CN1093944A - Preparation method and composition of pervaporation water permeable membrane - Google Patents
Preparation method and composition of pervaporation water permeable membrane Download PDFInfo
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- CN1093944A CN1093944A CN 94102067 CN94102067A CN1093944A CN 1093944 A CN1093944 A CN 1093944A CN 94102067 CN94102067 CN 94102067 CN 94102067 A CN94102067 A CN 94102067A CN 1093944 A CN1093944 A CN 1093944A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000000203 mixture Substances 0.000 title claims abstract description 17
- 239000012528 membrane Substances 0.000 title abstract description 23
- 238000005373 pervaporation Methods 0.000 title abstract 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 43
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 43
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 239000012153 distilled water Substances 0.000 claims abstract description 11
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011521 glass Substances 0.000 claims abstract description 8
- 229960000583 acetic acid Drugs 0.000 claims abstract description 4
- 239000002253 acid Substances 0.000 claims abstract description 4
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 4
- 238000000935 solvent evaporation Methods 0.000 claims abstract description 3
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 41
- 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
- 239000007788 liquid Substances 0.000 claims description 15
- 210000002469 basement membrane Anatomy 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 238000001704 evaporation Methods 0.000 claims description 9
- 230000008020 evaporation Effects 0.000 claims description 9
- 229920002101 Chitin Polymers 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000007872 degassing Methods 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 4
- 239000012043 crude product Substances 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 2
- 230000006196 deacetylation Effects 0.000 claims description 2
- 238000003381 deacetylation reaction Methods 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 239000012286 potassium permanganate Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims 3
- 235000006408 oxalic acid Nutrition 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 9
- 238000005516 engineering process Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- 229920001661 Chitosan Polymers 0.000 abstract description 2
- 244000248349 Citrus limon Species 0.000 abstract 1
- 235000005979 Citrus limon Nutrition 0.000 abstract 1
- 238000003795 desorption Methods 0.000 abstract 1
- 238000007790 scraping Methods 0.000 abstract 1
- 230000003068 static effect Effects 0.000 abstract 1
- 229940068984 polyvinyl alcohol Drugs 0.000 description 30
- 210000004379 membrane Anatomy 0.000 description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 238000001764 infiltration Methods 0.000 description 8
- 239000002131 composite material Substances 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 7
- 230000008595 infiltration Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 229920002492 poly(sulfone) Polymers 0.000 description 4
- 229920002239 polyacrylonitrile Polymers 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000909 electrodialysis Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000001471 micro-filtration Methods 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 210000002808 connective tissue Anatomy 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 238000009661 fatigue test Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
本发明公开了一种渗透汽化透水膜的制备方法 及组成。它包括a)制膜液的配制：聚乙烯醇按比例 加入蒸馏水，在恒温条件下搅拌溶解，所得溶液抽滤 除去不溶物。壳聚糖按比例加入蒸馏水，再加入CS 等量的冰醋酸在恒温条件下搅拌溶解，所得溶液抽滤 除去不溶物。将上述两溶液共混，再加入1％的柠檬 酸交联剂，在恒温条件下搅拌，所得制膜液，静止脱 泡；b)刮膜：将经水浸泡过的PSF或PAN平贴于洁 净的玻璃板上，将上述制膜液刮在基膜上；c)溶剂蒸 发，湿膜在红外灯照射下蒸发。本发明工艺简单，操 作方便，材料PVA、CS价格低廉，膜的均匀性和重复 性好，分离性能好。The invention discloses a preparation method of a pervaporation water permeable membrane and composition. It includes a) preparation of film-making solution: polyvinyl alcohol in proportion Add distilled water, stir and dissolve under constant temperature conditions, and filter the resulting solution with suction Remove insolubles. Add chitosan to distilled water in proportion, then add CS An equal amount of glacial acetic acid was stirred and dissolved under constant temperature conditions, and the resulting solution was suction filtered Remove insolubles. Blend the above two solutions, then add 1% lemon Acid cross-linking agent, stirring under constant temperature conditions, the resulting film-making solution, static desorption bubble; b) scraping film: put PSF or PAN soaked in water on the clean On a clean glass plate, scrape the above-mentioned film-making solution on the base film; c) solvent evaporation The wet film was evaporated under the irradiation of infrared lamps. The technology of the present invention is simple, operates Easy to operate, low price of materials PVA and CS, uniformity and repeatability of the film Good performance, good separation performance.
Description
The present invention relates to the preparation method and the composition of diffusion barrier, especially relate to the preparation and the composition of vapor permeable membrance.
The commercial Application of membrane technology has more than 30 year history.Mainly contain micro-filtration, ultrafiltration, electrodialysis, counter-infiltration, gas separation and infiltration evaporation etc. with the membrane technology that is separated into purpose.Membrane technology also begins to be used for aspects such as reaction and detection in recent years, discharges as membrane bioreactor, membrane catalytic reactor, film sensors and control etc.Membrane technology is because its process is simple, and application is wide, and low power consumption and other advantages is subjected to countries in the world and payes attention to.Domestic also existing many-sided research and application have been used for as processes such as micro-filtration, ultrafiltration, electrodialysis, counter-infiltration and gas separation that high purity water is produced and chemical industry, environmental protection, food, agricultural and medicine and other fields.
Produce the higher alcohol of purity by Diluted Alcohol is concentrated, particularly produce absolute alcohol and select for use the infiltration evaporation membrane separation process and the extracting rectifying of routine to compare the special superiority of demonstration with sequence of constant boiling and rectification.Paid close attention to by countries in the world with the infiltrating and vaporizing membrane technical finesse azeotrope and the thing that closely boils, its high selectivity film is called as third generation film, is one of main goal of attack in the present domestic adventitia research.
Material selection and film development to this film both at home and abroad had a lot of reports, for example: polytetrafluoroethylene (PTFE) and vinylpyrrolidone grafting (PTFE-PVP), polyacrylonitrile (PAN), polysulfones (PSF), polyvinyl alcohol (PVA), shitosan (CS), cellulose acetate (CTA) etc., but the used film of external industry and pilot-scale (as the Betheniville of France, the Lurgi of Germany etc.) has only one kind of GFT, and this is a kind of composite membrane.Scrape in the polyacrylonitrile basement membrane by suitable crosslinked PVA and to form.Once reported separation α=400～450 of gained, infiltration flow rate J=1～2kg/m
2H.Once handle the alcohol-water azeotrope in this laboratory with the GFT film, recorded its α 〉=100, J=0.15kg/m
2H, industrial film size is about 50 * 50cm
2Mechanical strength and the service life of finding film in the lab scale of laboratory have much room for improvement.
The preparation method and the composition that the purpose of this invention is to provide a kind of vapor permeable membrance.
The preparation method of vapor permeable membrance is: a) preparation liquid preparation: polyvinyl alcohol (PVA-124) and distilled water are poured in the container in 1～1/2.4 ratio, and under 80～85 ℃ constant temperature, constantly stir, treat that PVA dissolves the back fully and continues to stir 20～30min.Should add distilled water at any time in the PVA course of dissolution, with the moisture content of compensate for evaporation, gained solution suction filtration is removed insoluble matter, and filtrate is stand-by.Shitosan (CS) and distilled water are poured in the container in 1/99 ratio, after the glacial acetic acid that adds weight such as CS again stirs 10min, placed 24 hours, CS promptly dissolves, and gained solution suction filtration is removed insoluble matter, and filtrate is stand-by.With above-mentioned PVA solution and CS solution blending, add 1% citric acid crosslinking agent (adding behind the crosslinking agent wiring solution-forming) solution again, and under 80～85 ℃ of constant temperatures, stir, part moisture content is removed in evaporation, obtains the preparation liquid of required viscosity, gets final product knifing behind the discontinuous degassing.B) knifing: will be affixed on the clean glass plate through PSF or the PAN basement membrane that water logging was steeped, catch up with, the preparation liquid behind the discontinuous degassing is scraped on basement membrane equably except that the bubble between basement membrane and the glass plate.C) solution evaporation: wet film allows solvent evaporate in the indoor infrared lamp irradiation of system film.D) preparation method of the shitosan (CS) among the said a is: the crab shell is cut into pieces; soaked 24 hours with diluted acid the washing back; after the hot water wash; in diluted alkaline, soak and took out in 24 hours; extremely neutral with hot water wash; repeat aforesaid operations and make the chitin crude product; crude product decolours with potassium permanganate and leather acid; get the white plates chitin; chitin soaked 24 hours down in 60～65 ℃ of constant temperatures with 50% NaOH, and hot water repeats once after cleaning, and sloughed that acetyl group makes the shitosan product in the chitin; deacetylation 85%, viscosity are 1200cp.E) PVA solution among the said a and CS solution blending, its preparation liquid blending ratio is the PVA/CS=4/1(weight ratio).
The composition of vapor permeable membrance is by polyvinyl alcohol (PVA～124) and shitosan (CS) blend, and 1% citric acid crosslinking agent modification, and the preparation liquid blending ratio is a PVA/CS=4/1(weight).
Owing to membrane material polyvinyl alcohol (PVA) has good water-solubility, dehydration is had separating property preferably, but water content is higher in the feed liquid of handling, when operating temperature was too high, the PVA film can be by water swelling, dissolving so that breakage gradually.The intermolecular strong hydrogen bond action of membrane material shitosan (CS) makes it not dissolve in water, and special alkali resistance and organic solvent resistance are arranged, but the CS film is lower to the separation factor of ethanol-water system, therefore consider the performance of comprehensive PVS and two kinds of materials of CS, learn from other's strong points to offset one's weaknesses, blend is a kind of to the improved method of polymeric membrane.
In the development process of infiltrating and vaporizing membrane, film crosslinked extremely important carries out crosslinking Treatment to water permeable membrane, and two purposes are generally arranged: the one, wish to improve the separating property of film; The 2nd, hope improves the resistance to water and the mechanical performance of film.At PVA/CS(=4/1) under the blending ratio, make the PVA=CS blend composite film that crosslinking agent adopts solution crosslinking (promptly preparation liquid being carried out modification handles) with polyacid.After crosslinked, PVA is intermolecular, and the intermolecular cross-linking reaction by crosslinking agent of CS has obtained bridging action, has formed the three-dimensional space network structure.PVA and CS are intermolecular also can to form the three-dimensional space network structure by the bridge formation of polyacid, i.e. a part of carboxyl of polyacid and the effect of PVA molecule hydroxyl, and the amido effect in another part carboxyl and the CS molecule has reduced the number of hydrophilic radical in the film.Generally speaking, crosslinked permeance property to the PVA-CS blend film has the influence of four aspects: (1) reduction film surface is the hydrophily of face to the adsorption capacity of water, thereby makes the separation factor of cross linking membrane lower than uncrosslinked film; (2) swellbility of reduction film has weakened the diffusivity of component molecule in film, makes the infiltration flow rate of film be lower than uncrosslinked film; (3) if crosslinking points is evenly distributed, the molecule gap of film evenly reduces, the sterically hindered increase of film, high polymer segment warm-up movement resistance increases, the resistance that component sees through film increases, because of the diameter of ethanol molecule is bigger than the diameter of hydrone, ethanol molecule infiltration flow rate decline scope is bigger than water, thereby makes the separation factor of cross linking membrane than uncrosslinked film height; (4) because the existence of cross-bond bridge also may make PVA intermolecular, and CS is intermolecular, PVA and CS be intermolecular to be difficult to realize tight arrangement, and intermolecular " hole " increases, and causes the component diffusivity to increase, and the infiltration flow rate of film increases, separation factor decline.Along with the difference of crosslinking degree, the number that hydrophilic radical reduces in the film, component increases degree by the resistance of film, and factors such as intermolecular " hole " increase degree are also with difference.
Embodiment:
The preparation liquid preparation:
Claim 20g polyvinyl alcohol (PVA～124), add 480g distilled water, under 80～85 ℃ of constant temperatures, constantly stir, treat that PVA dissolves the back fully and continues to stir 20～30min, in the PVA course of dissolution, should add distilled water at any time, with the moisture content that compensate for evaporation is gone, gained solution suction filtration is removed insoluble matter, and filtrate is stand-by.
Claim 5g shitosan, add 490g distilled water, add after the 5g glacial acetic acid stirs 10min again, places 24 hours shitosans and dissolve, gained solution suction filtration is removed insoluble matter, and filtrate is stand-by.
With poly-vinyl alcohol solution and chitosan solution blend, add 1 gram, 1% citric acid crosslinking agent, and under 80～85 ℃ constant temperature, stir, part moisture content is removed in evaporation, and being concentrated into volume is about 450g, cooling, discontinuous degassing.
Knifing:
Will be smooth on the glass plate of cleaning through the PSF milipore filter that water logging was steeped, catch up with except that bubble between basement membrane and the glass, the stainless steel wire of certain thickness is fixed on the face, as striking thickness of liquid film benchmark, the preparation liquid behind the discontinuous degassing is scraped on basement membrane equably.
The solvent evaporation:
Regulate 30～35 ℃ of system film room temperatures with infrared lamp, allow solvent evaporate.
Take off the dehydration of this composite membrane to ethanol from above-mentioned glass plate, its performance is as follows:
Separating property
Xe(wt%) Jt(g/m
2h) α
95.9 91.7 547
94.7 137 8916
91.6 168 2170
89.3 200 1034
87.7 223 1011
Test condition: feed temperature t=50 ℃, downstream vacuum 600Pa
Mechanical performance
Membrane sample (long * wide * thick) (mm
3) maximum pull (N) fracture strength
σ
B(N/mm
2)
PVA-CS 20×5×10×10
-33.82 76.4
GFT (Germany) 20 * 5 * 2.5 * 10
-30.57 42.4
Remarks: σ
B=(maximum pull (N))/(stretching sectional area (mm
2)), stretching sectional area=wide * thick (mm
2)
The method of testing of mechanical strength is that the composite bed with composite membrane peels from basement membrane, with the WD-10 type, electronic universal tester is 5 ℃ of environment temperatures, relative humidity 73%, under the condition of test speed 10mm/min, the maximum pull that the test compound layer can bear calculates its fracture strength σ by maximum pull
BMechanical performance with characterization of membrane.
Water resistance
| Film | Sample heavy (mg) | Weightless (mg) relative weight loss (wt%) |
| After soaking before soaking | ||
| PVA-CS | 73.8 76.6 | 0.2 0.27 |
| GFT (Germany) | 69.9 69.6 | 0.3 0.43 |
The test of resistance to water is to be immersed in after the composite bed constant weight that will peel from basement membrane 50 ℃ the ethanolic solution (Xw=11.2wt%), soaks and takes out sample constant weight again after five days, and the weightlessness before and after calculation sample soaks, relative weight loss characterizes water resistance.
Fatigue test
Test condition: feed temperature t=50 ℃, concentration Xw=5.2wt%, downstream vacuum 600Pc.
Technology of the present invention is simple, and is easy to operate, and material PVA, CS are cheap, and the modified PVA that makes-CS blend composite permeable membrane size has reached 250 * 200mm
2The uniformity of film and good reproducibility, separating property is good, can be applicable to the dehydration of ethanol, isopropyl alcohol, butyric acid, acetone, C
5Middle separating methanol etc.
Claims (5)
1, a kind of preparation method of vapor permeable membrance is characterized in that it comprises:
A. preparation liquid preparation:
Polyvinyl alcohol (PVA-124) and distilled water are poured in the container in 1～1/24 ratio, and under 80～85 ℃ of constant temperatures, constantly stir, treat that PVA dissolves the back fully and continues to stir 20～30min, in the PVA course of dissolution, should add the moisture content that distilled water goes with compensate for evaporation at any time, gained solution suction filtration is removed insoluble matter, and filtrate is stand-by;
Shitosan (CS) and distilled water are poured in the container in 1/99 ratio, after the glacial acetic acid that adds weight such as CS again stirs 10min, placed 24 hours, CS promptly dissolves, and gained solution suction filtration is removed insoluble matter, and filtrate is stand-by;
With above-mentioned PVA solution and CS solution blending, add 1% citric acid crosslinking agent (adding behind the crosslinking agent wiring solution-forming) solution again, and under 80～85 ℃ constant temperature, stir, part moisture content is removed in evaporation, obtains the preparation liquid of required viscosity, gets final product knifing behind the discontinuous degassing;
B. knifing:
Will be smooth on the glass plate of cleaning through PSF or PAN basement membrane that water logging was steeped, catch up with except that the bubble between basement membrane and the glass, with the preparation liquid behind the discontinuous degassing, scrape equably on basement membrane;
C. solvent evaporation:
Wet film allows solvent evaporate in the indoor infrared lamp irradiation of system film.
2, the preparation method of a kind of vapor permeable membrance according to claim 1 is characterized in that it comprises:
The preparation method of the shitosan (CS) among the d. said a is: the crab shell is cut into pieces; soaked one day with diluted acid the washing back; in diluted alkaline, soak after the hot water wash and took out in 24 hours; extremely neutral with hot water wash; repeat aforesaid operations and make the chitin crude product; crude product gets the white plates chitin with potassium permanganate and oxalic acid deaeration; chitin soaked 24 hours under 60～65 ℃ of constant temperatures with 50% NaOH; hot water repeats once after cleaning; slough that acetyl group makes the shitosan product in the chitin; deacetylation 85%, viscosity are 1200cp.
3, the preparation method of a kind of vapor permeable membrance according to claim 1 and 2 is characterized in that it comprises:
E. PVA solution among the said a and CS solution blending, its mixing ratio of its preparation liquid is the PVA/CS=4/1(weight ratio).
4, a kind of composition of the vapor permeable membrance of preparation according to the method described above is characterized in that it is by polyvinyl alcohol (PVA-124) and shitosan (CS) blend, and 1% citric acid crosslinking agent modification.
5, a kind of composition of the vapor permeable membrance of preparation as stated above according to claim 4 is characterized in that said PVA solution and CS solution blending, and its preparation liquid blending ratio is the PVA/CS=4/1(weight ratio).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94102067 CN1093944A (en) | 1994-03-22 | 1994-03-22 | Preparation method and composition of pervaporation water permeable membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94102067 CN1093944A (en) | 1994-03-22 | 1994-03-22 | Preparation method and composition of pervaporation water permeable membrane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1093944A true CN1093944A (en) | 1994-10-26 |
Family
ID=5030490
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 94102067 Pending CN1093944A (en) | 1994-03-22 | 1994-03-22 | Preparation method and composition of pervaporation water permeable membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1093944A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100482329C (en) * | 2006-02-15 | 2009-04-29 | 中国科学院大连化学物理研究所 | A kind of preparation method of chitosan hollow fiber membrane for pervaporation separation |
| CN100493688C (en) * | 2006-01-26 | 2009-06-03 | 中国科学院大连化学物理研究所 | A kind of preparation method of polyvinyl alcohol/chitosan blend film |
| CN105727761A (en) * | 2016-03-10 | 2016-07-06 | 上海工程技术大学 | Protein-fouling-resistant zwitter-ion ultrafiltration membrane and preparation method thereof |
| CN106925142A (en) * | 2017-05-04 | 2017-07-07 | 中国矿业大学(北京) | A kind of many separating layer infiltrating and vaporizing membranes and preparation method thereof |
| CN110922300A (en) * | 2019-12-07 | 2020-03-27 | 江苏久吾高科技股份有限公司 | Alcohol recovery method and device |
-
1994
- 1994-03-22 CN CN 94102067 patent/CN1093944A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100493688C (en) * | 2006-01-26 | 2009-06-03 | 中国科学院大连化学物理研究所 | A kind of preparation method of polyvinyl alcohol/chitosan blend film |
| CN100482329C (en) * | 2006-02-15 | 2009-04-29 | 中国科学院大连化学物理研究所 | A kind of preparation method of chitosan hollow fiber membrane for pervaporation separation |
| CN105727761A (en) * | 2016-03-10 | 2016-07-06 | 上海工程技术大学 | Protein-fouling-resistant zwitter-ion ultrafiltration membrane and preparation method thereof |
| CN105727761B (en) * | 2016-03-10 | 2018-07-24 | 上海工程技术大学 | A kind of anti-protein-contamination amphoteric ion ultrafiltration membrane and preparation method thereof |
| CN106925142A (en) * | 2017-05-04 | 2017-07-07 | 中国矿业大学(北京) | A kind of many separating layer infiltrating and vaporizing membranes and preparation method thereof |
| CN110922300A (en) * | 2019-12-07 | 2020-03-27 | 江苏久吾高科技股份有限公司 | Alcohol recovery method and device |
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