CN1569317A - Solvent modifying method for polyamide composite film - Google Patents
Solvent modifying method for polyamide composite film Download PDFInfo
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- CN1569317A CN1569317A CN 03141702 CN03141702A CN1569317A CN 1569317 A CN1569317 A CN 1569317A CN 03141702 CN03141702 CN 03141702 CN 03141702 A CN03141702 A CN 03141702A CN 1569317 A CN1569317 A CN 1569317A
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- polyamide
- composite film
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- modifier
- acid
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Abstract
The invention is a solvent modification method for film. The polyamide compound film is immersed in the polyamide solvent, bleached in deioned water, dried in room temperature, and the modified polyamide penetration vaporous compound film can be acquired. The pressure of the modified film to water compound containing 87wt% of isopropyl alcohol under 25deg.C is less than 1000 Pa, the water flux is 174g/m2h-405g/m2h, the separation factor is 174-276, the percent swell rate to water and isopropyl alcohol are 31.7-40.89 and 10.24-15.73, after modified, the water flux is decreased about 51%, the upgrading rate of separation factor reaches to 144%, the percent swell rate to water is upgraded about 10%-42%, the percent swell rate to is decreased to 4%-39%. The invention is simple.
Description
Technical field
The invention belongs to the solvent modified processing of polyamide composite film, the polyamide reverse osmosis composite film of using in particular for the water treatment desalination is treated as the method for the infiltrating and vaporizing membrane of the separation of organic substances aqueous solution by solvent.
Background technology
Polyamide is a kind of diffusion barrier manufactured materials of function admirable.By compound filming technology, polyamide has been formed into the reverse osmosis membrane that the water treatment desalination is used, polyamide reverse osmosis composite film manufacturing technology maturation, and it is a lot of to found the factory all over the world, and product yield increases year by year, and application market is wide.But,, finding is not arranged more on the market because of its production technology more complicated for polyamide infiltration vaporization film.
Chinese invention patent (application number: 98120000.1 modifying reverse osmosis composite membrane by inner interface adsorption of surfactant method and 98125653.8 reverse osmosis composite membrane by inner interface alcohol-water system modifying process) disclose respectively inner boundary to composite membrane be the PS membrane surface of porous supporting body with surfactant or carry out modification with alcohol-water system solution and handle, improve the counter-infiltration performance methodology of polyamide composite film; " Journal of Membrane Science " (139 phases: 175-181,1998) have reported people such as S.Belfer at commodity polyamide reverse osmosis composite film surface emissivity grafting methacrylic acid monomer, improve the counter-infiltration mass-transfer performance of Modified Membrane." Journal of Membrane Science " (114 phases: 39-50,1996) report people such as Ashish Kulkarni and utilize hydrophilic reagents such as hydrofluoric acid to make polyamide generation hydrolysis, the PA membrane of modification produces carboxyl and the amino hydrophilic radical that exists with ionic species, improves the water flux and the salt rejection rate of reverse osmosis composite membrane.Described document only relates to the raising of the counter-infiltration performance of polyamide composite film, does not all relate to the function problem that the polyamide reverse osmosis composite film modification is become infiltration vaporization separation film.
The inventor is once in " water technology " (27 phases: 314-317, calendar year 2001) and the method for having reported respectively with the aqueous acetone solution immersion treatment on " Desalination " (151:117-121,2002) the Cellulose Triacetate Membranes For Reverse Osmosis modification is become infiltrating and vaporizing membrane.Before this, be processed into infiltrating and vaporizing membrane for polyamide reverse osmose membrane with solvent, do not see the document record as yet, the inventor has made further exploration to it for this reason.
Summary of the invention
The invention provides a kind of by the commodity polyamide composite film by its separatory aramid layer is processed into the method for modifying of infiltrating and vaporizing membrane through solvent.
The principle of the inventive method is based on interpenetrating effect between small solvent molecule in the modifier and the big molecule of membrane material.Polyamide composite film adopts the commodity finished product, comprise aromatic polyamide film and fatty polyamide film, modifier adopts the good solvent of polyamide, be phosphoric acid, the hydrochloric acid in the inorganic acid, formic acid in the organic acid, acetate, the phenol in the phenolic compounds is by regulating the solvent strength and the modification processing time of modifier, in the control reverse osmosis membrane the big molecule of polyamide and small solvent molecule interpenetrate motion, make the structural change of diffusion barrier and obtain the modification of film.
The solvent modified method of polyamide composite film of the present invention is characterized in that its processing step comprises:
1), the preparation of modifier
The solvent of polyamide is mixed with modifier aqueous solution with deionized water;
2), the immersion modification of commodity polyamide reverse osmosis composite film is handled
At ambient temperature, polyamide reverse osmosis composite film is immersed in the modifier solution, soak time is 0.5～10 hour;
3), the rinsing of Modified Membrane and drying
Will be through soaking polyamide composite film rinsing in deionized water that modification is handled, behind the flush away modifier, room temperature is dried fully, finished product.
Described modifier solvent is phosphoric acid, the hydrochloric acid in the inorganic acid series; The modifier aqueous solution concentration of inorganic acid is 9.5%～24.5% phosphoric acid or aqueous hydrochloric acid solution.
Described modifier solvent is formic acid, the acetate in the organic acid series; Organic acid modifier aqueous solution concentration is 4%～16% formic acid or acetic acid aqueous solution.
Described modifier solvent is the phenol in the phenols; Phenol-modified dose of concentration of aqueous solution is 0.02%～0.5% phenol solution.
The inventive method need not membrane equipment and macromolecular material, only uses commodity polyamide reverse osmosis composite film and chemical reagent commonly used, and technology is simple, and is easy to operate and safe, and reagent is cheap and easy to get, and modified condition is easily controlled.Because modifier only is the solvent of the separating layer polyamide of composite membrane, so modifying process is to the structure and the not influence of physical and mechanical properties of the porous support layer PS membrane of composite membrane, simultaneously to the also not influence of chemical stability of composite membrane.The present invention makes the commodity polyamide reverse osmosis composite film become good infiltrating and vaporizing membrane under the modified condition of common chemical reagent, simple technology and easily control, and the osmosis vaporizing compound membrane that institute's modification becomes has higher separating property.
Description of drawings
Accompanying drawing is the structural change principle schematic of PA membrane in solvent processing modifying process.
Wherein:
I is that solvent molecule contacts with PA membrane.
II is that solvent molecule enters in the hole and micro-capsule between micro-capsule, and the polyamide macromolecular chain segment outwards moves in the micro-capsule.
III is the polyamide macromolecular chain vitrifying effect that enters space between micro-capsule.
The specific embodiment
Referring to accompanying drawing.The interpenetrative effect of solvent processing procedure molecule of PA membrane lives through three phases: I represents the incipient stage, and solvent molecule contacts with PA membrane.Because the asymmetry compacted zone of reverse osmosis composite membrane as thin as a wafer, therefore, when PA membrane is immersed in the solvent medium, PA membrane fully contacts with solvent, polyamide macromolecular chain 1 and the strong interaction of solvent molecule 2 generations.II represents to permeate dissolution phase, and solvent molecule enters in the space and micro-capsule between micro-capsule, and the big molecule of polyamide in the micro-capsule spreads to solvent medium.PA membrane is in solvent medium, macromolecular chain is subjected to the effect of the thermodynamic driving force of enthalpy character, solvent molecule penetrates into the space between micro-capsule easily, and and then infiltrate in the micro-capsule between closelypacked folding macromolecular chain, and the macromolecule network of the polymer segment in the micro-capsule around penetrating spreads to solvent medium.III represents ending phase, enters the polyamide macromolecular chain vitrifying in space between micro-capsule.Behind removal of solvents, the polyamide macromolecular chain that occupies space between micro-capsule freezes, the micro-capsule size decreases, and the space between micro-capsule forms more fine and close macromolecule phase 3.At this time, the polyamide reverse osmosis composite film of asymmetry porous is modified becomes the osmosis vaporizing compound membrane of homogeneous phase densification.Reduce through the swelling ratio of solvent modified polyamide composite film to isopropyl alcohol, to the swelling ratio increase of water, therefore, the water flux of separating isopropanol aqueous mixtures is also bigger, and especially the separation factor of polyamide composite film improves greatly after the modification.
Practice shows, no matter polyamide composite film is through being that hydrophily obviously increased after inorganic acid, organic acid or phenol solution were handled, and close organic matter ability significantly reduces, and helps improving the separation rate of film to the organic matter aqueous mixtures.The concentration of different modifier and action time, each was variant to the swelling ratio of polyamide composite film and infiltration evaporation performance impact.
Composite membrane after solvent is handled is that the aqueous mixtures of 87wt% is listed in table 1 in 25 ℃ of room temperatures and the film downstream pressure Pervaporation Separation during less than 1000Pa to isopropyl alcohol.
The polyamide composite film Pervaporation Separation of table 1 modification
Modifier phosphoric acid hydrochloric acid arboxylic acid phenol
Concentration 15wt% 15wt% 8wt% 8wt% 0.05wt%
Processing time 1h 1h 1h 1h 3h
Separation factor, α 174 189 207 276 264
Permeation flux, J (g/m
2.h) 286 298 306 307 308
Table 1 shows that after acid selected with experiment or phenol processing, polyamide composite film all has Pervaporation Separation preferably to isopropanol water solution, and its Changing Pattern and Modified Membrane are to the swelling ratio basically identical of water, isopropyl alcohol.
Polyamide composite film aqueous mixtures separating property to the 87wt% isopropyl alcohol under identical experiment condition with modification is made comparisons: water flux 174g/m
2H～405g/m
2H, separation factor 174～276, swelling ratio to water and isopropyl alcohol is respectively 31.7～40.89 and 10.24～15.73, with unmodified commodity polyamide reverse osmosis composite film the isopropanol-water mixture separating property is compared, the relative reduced rate of water flux reaches more than 51%, separation factor raising rate relatively reaches more than 144%, swelling ratio raising rate to water reaches 10%～42%, swelling ratio reduced rate to isopropyl alcohol reaches 7%～39%, and promptly not having the commodity polyamide reverse osmosis composite film of separating power to be modified to the organic matter aqueous mixtures becomes good infiltration vaporization separation film.
Specific embodiment of the present invention is as follows:
Embodiment 1: getting commodity polyamide reverse osmosis composite film immersion acetic acid concentration is in the modifier aqueous solution of 8wt%, 25 ℃ of temperature, processing time 1h, the performance of the polyamide composite film infiltration evaporation separating isopropanol aqueous mixtures of gained modification: separation factor 276, water flux 307g/m
2H.
Embodiment 2: only change modifier acetic acid concentration 4wt%, all the other conditions are with embodiment 1, the performance of the polyamide composite film infiltration evaporation separating isopropanol aqueous mixtures of gained modification: separation factor 210, water flux 332g/m
2H.
Embodiment 3: only change modifier acetic acid concentration 16wt%, all the other conditions are with embodiment 1, the performance of the polyamide composite film infiltration evaporation separating isopropanol aqueous mixtures of gained modification: separation factor 184, water flux 398g/m
2H.
Embodiment 4: only change modification processing time 5h, all the other conditions are with embodiment 1, the performance of the polyamide composite film infiltration evaporation separating isopropanol aqueous mixtures of gained modification: separation factor 178, water flux 405g/m
2H.
Embodiment 5: the commodity polyamide reverse osmosis composite film immerses the modifier aqueous solution of formic acid concn 8wt%, 25 ℃ of temperature, processing time 1h, the performance of the polyamide composite film infiltration evaporation separating isopropanol aqueous mixtures of gained modification: separation factor 207, water flux 306g/m
2H.
Embodiment 6: the commodity polyamide reverse osmosis composite film immerses the modifier aqueous solution of concentration of hydrochloric acid 15wt%, 25 ℃ of temperature, processing time 1h, the performance of the polyamide composite film infiltration evaporation separating isopropanol aqueous mixtures of gained modification: separation factor 189, water flux 298g/m
2H.
Embodiment 7: the commodity polyamide reverse osmosis composite film immerses the modifier aqueous solution of phosphoric acid concentration 15wt%, 25 ℃ of temperature, processing time 1h, the performance of the polyamide composite film infiltration evaporation separating isopropanol aqueous mixtures of gained modification: separation factor 174, water flux 286g/m
2H.
Embodiment 8: the commodity polyamide reverse osmosis composite film immerses the modifier aqueous solution of phenol concentration 0.05wt%, 25 ℃ of temperature, processing time 3h, the performance of the polyamide composite film infiltration evaporation separating isopropanol aqueous mixtures of gained modification: separation factor 264, water flux 308g/m
2H.
Claims (4)
1, a kind of solvent modified method of polyamide composite film is characterized in that its processing step comprises:
1), the preparation of modifier
The solvent of polyamide is mixed with modifier aqueous solution with deionized water;
2), the immersion modification of commodity polyamide reverse osmosis composite film is handled
At ambient temperature, polyamide reverse osmosis composite film is immersed in the modifier aqueous solution, soak time is 0.5～10 hour;
3), the rinsing of Modified Membrane and drying
Will be through soaking polyamide composite film rinsing in deionized water that modification is handled, behind the flush away modifier, room temperature is dried, i.e. finished product fully.
2, the solvent modified method of polyamide composite film described in claim 1 is characterized in that described modifier solvent is phosphoric acid, the hydrochloric acid in the inorganic acid series, and the modifier aqueous solution concentration of inorganic acid is 9.5%～24.5% phosphoric acid or aqueous hydrochloric acid solution.
3, the solvent modified method of polyamide composite film described in claim 1 is characterized in that described modifier solvent is formic acid, the acetate in the organic acid series, and organic acid modifier aqueous solution concentration is 4%～16% formic acid or acetic acid aqueous solution.
4, the solvent modified method of polyamide composite film described in claim 1 is characterized in that described modifier solvent is the phenol in the phenols, and modifier aqueous solution concentration is 0.02%～0.5% phenol solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03141702 CN1569317A (en) | 2003-07-16 | 2003-07-16 | Solvent modifying method for polyamide composite film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03141702 CN1569317A (en) | 2003-07-16 | 2003-07-16 | Solvent modifying method for polyamide composite film |
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|---|---|
| CN1569317A true CN1569317A (en) | 2005-01-26 |
Family
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| CN 03141702 Pending CN1569317A (en) | 2003-07-16 | 2003-07-16 | Solvent modifying method for polyamide composite film |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008025259A1 (en) * | 2006-08-25 | 2008-03-06 | Vontron Membrane Technology Co., Ltd. | Oxidation-resistant composite reverse osmosis membrane |
| CN102274692A (en) * | 2011-02-10 | 2011-12-14 | 天津工业大学 | Method for modifying surface of polymer film |
| CN101511459B (en) * | 2006-09-07 | 2012-08-08 | 熊津豪威株式会社 | Amine aqueous solution for forming an active layer of polyamide reverse osmosis composite membrane, polyamide reverse osmosis composite membrane prepared thereby, and preparation method thereof |
| CN103657454A (en) * | 2013-12-17 | 2014-03-26 | 北京碧水源膜科技有限公司 | Preparation method for novel polyamide reverse osmosis membrane |
| CN108889128A (en) * | 2018-07-26 | 2018-11-27 | 四川美富特水务有限责任公司 | A kind of preparation method of polyamide composite reverse osmosis membrane |
| CN112619437A (en) * | 2020-12-11 | 2021-04-09 | 天津海普尔膜科技有限公司 | Preparation method of lipophilic film for waste oil purification treatment |
-
2003
- 2003-07-16 CN CN 03141702 patent/CN1569317A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008025259A1 (en) * | 2006-08-25 | 2008-03-06 | Vontron Membrane Technology Co., Ltd. | Oxidation-resistant composite reverse osmosis membrane |
| CN101511459B (en) * | 2006-09-07 | 2012-08-08 | 熊津豪威株式会社 | Amine aqueous solution for forming an active layer of polyamide reverse osmosis composite membrane, polyamide reverse osmosis composite membrane prepared thereby, and preparation method thereof |
| CN102274692A (en) * | 2011-02-10 | 2011-12-14 | 天津工业大学 | Method for modifying surface of polymer film |
| CN102274692B (en) * | 2011-02-10 | 2013-11-27 | 天津工业大学 | Method for modifying surface of polymer film |
| CN103657454A (en) * | 2013-12-17 | 2014-03-26 | 北京碧水源膜科技有限公司 | Preparation method for novel polyamide reverse osmosis membrane |
| CN103657454B (en) * | 2013-12-17 | 2015-12-30 | 北京碧水源膜科技有限公司 | A kind of preparation method of novel polyamide reverse osmosis membrane |
| CN108889128A (en) * | 2018-07-26 | 2018-11-27 | 四川美富特水务有限责任公司 | A kind of preparation method of polyamide composite reverse osmosis membrane |
| CN112619437A (en) * | 2020-12-11 | 2021-04-09 | 天津海普尔膜科技有限公司 | Preparation method of lipophilic film for waste oil purification treatment |
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