CN1093944A - The preparation method of vapor permeable membrance and composition - Google Patents
The preparation method of vapor permeable membrance and composition Download PDFInfo
- Publication number
- 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
- Authority
- CN
- China
- Prior art keywords
- preparation
- pva
- solution
- vapor permeable
- preparation liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a kind of preparation method and composition of vapor permeable membrance.It comprises a) preparation of preparation liquid: polyvinyl alcohol adds distilled water in proportion, stirring and dissolving under constant temperature, and gained solution suction filtration is removed insoluble matter.Shitosan adds distilled water in proportion, adds glacial acetic acid stirring and dissolving under constant temperature of CS equivalent again, and gained solution suction filtration is removed insoluble matter.With above-mentioned two solution blendings, add 1% citric acid crosslinking agent again, under constant temperature, stir gained preparation liquid, discontinuous degassing; B) knifing: will be smooth on the glass plate of cleaning through PSF or PAN that water logging was steeped, above-mentioned preparation liquid is scraped on basement membrane; C) solvent evaporation, wet film evaporation under the infrared lamp irradiation.Technology of the present invention is simple, and is easy to operate, and material PVA, CS are cheap, the uniformity of film and good reproducibility, and separating property is good.
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 | The preparation method of vapor permeable membrance and composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94102067 CN1093944A (en) | 1994-03-22 | 1994-03-22 | The preparation method of vapor permeable membrance and composition |
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 | The preparation method of vapor permeable membrance and composition |
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 | Prepn process of hollow chitosam fiber film 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 | Preparation method of polyvinyl chitosan mixed 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 | Preparation method of polyvinyl chitosan mixed film |
| CN100482329C (en) * | 2006-02-15 | 2009-04-29 | 中国科学院大连化学物理研究所 | Prepn process of hollow chitosam fiber film 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 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3195377B2 (en) | Organic solvent selective permeable membrane | |
| EP0369787B1 (en) | Membrane for separation of water-alcohol mixed liquid and process for preparation thereof | |
| CN102327746A (en) | Anti-pollution cyclodextrin-polymer composite nano-filtration membrane and preparation method thereof | |
| CN100515551C (en) | Method for manufacturing composite membrane of polyvinyl alcohol for treating sewerage of containing oil | |
| CN105617882A (en) | Chitosan modified graphene oxide nano composite positive osmotic membrane and preparation method thereof | |
| CN102580581B (en) | Composite ultrafiltration film and preparation method thereof | |
| CN112588118B (en) | Pervaporation membrane for separating N, N-dimethylformamide aqueous solution and preparation method thereof | |
| CN1907550A (en) | Preparation method for hollow fiber osmosis vaporation permeable complex film | |
| CN110066415A (en) | A kind of preparation method of the perforated membrane of functionalized surface | |
| CN107138052B (en) | Preparation method of antibacterial cellulose acetate reverse osmosis membrane containing bromoalkane | |
| CN1093944A (en) | The preparation method of vapor permeable membrance and composition | |
| CN101259385B (en) | Quaterisation chitosan penetrating and evaporating film, preparation and application thereof | |
| Schwarz et al. | Membranes based on polyelectrolyte–surfactant complexes for methanol separation | |
| CN113522039A (en) | Preparation method of forward osmosis membrane based on PVA (polyvinyl alcohol) grafting modification | |
| CN101053783A (en) | Surface processing method for hollow fiber ultrafiltering membrane | |
| CN1119553A (en) | Preparation of chitosan charged microporous filtering film by dip-coating method | |
| CN1872400A (en) | Method for preparing Nano filtering composite membrane of hollow fiber | |
| CN112058100A (en) | Preparation method of filtering membrane applied to sewage treatment | |
| US20030034304A1 (en) | N-acetylated chitosan membranes | |
| CN1107532C (en) | Process for preparing compound polyelectrolyte (chitosan/sodium polyphosphate) membrane | |
| WO2022199554A1 (en) | Composite ultrafiltration membrane material and preparation method therefor | |
| CN108905642A (en) | A kind of sodium lignosulfonate being preferentially dehydrated/sodium alginate blending infiltrating and vaporizing membrane | |
| CN113069933B (en) | Organic/inorganic composite membrane for separating N, N-dimethylformamide/water mixture and preparation method thereof | |
| Vaulina et al. | The effect of cellulose acetate concentration from coconut nira on ultrafiltration membrane characters | |
| CN110201559A (en) | A kind of big flux Enhanced type hollow fiber film and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |