1896). Under the optimal membrane making process condition, the H of the reverse osmosis membrane is prepared 3 BO 3 The retention rate is improved from 47.85% to 77.32%, and the NaCl retention rate is improved from 90.36% to 96.46%. However, the hydrophilicity of the membrane surface is reduced due to the intercalation of the nonpolar decanoic acid molecules. Therefore, the water flux of the reverse osmosis membrane is from-37.6L.m -2 ·h -1 Reduced to-28.0 L.m -2 ·h -1 (the raw material liquid is 2000mg/L sodium chloride and 5mg/L boric acid aqueous solution, and the test pressure is 1.55 MPa). It is noted that swelling of the reverse osmosis membrane PA separation layer may cause some PA material with a lower molecular weight to dissolve out of the membrane separation layer, which may cause irreparable damage to the membrane structure. In conclusion, on the premise of not damaging the water production flux of the reverse osmosis membrane, the method has great difficulty in improving the boric acid retention rate of the reverse osmosis membrane. However, the invention provides a combination of ultraviolet light reinforced interfacial polymerization process and ultraviolet grafting modification process for preparing high boric acid interception rate reverse osmosisThe method of the membrane can ensure the water production flux of the prepared membrane and simultaneously realize the great improvement of the boric acid interception rate.
Disclosure of Invention
The invention provides a method for preparing a reverse osmosis membrane with high boric acid rejection rate by utilizing an ultraviolet light modification process. The method can improve the compactness of the reverse osmosis membrane and simultaneously optimize the interaction between the membrane material and boric acid molecules. The method can ensure the water production flux of the prepared membrane and simultaneously improve the boric acid interception rate and the sodium chloride interception rate of the reverse osmosis membrane. The invention is realized by the following technical scheme as shown in figure 2:
the invention relates to a method for preparing a reverse osmosis membrane with high boric acid rejection rate by utilizing an ultraviolet light modification process, which comprises the following steps:
1) Immersing the support film in an aqueous solution containing a 2-sulfoethyl methacrylate additive and an ultraviolet initiator;
2) Soaking the film in the oil phase solution for interfacial polymerization reaction, and placing the film under an ultraviolet lamp for irradiation in the process;
3) Rinsing the film surface with a solution containing n-hexyl methacrylate, and then applying ultraviolet light irradiation;
4) And (3) placing the membrane in a temperature of 70-90 ℃ for heat treatment to prepare a reverse osmosis membrane containing 2-sulfoethyl methacrylate ultraviolet polymerization reaction products and n-hexyl methacrylate chemical grafting.
The mass fraction of the 2-sulfoethyl methacrylate in the aqueous phase solution in the step 1) is 0.1-1.5%.
The step 1) is to soak the membrane in the aqueous phase solution for 10 to 90 seconds.
The ultraviolet initiator in the step 1) is 2, 2-diethoxyacetophenone, and the mass fraction of the ultraviolet initiator is 0.02-0.5%.
The oil phase solution in the step 2) is an n-heptane solution containing trimesoyl chloride, and the mass fraction of the trimesoyl chloride is 0.15%.
And 2) soaking the membrane in the oil phase solution for 10-90 s to carry out interfacial polymerization reaction.
And 3) irradiating the ultraviolet light for 10-90 s.
The mass fraction of the n-hexyl methacrylate in the solution containing the n-hexyl methacrylate in the step 3) is 0.1-8.0%.
And 4) heat treatment is carried out for 3-10 min.
By adopting the technical scheme, the polysulfone ultrafiltration membrane is used as a substrate, and the reverse osmosis membrane is prepared by an interfacial polymerization process between an aqueous phase solution containing m-phenylenediamine and an n-heptane oil phase solution containing trimesoyl chloride. The aqueous phase solution used in the interfacial polymerization process comprises 2-sulfoethyl methacrylate, m-phenylenediamine, (±) -camphor-10-sulfonic acid, triethylamine, sodium dodecyl sulfate and 2, 2-diethoxyacetophenone; the oil phase solutions are all n-heptane solutions only containing trimesic acid chloride with the mass concentration of 0.15%. 2-Sulfoethyl Methacrylate (SMA) with ultraviolet light initiated polymerization activity is selected as a water phase additive, and in the ultraviolet light enhanced interfacial polymerization process, the SMA polymerization product is successfully enriched in the main body part of the PA separation layer by utilizing the characteristic that the SMA containing sulfonic acid groups is difficult to diffuse into the deep part of an interfacial polymerization reaction zone in an oil phase. The method improves the compactness of the separation layer main body and simultaneously utilizes the sulfonic acid group and H 3 BO 3 Stronger intermolecular interaction force and strengthens H in the separation layer main body part pair membrane 3 BO 3 Is slow down H 3 BO 3 The transfer rate within the membrane allows for optimization of the PA separation layer body portion.
After interfacial polymerization, n-Hexyl Methacrylate (HMA) having ultraviolet light initiated polymerization activity is added to n-hexane solvent rinsing reverse osmosis membrane surface, HMA containing nonpolar alkyl chain is grafted to the surface region of PA separation layer by ultraviolet grafting modification process. The method significantly weakens the polarity of the separation layer surface and inhibits H containing polar groups 3 BO 3 Enrichment on the membrane surface realizes optimization of the surface area of the PA separation layer.
By combining the above strategies, a reverse osmosis membrane with optimized main body and surface is prepared, and H of the reverse osmosis membrane prepared by the method 3 BO 3 The retention rate is improved from 83.82% to 92.47%, and the NaCl retention rate is improved from 98.89%Rise to 99.19%. (the raw material liquid was an aqueous solution containing 32000mg/L of sodium chloride and 5mg/L of boron, the operating pressure was 5.50MPa, and the test temperature was 25 ℃). The method for preparing the reverse osmosis membrane with high boric acid retention rate by utilizing the ultraviolet light modification process can improve the boric acid retention rate of the prepared membrane under the condition of not damaging the water yield and the sodium chloride retention rate of the reverse osmosis membrane. The invention has the advantages that: the method has the advantages of simple operation, time saving, high efficiency, mild modification conditions and difficult damage to the separation layer structure of the reverse osmosis membrane. In addition, the prepared reverse osmosis membrane with high boric acid rejection rate has the characteristics of high water yield and high sodium chloride rejection rate. The invention is not only suitable for preparing reverse osmosis membranes, but also suitable for developing other separation membranes prepared based on interfacial polymerization technology and grafting modification technology.
Description of the drawings:
FIG. 1 is a Scanning Electron Microscope (SEM) chart of the surface structure of the reverse osmosis membrane prepared in example 4.
FIG. 2 is a schematic diagram of the membrane process of the high boric acid rejection reverse osmosis membrane of the invention.
Detailed Description
The present invention will be described in further detail with reference to the following examples, wherein a reverse osmosis membrane is prepared by an interfacial polymerization process between an aqueous phase solution containing m-phenylenediamine and an n-heptane phase solution containing trimesoyl chloride using a polysulfone ultrafiltration membrane as a substrate. The aqueous phase solution used in the interfacial polymerization process comprises 2-sulfoethyl methacrylate, m-phenylenediamine, (±) -camphor-10-sulfonic acid, triethylamine, sodium dodecyl sulfate and 2, 2-diethoxyacetophenone; the oil phase solutions are all n-heptane solutions only containing trimesic acid chloride with the mass concentration of 0.15%. 2-Sulfoethyl Methacrylate (SMA) with ultraviolet light initiated polymerization activity is selected as a water phase additive, and in the ultraviolet light enhanced interfacial polymerization process, the SMA polymerization product is enriched in the main body part of the PA separation layer by utilizing the characteristic that the SMA containing sulfonic acid groups is difficult to diffuse into the deep part of an interfacial polymerization reaction zone in an oil phase; then, through an ultraviolet grafting modification process, HMA is chemically grafted to the surface of the reverse osmosis membrane separation layer, so that the polarity of the membrane surface is weakened, and the H-facing property of the membrane surface is reduced 3 BO 3 To achieve an optimization of the separation surface area; it is expected that the main body part and the surface area of the reverse osmosis membrane separation layer are respectively and purposefully optimized by combining the ultraviolet reinforced interfacial polymerization process and the ultraviolet irradiation modification process, so that the H of the reverse osmosis membrane is improved 3 BO 3 Retention properties.
Example 1
1) Preparing an aqueous phase solution containing 0.20% of 2-sulfoethyl methacrylate, 3.0% of m-phenylenediamine, 3.9% of (+/-) -camphor-10-sulfonic acid, 1.9% of triethylamine, 0.15% of sodium dodecyl sulfate and 0.02% of 2, 2-diethoxyacetophenone by mass fraction, soaking a support film in the aqueous phase solution for 10s, removing the aqueous phase solution, and drying;
2) Preparing an n-heptane oil phase solution containing trimesic chloride with the mass concentration of 0.15%, soaking the film obtained in the step 1) in the oil phase solution for 10s to perform interfacial polymerization reaction, and placing the film under an ultraviolet lamp for irradiation in the process;
3) Preparing an n-hexane solution containing 0.1% by mass of n-hexyl methacrylate, then rinsing the film surface with 0.1% by weight of n-hexane solution of n-hexyl methacrylate, and then applying ultraviolet light irradiation for 10 seconds;
4) And 3) placing the membrane obtained in the step 3) at 70 ℃ for heat treatment for 3min to obtain the composite reverse osmosis membrane with high boric acid retention rate.
Tested at 5.50MPa and 25 ℃ by using 5mg/L boric acid molecules and 32000mg/L sodium chloride aqueous solution, the produced water flux of the prepared reverse osmosis membrane is lower than 44.69L/(m) 2 H), the rejection rate of sodium chloride exceeds 98.89%, and the rejection rate of boric acid exceeds 83.82%.
Example 2
1) Preparing an aqueous phase solution containing 1.5% of 2-sulfoethyl methacrylate, 3.0% of m-phenylenediamine, 3.9% of (+/-) -camphor-10-sulfonic acid, 1.9% of triethylamine, 0.15% of sodium dodecyl sulfate and 0.5% of 2, 2-diethoxyacetophenone by mass fraction, soaking a support film in the aqueous phase solution for 90s, removing the aqueous phase solution, and drying;
2) Preparing an n-heptane oil phase solution containing trimesic chloride with the mass concentration of 0.15%, soaking the film obtained in the step 1) in the oil phase solution for 90s for interfacial polymerization reaction, and placing the film under an ultraviolet lamp for irradiation in the process;
3) Preparing an n-hexane solution containing 8% by mass of n-hexyl methacrylate, then rinsing the film surface by using 8% by weight of n-hexane solution of n-hexyl methacrylate, and then applying ultraviolet light irradiation for 90 seconds;
4) And (3) placing the membrane obtained in the step (3) at 90 ℃ for heat treatment for 10min to obtain the composite reverse osmosis membrane with high boric acid rejection rate.
Tested at 5.50MPa and 25 ℃ by using 5mg/L boric acid molecules and 32000mg/L sodium chloride aqueous solution, the produced water flux of the prepared reverse osmosis membrane is lower than 40.95L/(m) 2 H), the rejection rate of sodium chloride is lower than 99.19%, and the rejection rate of boric acid is lower than 92.47%.
Example 3
1) Preparing an aqueous phase solution containing 0.10% of 2-sulfoethyl methacrylate, 3.0% of m-phenylenediamine, 3.9% of (+/-) -camphor-10-sulfonic acid, 1.9% of triethylamine, 0.15% of sodium dodecyl sulfate and 0.04% of 2, 2-diethoxyacetophenone by mass fraction, soaking a support film in the aqueous phase solution for 60s, removing the aqueous phase solution, and drying;
2) Preparing an n-heptane oil phase solution containing trimesic chloride with the mass concentration of 0.15%, soaking the film obtained in the step 1) in the oil phase solution for 60s to perform interfacial polymerization reaction, and placing the film under an ultraviolet lamp for irradiation in the process;
3) Preparing an n-hexane solution containing 6% by mass of n-hexyl methacrylate, then rinsing the film surface by using the n-hexane solution containing 6% by weight of n-hexyl methacrylate, and then applying ultraviolet light irradiation for 60 seconds;
4) And 3) placing the membrane obtained in the step 3) at 80 ℃ for heat treatment for 5min to obtain the composite reverse osmosis membrane with high boric acid retention rate.
Tested at 5.50MPa and 25 ℃ by using 5mg/L boric acid molecules and 32000mg/L sodium chloride aqueous solution, the produced reverse osmosis membrane has a water flux exceeding 38.64L/(m) 2 H), the rejection rate of sodium chloride exceeds 98.89%, and the rejection rate of boric acid exceeds 83.82%.
Example 4
1) Preparing an aqueous solution containing 0.20% of 2-sulfoethyl methacrylate, 3.0% of m-phenylenediamine, 3.9% of (+ -) -camphor-10-sulfonic acid, 1.9% of triethylamine, 0.15% of sodium dodecyl sulfate and 0.02% of 2, 2-diethoxyacetophenone by mass fraction; soaking the support film in the aqueous phase solution for 60s, removing the aqueous phase solution, and drying;
2) Preparing an n-heptane oil phase solution containing trimesic chloride with the mass concentration of 0.15%, soaking the film obtained in the step 1) in the oil phase solution for 60s to perform interfacial polymerization reaction, and placing the film under an ultraviolet lamp for irradiation in the process;
3) Preparing an n-hexane solution containing 6% by mass of n-hexyl methacrylate, then rinsing the film surface by using the n-hexane solution containing 6% by weight of n-hexyl methacrylate, and then applying ultraviolet light irradiation for 60 seconds;
4) And 3) placing the membrane obtained in the step 3) at 80 ℃ for heat treatment for 5min to obtain the composite reverse osmosis membrane with high boric acid retention rate. An electron microscope image of the surface of the film is shown in fig. 1.
Tested at 5.50MPa and 25 ℃ by using a sodium chloride aqueous solution containing 5mg/L boric acid molecules and 32000mg/L to obtain the reverse osmosis membrane with the water yield, the sodium chloride retention rate and the boric acid retention rate of 40.95L/(m) 2 H), 99.19% and 92.47%.
Comparative example
Li et al (Li Y., wang S., song X., zhou Y., shen H., cao X., zhang P., gao C., high boron removal polyamide reverse osmosis membranes by swelling induced embedding of a sulfonyl molecular plug, journal of Membrane Science [ J ]]2020,597:117716.) and tested at 5.50MPa and 25 ℃ with an aqueous solution of sodium chloride containing 5mg/L boric acid molecules and 32000mg/L, the produced water flux, sodium chloride retention rate and boric acid retention rate of the produced reverse osmosis membrane are 16.90L/(m), respectively 2 H), 99.57% and 93.10%.
The method of the invention is adopted in examples 1 to 4, and the reverse osmosis membrane with optimized main body and surface is prepared, and on the premise of small-amplitude loss of water flux, the sodium chloride retention rate and the boric acid retention rate are both improved; wherein the optimum concentration of the additiveThe degree of concentration was 0.2% by weight, the optimum concentration of n-hexyl methacrylate in n-hexane solution was 6.0% by weight, and the water production flux, sodium chloride rejection and boric acid rejection of the reverse osmosis membrane prepared under the conditions were 40.95L/(m), respectively, as shown in example 4 2 H), 99.19% and 92.47%. Both have higher sodium chloride retention and boric acid retention than the comparative example, but experimental example 4 has more excellent water flux. In conclusion, the high boric acid entrapment rate composite reverse osmosis membrane prepared by combining the ultraviolet light reinforced interfacial polymerization process and the ultraviolet grafting modification process has more excellent water flux, sodium chloride entrapment rate and boric acid entrapment rate.
The invention relates to a method for preparing a reverse osmosis membrane with high boric acid rejection rate by an ultraviolet light modification process, which combines an ultraviolet reinforced interfacial polymerization process and an ultraviolet light external modification process, and respectively optimizes the main body part and the surface area of a reverse osmosis membrane separation layer in a targeted manner; preparing an aqueous phase solution containing a 2-sulfoethyl methacrylate additive and an ultraviolet initiator; soaking the support film in the aqueous phase solution to fully soak the support film; removing excessive aqueous phase solution on the membrane surface, soaking the membrane in the oil phase solution to perform interfacial polymerization reaction, and applying ultraviolet irradiation to the membrane surface; removing excessive oil phase solution on the membrane surface, rinsing the membrane surface by using solution containing n-hexyl methacrylate, and applying ultraviolet light irradiation to the membrane surface after rinsing. And drying the membrane to obtain the reverse osmosis membrane with high boric acid rejection rate. The preparation method is simple and efficient, is easy to implement, and can greatly improve the boric acid retention rate of the prepared membrane on the premise of ensuring the water flux.
The method for preparing the reverse osmosis membrane with high boric acid interception rate by utilizing the ultraviolet light modification technology disclosed and proposed by the invention can be realized by a person skilled in the art through the links of properly changing the condition route and the like by referring to the content of the specification, although the method and the preparation technology of the invention have been described by the preferred embodiment examples, the related person can obviously change or recombine the method and the technical route described herein to realize the final preparation technology without departing from the content, the spirit and the scope of the invention. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be included within the spirit, scope and content of the invention.
Claims (9)
1. The method for preparing the reverse osmosis membrane with high boric acid rejection rate by utilizing the ultraviolet light modification process is characterized by comprising the following steps of:
1) Immersing the support film in an aqueous solution containing a 2-sulfoethyl methacrylate additive and an ultraviolet initiator;
2) Soaking the film in the oil phase solution for interfacial polymerization reaction, and placing the film under an ultraviolet lamp for irradiation in the process;
3) Rinsing the film surface with a solution containing n-hexyl methacrylate, and then applying ultraviolet light irradiation;
4) And (3) placing the membrane in a temperature of 70-90 ℃ for heat treatment to prepare a reverse osmosis membrane containing 2-sulfoethyl methacrylate ultraviolet polymerization reaction products and n-hexyl methacrylate chemical grafting.
2. The method according to claim 1, wherein the mass fraction of 2-sulfoethyl methacrylate in the aqueous phase solution of step 1) is 0.1% to 1.5%.
3. The method of claim 1, wherein the step 1) is immersing the membrane in the aqueous solution for 10 to 90 seconds.
4. The method according to claim 1, wherein the ultraviolet initiator in the step 1) is 2, 2-diethoxyacetophenone, and the mass fraction thereof is 0.02% -0.5%.
5. The method according to claim 1, wherein the oil phase solution in the step 2) is an n-heptane solution containing trimesic acid chloride, and the mass fraction of trimesic acid chloride is 0.15%.
6. The method of claim 1, wherein the step 2) is performed by immersing the membrane in the oil phase solution for 10 to 90 seconds to perform interfacial polymerization.
7. The method of claim 1, wherein said step 3) is ultraviolet light irradiation for 10 to 90 seconds.
8. The method according to claim 1, wherein the mass fraction of n-hexyl methacrylate in the solution containing n-hexyl methacrylate in step 3) is 0.1% to 8.0%.
9. The method according to claim 1, wherein the step 4) is a heat treatment for 3 to 10 minutes.
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