CN1270078A - Process for preparing compound polyelectrolyte (chitosan/sodium polyphosphate) membrane - Google Patents
Process for preparing compound polyelectrolyte (chitosan/sodium polyphosphate) membrane Download PDFInfo
- Publication number
- CN1270078A CN1270078A CN 00109129 CN00109129A CN1270078A CN 1270078 A CN1270078 A CN 1270078A CN 00109129 CN00109129 CN 00109129 CN 00109129 A CN00109129 A CN 00109129A CN 1270078 A CN1270078 A CN 1270078A
- Authority
- CN
- China
- Prior art keywords
- film
- shitosan
- preparation
- aqueous solution
- chitosan
- 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.)
- Granted
Links
Abstract
A process for preparing compound polyelectrolyte membrane includes such steps as adding chitosan to diluted aqueous solution of acetic acid to prepare chitosan membrane liquid, filtering, defoaming, coating said membrane liquid on PAN substrate film, baking to obtain chitosan acetate membrane, immersing it in the aqueous solution of sodium polyphosphate for polyionizing reaction, flushing with water and drying in air. Its preparing process is simple. When said membrane is used to dewater organic substance, it has high penetration throughput and separation coefficient.
Description
The present invention relates to the preparation method of a kind of shitosan/polyphosphate sodium compound polyelectrolyte film, belong to the infiltrating and vaporizing membrane separation field.
Shitosan (Chitosan is abbreviated as Cs) is the product of de-acetyl chitin, and mean molecule quantity is 1.0～9.5 * 10
5Between.Chitin is a kind of natural polymer, mainly is present in the sclerotin of nature shrimp, crab, will just obtain shitosan behind the de-acetyl chitin.Shitosan is water insoluble, alkali and general organic solvent, but can be dissolved in the weak solution of formic acid, acetate.Degree of deacetylation can be used as hydrophilic membrane material at the shitosan more than 80%.It is dissolved in makes film liquid in the dilute acetic acid solution, film, behind the airing, the shitosan acetate film that obtains is met just dissolving of water, in order to improve the resistance to water of film, can make vapor permeable membrance just must handle through depickling.But the depickling treatment process is numerous and diverse, difficult, is unfavorable for industrialization promotion.Because the selectivity of film is on the low side, generally adopt crosslinking Treatment can improve the selectivity of film simultaneously, this has increased the complexity of filming technology again.
The objective of the invention is to propose the preparation method of a kind of shitosan/polyphosphate sodium compound polyelectrolyte film, replace complicated depickling processing procedure, thereby simplify the preparation technology of film, improve the performance of film.
The preparation method of shitosan/polyphosphate sodium compound polyelectrolyte film that the present invention proposes comprises the following steps:
1, chitosan film liquid preparation: it is in 0.5～2% the dilute acetic acid aqueous solution that certain amount of chitosan is joined mass percentage concentration, is mixed with mass percentage concentration at 1%～2% chitosan film liquid, after filtration, stand-by after the deaeration.
2, the preparation of chitosan film: above-mentioned film liquid is coated on PAN (polyacrylonitrile) basement membrane equably, and coating thickness is 150～300 μ m, after oven dry under 40～50 ℃ the temperature, obtains shitosan acetate film.
3, polyphosphate sodium aqueous solution preparation: the preparation mass percentage concentration is 1～10% polyphosphate sodium aqueous solution.
4, the preparation of shitosan/polyphosphate sodium compound polyelectrolyte film: with the shitosan acetate film for preparing in above-mentioned the 2nd step, immerse in the polyphosphate sodium aqueous solution for preparing in the 3rd step and carry out the polyion reaction, reaction time is 1～30 minute, take out water flushing back airing, be the compound polyelectrolyte film of the present invention's preparation.
Use the compound polyelectrolyte film of method preparation of the present invention, its preparation technology is simple, when the film of preparation is used for organics dehydration, has high permeation flux and separation.
Shitosan is a kind of long-chain polycation polysaccharide, is dissolved in the shitosan in spirit of vinegar (brief note the is HAc) solution, contains active group-Cs-NH in its molecular chain structure unit
3 +Ac
-At this specific character, the present invention has selected this short chain polyanionic compound of polyphosphate sodium, and it comprises-P-O
-Na
+Active group.When the shitosan of acetic acid form contacts with polyphosphate sodium, compound between the functional ionic key taken place between the two, form new ionic bond-N
+H
3 -O-P～, generate new polyion compound (Ployionic Compound, PIC).Because the formation of new ionic bond is played crosslinked action to chitosan molecule, exempted the depickling of common chitosan film and handled, film is not dissolved in water, obtain all excellent film of permeation flux and selectivity.
Introduce embodiments of the invention below.
Embodiment one.
With molecular weight is 720,000, and deacetylation is 90.3% shitosan 2g, joins mass percentage concentration and is among 1% the dilute acetic acid aqueous solution 198ml, makes the shitosan acetate film liquid of mass percentage concentration about 1%.After filtration, after the deaeration, evenly coat on the PAN basement membrane, coating thickness is 250 μ m, is promptly making shitosan acetate film of the present invention after the oven dry under 45 ℃ of temperature.Preparation 300ml mass percentage concentration is 1% sodium triphosphate (molecular formula Na
5P
3O
10, molecular weight 368) and the aqueous solution, the shitosan acetate film for preparing is immersed in the above-mentioned sodium triphosphate aqueous solution reaction 5 minutes, make shitosan/polyphosphate sodium compound polyelectrolyte film.Being used for the ethanol mass percentage concentration is that 95% ethanol water carries out infiltration evaporation and separates, and when feeding temperature was 60 ℃, permeation flux was 420g/m
2.h, separation is 3800.
Embodiment two.
With molecular weight is 720,000, and deacetylation is 90.3% shitosan 2g, joins mass percentage concentration and is among 2% the dilute acetic acid aqueous solution 98ml, makes the shitosan acetate film liquid of mass percentage concentration about 2%.After filtration, after the deaeration, evenly coat on the PAN basement membrane, coating thickness is 160 μ m, is promptly making shitosan acetate film of the present invention after the oven dry under 40 ℃ of temperature.Preparation 300ml mass percentage concentration is 6% the sodium triphosphate aqueous solution, film is immersed wherein reacted 2 minutes, makes shitosan/polyphosphate sodium compound polyelectrolyte film.The infiltration evaporation that is used for ethanol water separates, and containing the ethanol mass percentage concentration in feed liquid is 95%, and when feed temperature was 60 ℃, permeation flux was 400g/m
2.h, separation is 1100.The ethanol mass percentage concentration is 90% in feed liquid, and when feed temperature was 60 ℃, permeation flux was 530g/m
2.h, separation is 520.
Embodiment three.
With molecular weight is 720,000, and deacetylation is 90.3% shitosan 2g, joins mass percentage concentration and is among 1.5% the dilute acetic acid aqueous solution 198ml, makes the shitosan acetate film liquid of mass percentage concentration about 1%.After filtration, after the deaeration, evenly coat on the PAN basement membrane, coating thickness is 280 μ m, is promptly making shitosan acetate film of the present invention after the oven dry under 50 ℃ of temperature.Preparation 300ml concentration is the sodium triphosphate aqueous solution of 1% (wt), the film immersion was wherein reacted 10 minutes, make shitosan/polyphosphate sodium compound polyelectrolyte film, be used for the infiltration evaporation separating alcohol aqueous solution, containing the ethanol mass percentage concentration in feed liquid is 95%, when feed temperature was 70 ℃, permeation flux was 300g/m
2.h, separation is 3000.
Embodiment four.
With molecular weight is 720,000, and deacetylation is 90.3% shitosan 2g, joins mass percentage concentration and is among 2% the dilute acetic acid aqueous solution 198ml, makes the shitosan acetate film liquid of mass percentage concentration about 1%.After filtration, after the deaeration, evenly coat on the PAN basement membrane, coating thickness is 260 μ m, is promptly making shitosan acetate film of the present invention after the oven dry under 45 ℃ of temperature.Preparation 300ml mass percentage concentration is 6% the sodium triphosphate aqueous solution, the film immersion was wherein reacted 15 minutes, make shitosan/polyphosphate sodium compound polyelectrolyte film, be used for the infiltration evaporation separating alcohol aqueous solution, containing the ethanol mass percentage concentration in feed liquid is 95%, when feed temperature was 70 ℃, permeation flux was 200g/m
2.h, separation is 2350.
Embodiment five.
With molecular weight is 720,000, and deacetylation is 90.3% shitosan 2g, joins mass percentage concentration and is among 1% the dilute acetic acid aqueous solution 198ml, makes the shitosan acetate film liquid of mass percentage concentration about 1%.After filtration, after the deaeration, evenly coat on the PAN basement membrane, coating thickness is 290 μ m, is promptly making shitosan acetate film of the present invention after the oven dry under 45 ℃ of temperature.Preparation 300ml mass percentage concentration is 1% the sodium triphosphate aqueous solution, the film immersion was wherein reacted 30 minutes, make shitosan/polyphosphate sodium compound polyelectrolyte film, be used for the infiltration evaporation separating alcohol aqueous solution, containing the ethanol mass percentage concentration in feed liquid is 95%, when feed temperature was 70 ℃, permeation flux was 200g/m
2.h, separation is 360.
Embodiment six.
With molecular weight is 720,000, and deacetylation is 90.3% shitosan 2g, joins mass percentage concentration and is among 0.5% the dilute acetic acid aqueous solution 198ml, makes the shitosan acetate film liquid of mass percentage concentration about 1%.After filtration, after the deaeration, evenly coat on the PAN basement membrane, coating thickness is 250 μ m, is promptly making shitosan acetate film of the present invention after the oven dry under 50 ℃ of temperature.Preparation 300ml mass percentage concentration is 10% the sodium triphosphate aqueous solution, the film immersion was wherein reacted 25 minutes, make shitosan/polyphosphate sodium compound polyelectrolyte film, be used for the infiltration evaporation separating alcohol aqueous solution, containing the ethanol mass percentage concentration in feed liquid is 95%, when feed temperature was 70 ℃, permeation flux was 130g/m
2.h, separation is 460.
Claims (1)
1, the preparation method of a kind of shitosan/polyphosphate sodium compound polyelectrolyte film is characterized in that this method comprises the following steps:
(1), chitosan film liquid preparation: it is in 0.5～2% the dilute acetic acid aqueous solution that certain amount of chitosan is joined mass percentage concentration, is mixed with mass percentage concentration at 1%～2% chitosan film liquid, after filtration, stand-by after the deaeration;
(2), the preparation of chitosan film: above-mentioned film liquid is coated on PAN (polyacrylonitrile) basement membrane equably, and coating thickness is 150～300 μ m, after oven dry under 40～50 ℃ the temperature, obtains shitosan acetate film;
(3), polyphosphate sodium aqueous solution preparation: the preparation mass percentage concentration is 1～10% polyphosphate sodium aqueous solution;
(4), the preparation of shitosan/polyphosphate sodium compound polyelectrolyte film: with the shitosan acetate film for preparing in above-mentioned the 2nd step, immerse in the 3rd polyphosphate sodium aqueous solution for preparing in relating to and carry out the polyion reaction, reaction time is 1～30 minute, take out water flushing back airing, be the compound polyelectrolyte film of the present invention's preparation;
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00109129 CN1107532C (en) | 2000-06-09 | 2000-06-09 | Process for preparing compound polyelectrolyte (chitosan/sodium polyphosphate) membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00109129 CN1107532C (en) | 2000-06-09 | 2000-06-09 | Process for preparing compound polyelectrolyte (chitosan/sodium polyphosphate) membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1270078A true CN1270078A (en) | 2000-10-18 |
| CN1107532C CN1107532C (en) | 2003-05-07 |
Family
ID=4579445
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 00109129 Expired - Fee Related CN1107532C (en) | 2000-06-09 | 2000-06-09 | Process for preparing compound polyelectrolyte (chitosan/sodium polyphosphate) membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1107532C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1326600C (en) * | 2004-08-06 | 2007-07-18 | 天津科技大学 | Method of preparing polypropylene plate micropore membrane using thermo phase separation |
| CN100351007C (en) * | 2006-03-20 | 2007-11-28 | 天津大学 | Method for preparing molecular engram CS/TEOS hybridized film by separation of phenylalanine isomer |
| CN100444941C (en) * | 2007-03-27 | 2008-12-24 | 天津大学 | Method for preparing chitosan and surface modified Y-type zeolite hybridization liquid separation film |
| CN102321277A (en) * | 2011-07-12 | 2012-01-18 | 杭州电子科技大学 | Ionic crosslinked chitosan organic acid salt and anionized chitosan electrolyte composite film and preparation method thereof |
| CN101664569B (en) * | 2009-09-18 | 2012-10-03 | 浙江大学 | Preparation method of high strength sodium polyphosphate/chitosan hollow composite bar material |
| 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 |
-
2000
- 2000-06-09 CN CN 00109129 patent/CN1107532C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1326600C (en) * | 2004-08-06 | 2007-07-18 | 天津科技大学 | Method of preparing polypropylene plate micropore membrane using thermo phase separation |
| CN100351007C (en) * | 2006-03-20 | 2007-11-28 | 天津大学 | Method for preparing molecular engram CS/TEOS hybridized film by separation of phenylalanine isomer |
| CN100444941C (en) * | 2007-03-27 | 2008-12-24 | 天津大学 | Method for preparing chitosan and surface modified Y-type zeolite hybridization liquid separation film |
| CN101664569B (en) * | 2009-09-18 | 2012-10-03 | 浙江大学 | Preparation method of high strength sodium polyphosphate/chitosan hollow composite bar material |
| CN102321277A (en) * | 2011-07-12 | 2012-01-18 | 杭州电子科技大学 | Ionic crosslinked chitosan organic acid salt and anionized chitosan electrolyte composite film 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1107532C (en) | 2003-05-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8394277B2 (en) | Regenerative purification of a pretreated biomass stream | |
| CN106925142B (en) | Multi-separation-layer pervaporation membrane and preparation method thereof | |
| CN102743981B (en) | Preparation and application of sodium alginate pervaporation hybrid membrane | |
| CN100398188C (en) | Preparation method for hollow fiber osmosis vaporation permeable complex film | |
| CN102125811B (en) | Method for preparing polyvinyl alcohol-chitosan nano filtration membrane | |
| CN103331108B (en) | Polymer pervaporation membrane prepared by dialysis method after membrane formation and preparation method of polymer pervaporation membrane | |
| CN103028331A (en) | Preparation method of hydroxyethyl cellulose-silicon dioxide pervaporation hybrid membrane | |
| CN110743400B (en) | Preparation method of copper ion-doped alginate hydrogel antibacterial filtering membrane | |
| CN109304088A (en) | A kind of sea water desalination membrane of strong alkali-acid resistance and the preparation method and application thereof | |
| JPH02135134A (en) | Membrane for separating water-alcohol mixed liquid | |
| CN1107532C (en) | Process for preparing compound polyelectrolyte (chitosan/sodium polyphosphate) membrane | |
| CN106512728A (en) | Preparing method of anti-pollution super-thin nanofiltration membrane | |
| CN101259385B (en) | Quaterisation chitosan penetrating and evaporating film, preparation and application thereof | |
| JPH0553528B2 (en) | ||
| CN112899814B (en) | Bionic fiber functional material and preparation method and application thereof | |
| CN103007783A (en) | Preparation method of cellulose ether-ethyl orthosilicate pervaporation hybrid membrane | |
| CN109499391A (en) | A kind of preparation method and applications of cross-linking modified regenerated cellulose nanofiltration membrane | |
| CN108905642A (en) | A kind of sodium lignosulfonate being preferentially dehydrated/sodium alginate blending infiltrating and vaporizing membrane | |
| CN103055717B (en) | Preparation method for cellulose ether-sodium alginate-tetraethylortho silicate pervaporation and hybrid membrane | |
| US9084981B2 (en) | Regenerative purification of a pretreated biomass stream | |
| CN1093944A (en) | The preparation method of vapor permeable membrance and composition | |
| KR920010859B1 (en) | Membrane producing method | |
| CN110711491A (en) | Preparation of calcium lignosulphonate/sodium alginate pervaporation membrane for alcohol-water separation | |
| CN115414803B (en) | Acid-resistant polyimide ultrafiltration membrane and preparation method and application thereof | |
| JP3101357B2 (en) | Separation membrane for pervaporation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20030507 |