CN102728247B - Preparation method of composite forward osmosis membrane - Google Patents
Preparation method of composite forward osmosis membrane Download PDFInfo
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- CN102728247B CN102728247B CN201210230602.7A CN201210230602A CN102728247B CN 102728247 B CN102728247 B CN 102728247B CN 201210230602 A CN201210230602 A CN 201210230602A CN 102728247 B CN102728247 B CN 102728247B
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- 239000012528 membrane Substances 0.000 title claims abstract description 42
- 238000009292 forward osmosis Methods 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000002131 composite material Substances 0.000 title abstract description 6
- 229920002492 poly(sulfone) Polymers 0.000 claims abstract description 56
- 229920000858 Cyclodextrin Polymers 0.000 claims abstract description 50
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000000243 solution Substances 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000005266 casting Methods 0.000 claims abstract description 22
- 239000007864 aqueous solution Substances 0.000 claims abstract description 20
- VLKZOEOYAKHREP-UHFFFAOYSA-N methyl pentane Natural products CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 239000000654 additive Substances 0.000 claims abstract description 7
- 230000000996 additive effect Effects 0.000 claims abstract description 7
- 230000001112 coagulating effect Effects 0.000 claims abstract description 5
- 238000000108 ultra-filtration Methods 0.000 claims description 19
- PIRBXSVZJGLDSD-UHFFFAOYSA-N CCCCCC.C(C1=CC=CC=C1)(=O)Cl Chemical compound CCCCCC.C(C1=CC=CC=C1)(=O)Cl PIRBXSVZJGLDSD-UHFFFAOYSA-N 0.000 claims description 18
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 claims description 18
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000012153 distilled water Substances 0.000 claims description 9
- 239000013557 residual solvent Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000000967 suction filtration Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- 229920001450 Alpha-Cyclodextrin Polymers 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- HFHDHCJBZVLPGP-RWMJIURBSA-N alpha-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO HFHDHCJBZVLPGP-RWMJIURBSA-N 0.000 claims description 6
- 229940043377 alpha-cyclodextrin Drugs 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- BCNBMSZKALBQEF-UHFFFAOYSA-N 1,3-dimethylpyrrolidin-2-one Chemical compound CC1CCN(C)C1=O BCNBMSZKALBQEF-UHFFFAOYSA-N 0.000 claims description 4
- GDSRMADSINPKSL-HSEONFRVSA-N gamma-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO GDSRMADSINPKSL-HSEONFRVSA-N 0.000 claims description 4
- 229940080345 gamma-cyclodextrin Drugs 0.000 claims description 4
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 230000004907 flux Effects 0.000 abstract description 11
- 230000010287 polarization Effects 0.000 abstract description 5
- 150000003839 salts Chemical class 0.000 abstract description 2
- 150000001263 acyl chlorides Chemical class 0.000 abstract 2
- 238000001914 filtration Methods 0.000 abstract 2
- 239000004745 nonwoven fabric Substances 0.000 abstract 1
- 238000007790 scraping Methods 0.000 abstract 1
- 239000003643 water by type Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 5
- 238000001764 infiltration Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
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- 238000012695 Interfacial polymerization Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 108010025880 Cyclomaltodextrin glucanotransferase Proteins 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- -1 cyclic oligosaccharide Chemical class 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
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- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229920001542 oligosaccharide Polymers 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920000052 poly(p-xylylene) Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
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Abstract
The invention relates to a preparation method of a composite forward osmosis membrane. At present, a phenomenon of inner concentration polarization exists in a forward osmosis process. The method disclosed by the invention comprises the following steps of: firstly, adding polysulfone and an additive into a solvent to be agitated and dissolved to obtain a polysulfone membrane casting solution which is uniformly dispersed; preparing a cyclodextrin aqueous solution with mass percent of 0.05-5% and a mellitic acyl chloride n-hexane solution; scraping the polysulfone membrane casting solution which is uniformly dispersed on non-woven fabric by using a scraper; immersing into de-ionized water of a coagulating bath to obtain a polysulfone ultra-filtering bottom membrane; and immersing the polysulfone ultra-filtering bottom membrane into the cyclodextrin aqueous solution and the mellitic acyl chloride n-hexane solution in sequence and curing to obtain the composite forward osmosis membrane. The method is simple in process; and the prepared composite forward osmosis membrane has the advantages of high mechanical strength, solvent resistance, relatively high water flux and high salt interception rate.
Description
Technical field
The invention belongs to the membrane separation technique field, be specifically related to a kind of preparation method of compound forward osmosis membrane.
Background technology
Positive infiltration technology (FO) is a kind of novel membrane separation technique of concentration drive that relies on that development in recent years is got up, and it is to using the permeable pressure head of permselectivity membrane both sides as the membrane process of driving force.Positive infiltration technology has broad application prospects, and can be used in sewage purification than counter-infiltration, and it has the following advantages: just permeating is a spontaneous process, does not need outside energy in separation process; Just permeating is non-pressure-driven system, does not almost have film to pollute; Only just permeating and need to overcome flow resistance, without any requirement to the material of membrane module; The rate of recovery of positive permeability and separation process water is high, and there is no the discharge of dense water, and environmental pollution is little.Therefore, with counter-infiltration, compare, just permeating and having obvious advantage, but adopt just permeating, still be faced with following problem: in FO technique, what still adopt is commercially available common RO (counter-infiltration) film at present.Experiment shows to adopt the RO film to carry out the research of FO technique, record the value of water flux well below expection, main cause is that the structure due to the RO film has caused concentration polarization very serious, therefore develop new forward osmosis membrane, the water flux, the minimizing concentration polarization tool that improve forward osmosis membrane are of great significance.
The commodity forward osmosis membrane only has U.S. Hydration Technology Inc. company by phase inversion production at present, Patents is WO2006110497A2, material selection cellulose acetate class, make to be subject in its application process the restriction of Treatment Solution pH condition, and its membrane flux is lower.But it has the chemical heat less stable, easily degraded, the shortcomings such as available PH narrow range.Another PBI forward osmosis membrane, expensive, be not suitable for large-scale industrial production.TFC-FO composite membrane chemical stability is good, and cost is lower, is a kind of proper forward osmosis membrane material.
Cyclodextrin (cyclodextrin, CD) is to act on by cyclodextrin glycosyltransferase one group of cyclic oligosaccharide that starch produces.Inner hydrophobic, outside hydrophilic is one of key character of cyclodextrin.Because its molecular structure is special, therefore can form the inclusion complex with multiple little molecule, most polymers all has good mechanical performance, is easy to machine-shaping.With chemical bonding or physical mixed method, cyclodextrin is introduced in polymer architecture, can be formed the superperformance that a class had both had polymer, again retaining ring dextrin design feature containing cyclodextrin.Therefore, cyclodextrin and derivative thereof have a wide range of applications at multiple fields such as Chemical Decomposition, chemical analysis, medicine, food, agricultural chemicals.At present, Chinese scholars concentrates on the aspect such as inclusion function, complex functionality new material of cyclodextrin molecular to the research great majority of cyclodextrin.In recent years, cyclodextrin is incorporated in polymeric membrane, utilizes the proterties such as cavity of cyclodextrin to come the reinforced film separating property to become a new study hotspot.Therefore, this paper is intended to prepare a kind ofly take polysulfones as counterdie, adopts the novel forward osmosis membrane that cyclodextrin is the interfacial polymerization material.
Summary of the invention
The objective of the invention is for solve positive process of osmosis exist in the concentration polarization phenomenon, a kind of preparation method of compound forward osmosis membrane is provided, there is preparation technology simple, high mechanical properties, solvent resistance improve simultaneously water flux and rejection etc. characteristics.
The concrete steps of the inventive method are:
Step (1). polysulfones and additive are added to stirring and dissolving in solvent, and whipping temp is 40～120 ℃, and mixing time is 12～48 hours; Then suction filtration 1～2 hour under vacuum, obtain finely dispersed polysulfones casting solution; In the polysulfones casting solution, the mass content of each material is: polysulfones 8～30 ﹪, solvent 50～80 ﹪, additive 2～20 ﹪;
Described solvent is one or more the mixture in dimethyl formamide, dimethylacetylamide, dimethyl sulfoxide (DMSO), hexamethyl phosphoramide, dimethyl pyrrolidone;
Described additive is a kind of in polyethylene glycol, polyvinylpyrrolidone, lithium chloride, zinc chloride, methyl alcohol, ethanol;
Step (2). cyclodextrin is dissolved in distilled water, is mixed with the cyclodextrin aqueous solution that the cyclodextrin mass percent is 0.05～5 ﹪; Equal benzoyl chloride is dissolved in n-hexane, and being mixed with equal benzoyl chloride mass percent is the equal benzoyl chloride hexane solution of 0.05～5 ﹪;
Described cyclodextrin is one or more in alpha-cyclodextrin, beta-schardinger dextrin-, gamma-cyclodextrin;
Step (3). with scraper, finely dispersed polysulfones casting solution is scraped on nonwoven, then immersed in the coagulating bath deionized water, after film forming, by deionized water, remove residual solvent, obtain polysulfones ultrafiltration counterdie;
The temperature of described coagulating bath deionized water is 5～30 ℃; Described blade thickness is 10～180 μ m;
Step (4). polysulfones ultrafiltration counterdie is immersed in cyclodextrin aqueous solution to 1～8 minute, is immersed in again equal benzoyl chloride hexane solution 0.5～5 minute after taking-up; Then solidify 2～15 minutes under 60～150 ℃, obtain compound forward osmosis membrane.
The inventive method is usingd polysulphone super-filter membrane as supporting counterdie, and (this ultrafiltration counterdie pure water flux can reach 120-250L/m to improve water flux
2the h0.1 MPa), for forward osmosis membrane preparation provides can a new way.
The inventive method adopts novel interfacial polymerization material cyclodextrin, is conducive to reduce the interior concentration polarization problem existed in positive process of osmosis, improves the water flux just permeated.Cyclodextrin has hydrophily preferably, resistance tocrocking as a kind of Green Polymer.The prepared forward osmosis membrane of the method has very high mechanical properties, solvent resistance, higher water flux and high salt rejection, opened up a new way for preparing forward osmosis membrane, can be for sewage disposal, desalinization, food processing, the fields such as medicine and textile industry.
The specific embodiment
Embodiment 1.
Step (1). 3Kg polysulfones and 2Kg polyethylene glycol are added in the 5Kg dimethyl formamide and stir 48 hours under 40 ℃, and under vacuum, suction filtration is 1 hour, obtains finely dispersed polysulfones casting solution
Step (2). alpha-cyclodextrin is dissolved in distilled water, is mixed with the cyclodextrin aqueous solution that the cyclodextrin mass percent is 0.05 ﹪; Equal benzoyl chloride is dissolved in n-hexane, and being mixed with equal benzoyl chloride mass percent is the equal benzoyl chloride hexane solution of 0.05 ﹪;
Step (3). the scraper that is 10 μ m with thickness is scraped finely dispersed polysulfones casting solution on nonwoven, then immerses in 5 ℃ of deionized waters, after film forming, by deionized water, removes residual solvent, obtains polysulfones ultrafiltration counterdie;
Step (4). polysulfones ultrafiltration counterdie is immersed in cyclodextrin aqueous solution to 1 minute, is immersed in again equal benzoyl chloride hexane solution 1 minute after taking-up; Then solidify 15 minutes under 60 ℃, obtain compound forward osmosis membrane.Embodiment 2.
Step (1). 1.8Kg polysulfones and 0.2Kg polyvinylpyrrolidone are added in the 8Kg dimethylacetylamide and stir 12 hours under 120 ℃, and under vacuum, suction filtration is 2 hours, obtains finely dispersed polysulfones casting solution
Step (2). beta-schardinger dextrin-is dissolved in distilled water, is mixed with the cyclodextrin aqueous solution that the cyclodextrin mass percent is 0.1 ﹪; Equal benzoyl chloride is dissolved in n-hexane, and being mixed with equal benzoyl chloride mass percent is the equal benzoyl chloride hexane solution of 0.1 ﹪;
Step (3). the scraper that is 20 μ m with thickness is scraped finely dispersed polysulfones casting solution on nonwoven, then immerses in 10 ℃ of deionized waters, after film forming, by deionized water, removes residual solvent, obtains polysulfones ultrafiltration counterdie;
Step (4). polysulfones ultrafiltration counterdie is immersed in cyclodextrin aqueous solution to 2 minutes, is immersed in again equal benzoyl chloride hexane solution 0.5 minute after taking-up; Then solidify 5 minutes under 120 ℃, obtain compound forward osmosis membrane.
Embodiment 3.
Step (1). 0.8Kg polysulfones and 1.2Kg lithium chloride are added in the 8Kg dimethyl sulfoxide (DMSO) and stir 24 hours under 80 ℃, and under vacuum, suction filtration is 1.5 hours, obtains finely dispersed polysulfones casting solution
Step (2). gamma-cyclodextrin is dissolved in distilled water, is mixed with the cyclodextrin aqueous solution that the cyclodextrin mass percent is 1 ﹪; Equal benzoyl chloride is dissolved in n-hexane, and being mixed with equal benzoyl chloride mass percent is the equal benzoyl chloride hexane solution of 1 ﹪;
Step (3). the scraper that is 100 μ m with thickness is scraped finely dispersed polysulfones casting solution on nonwoven, then immerses in 20 ℃ of deionized waters, after film forming, by deionized water, removes residual solvent, obtains polysulfones ultrafiltration counterdie;
Step (4). polysulfones ultrafiltration counterdie is immersed in cyclodextrin aqueous solution to 5 minutes, is immersed in again equal benzoyl chloride hexane solution 3 minutes after taking-up; Then solidify 10 minutes under 100 ℃, obtain compound forward osmosis membrane.Embodiment 4.
Step (1). 2Kg polysulfones and 2Kg zinc chloride are added in the mixed solvent of 3Kg dimethyl sulfoxide (DMSO) and 3Kg dimethyl pyrrolidone and stir 30 hours under 60 ℃, under vacuum, suction filtration is 1 hour, obtains finely dispersed polysulfones casting solution
Step (2). beta-schardinger dextrin-is dissolved in distilled water, is mixed with the cyclodextrin aqueous solution that the cyclodextrin mass percent is 0.3 ﹪; Equal benzoyl chloride is dissolved in n-hexane, and being mixed with equal benzoyl chloride mass percent is the equal benzoyl chloride hexane solution of 0.3 ﹪;
Step (3). the scraper that is 150 μ m with thickness is scraped finely dispersed polysulfones casting solution on nonwoven, then immerses in 25 ℃ of deionized waters, after film forming, by deionized water, removes residual solvent, obtains polysulfones ultrafiltration counterdie;
Step (4). polysulfones ultrafiltration counterdie is immersed in cyclodextrin aqueous solution to 6 minutes, is immersed in again equal benzoyl chloride hexane solution 2 minutes after taking-up; Then solidify 2 minutes under 150 ℃, obtain compound forward osmosis membrane.Embodiment 5.
Step (1). 2.5Kg polysulfones and 0.5Kg methyl alcohol are added in the 7Kg hexamethyl phosphoramide and stirs 45 hours under 50 ℃, and under vacuum, suction filtration is 1.5 hours, obtains finely dispersed polysulfones casting solution
Step (2). the alpha-cyclodextrin that is 1:1:1 by mass ratio, beta-schardinger dextrin-and gamma-cyclodextrin are dissolved in distilled water, are mixed with the cyclodextrin aqueous solution that the cyclodextrin mass percent is 5 ﹪; Equal benzoyl chloride is dissolved in n-hexane, and being mixed with equal benzoyl chloride mass percent is the equal benzoyl chloride hexane solution of 2 ﹪;
Step (3). the scraper that is 50 μ m with thickness is scraped finely dispersed polysulfones casting solution on nonwoven, then immerses in 15 ℃ of deionized waters, after film forming, by deionized water, removes residual solvent, obtains polysulfones ultrafiltration counterdie;
Step (4). polysulfones ultrafiltration counterdie is immersed in cyclodextrin aqueous solution to 8 minutes, is immersed in again equal benzoyl chloride hexane solution 5 minutes after taking-up; Then solidify 12 minutes under 80 ℃, obtain compound forward osmosis membrane.Embodiment 6.
Step (1). 1.5Kg polysulfones and 1Kg ethanol are added in the 7.5Kg dimethyl pyrrolidone and stirs 15 hours under 100 ℃, and under vacuum, suction filtration is 1 hour, obtains finely dispersed polysulfones casting solution
Step (2). the alpha-cyclodextrin that is 1:1 by mass ratio and beta-schardinger dextrin-are dissolved in distilled water, are mixed with the cyclodextrin aqueous solution that the cyclodextrin mass percent is 2 ﹪; Equal benzoyl chloride is dissolved in n-hexane, and being mixed with equal benzoyl chloride mass percent is the equal benzoyl chloride hexane solution of 5 ﹪;
Step (3). the scraper that is 180 μ m with thickness is scraped finely dispersed polysulfones casting solution on nonwoven, then immerses in 30 ℃ of deionized waters, after film forming, by deionized water, removes residual solvent, obtains polysulfones ultrafiltration counterdie;
Step (4). polysulfones ultrafiltration counterdie is immersed in cyclodextrin aqueous solution to 7 minutes, is immersed in again equal benzoyl chloride hexane solution 4 minutes after taking-up; Then solidify 8 minutes under 110 ℃, obtain compound forward osmosis membrane.Embodiment 7.
Step (1). 1Kg polysulfones and 1Kg zinc chloride are added in the mixed solvent of 4Kg dimethyl formamide and 4Kg dimethylacetylamide and stir 18 hours under 90 ℃, under vacuum, suction filtration is 1.5 hours, obtains finely dispersed polysulfones casting solution
Step (2). alpha-cyclodextrin is dissolved in distilled water, is mixed with the cyclodextrin aqueous solution that the cyclodextrin mass percent is 0.5 ﹪; Equal benzoyl chloride is dissolved in n-hexane, and being mixed with equal benzoyl chloride mass percent is the equal benzoyl chloride hexane solution of 0.5 ﹪;
Step (3). the scraper that is 50 μ m with thickness is scraped finely dispersed polysulfones casting solution on nonwoven, then immerses in 20 ℃ of deionized waters, after film forming, by deionized water, removes residual solvent, obtains polysulfones ultrafiltration counterdie;
Step (4). polysulfones ultrafiltration counterdie is immersed in cyclodextrin aqueous solution to 3 minutes, is immersed in again equal benzoyl chloride hexane solution 2 minutes after taking-up; Then solidify 10 minutes under 90 ℃, obtain compound forward osmosis membrane.
The water flux test result of the composite membrane that above each embodiment makes is as shown in table 1:
| ? | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 |
| Water flux (L/m 2h） | 24.9 | 28.7 | 35.8 | 30.8 | 31.2 | 29.8 | 32.7 |
Claims (3)
1. the preparation method of a compound forward osmosis membrane is characterized in that the concrete steps of the method are:
Step (1). polysulfones and additive are added to stirring and dissolving in solvent, and whipping temp is 40～120 ℃, and mixing time is 12～48 hours; Then suction filtration 1～2 hour under vacuum, obtain finely dispersed polysulfones casting solution; In the polysulfones casting solution, the mass content of each material is: polysulfones 8～30 ﹪, solvent 50～80 ﹪, additive 2～20 ﹪;
Described solvent is one or more the mixture in dimethyl formamide, dimethylacetylamide, dimethyl sulfoxide (DMSO), hexamethyl phosphoramide, dimethyl pyrrolidone;
Described additive is a kind of in polyethylene glycol, polyvinylpyrrolidone, lithium chloride, zinc chloride, methyl alcohol, ethanol;
Step (2). cyclodextrin is dissolved in distilled water, is mixed with the cyclodextrin aqueous solution that the cyclodextrin mass percent is 0.05～5 ﹪; Equal benzoyl chloride is dissolved in n-hexane, and being mixed with equal benzoyl chloride mass percent is the equal benzoyl chloride hexane solution of 0.05～5 ﹪;
Step (3). with scraper, finely dispersed polysulfones casting solution is scraped on nonwoven, then immersed in the coagulating bath deionized water, after film forming, by deionized water, remove residual solvent, obtain polysulfones ultrafiltration counterdie;
Step (4). polysulfones ultrafiltration counterdie is immersed in cyclodextrin aqueous solution to 1～8 minute, is immersed in again equal benzoyl chloride hexane solution 0.5～5 minute after taking-up; Then solidify 2～15 minutes under 60～150 ℃, obtain compound forward osmosis membrane.
2. the preparation method of a kind of compound forward osmosis membrane as claimed in claim 1, it is characterized in that: the cyclodextrin described in step (2) is one or more in alpha-cyclodextrin, beta-schardinger dextrin-, gamma-cyclodextrin.
3. the preparation method of a kind of compound forward osmosis membrane as claimed in claim 1, it is characterized in that: the temperature of the coagulating bath deionized water described in step (3) is 5～30 ℃; Described blade thickness is 10-180 μ m.
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| CN102921307B (en) * | 2012-11-13 | 2014-10-08 | 哈尔滨工业大学 | Preparation method of high-performance forward osmosis membrane |
| CN103432913B (en) * | 2013-08-05 | 2015-08-19 | 株洲时代新材料科技股份有限公司 | High temperature resistant pair of positive osmosis composite membrane of cortex and preparation method thereof |
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| CN112535957B (en) * | 2020-11-10 | 2021-12-07 | 同济大学 | Composite membrane with intermediate layer for forward osmosis of organic solvent and preparation method and application thereof |
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| JP4539341B2 (en) * | 2005-01-18 | 2010-09-08 | 東レ株式会社 | Composite reverse osmosis membrane and method for producing the same |
| CN101837250B (en) * | 2010-06-22 | 2012-05-23 | 苏州汇龙膜技术发展有限公司 | Modified polrvinyl chloride hollow fiber ultrafiltration membrane, preparation method and application thereof |
| CN102160969B (en) * | 2011-02-25 | 2013-07-10 | 中国科学院宁波材料技术与工程研究所 | Method for preparing fluorocarbon polymer microporous film with interpenetrating network bicontinuous pore structure |
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