CN102743981A - Preparation and application of sodium alginate pervaporation hybrid membrane - Google Patents
Preparation and application of sodium alginate pervaporation hybrid membrane Download PDFInfo
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- CN102743981A CN102743981A CN2012102479990A CN201210247999A CN102743981A CN 102743981 A CN102743981 A CN 102743981A CN 2012102479990 A CN2012102479990 A CN 2012102479990A CN 201210247999 A CN201210247999 A CN 201210247999A CN 102743981 A CN102743981 A CN 102743981A
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Abstract
The invention discloses a sodium alginate pervaporation hybrid membrane for separating aqueous methanol solution, a preparation method and an application of the sodium alginate pervaporation hybrid membrane. Raw materials of the sodium alginate pervaporation hybrid membrane include sodium alginate and inorganic aid. The preparation method for the sodium alginate pervaporation hybrid membrane includes the following steps: mixing the sodium alginate and the inorganic aid to obtain membrane casting solution; and preparing the sodium alginate pervaporation hybrid membrane for separating the aqueous methanol solution by the aid of a solution casting method. The prepared organic-inorganic hybrid membrane is a highly hydrophilic pervaporation membrane, applicable to dehydrating of organic solvent, has good separation effect compared with other membranes which are difficult to separate the aqueous methanol solution, and meanwhile, has good separation effect for aqueous solutions such as aqueous ethanol solution, aqueous isopropanol solution.
Description
Technical field
The invention belongs to the diffusion barrier field, be specifically related to a kind of infiltration evaporation hybridized film, preparation method and application thereof that is used to separate alcohol solution.
Background technology
Methanol diesel-oil is because best in quality, good stability, and market is workable, makes it in field of biodiesel oil great application prospect arranged, and its popularization meets China's new forms of energy policy and the strategy of sustainable development.At present, production of biodiesel enterprise adopts methods such as ion exchange resin, rectifying to separate the purification methanol aqueous solution usually, but its process is complicated, and energy consumption is higher, and the production cost of biodiesel is increased, and advantage is not obvious in market competition.
Infiltration evaporation is to be used for the new membrane technology that liquid mixture separates, and utilizes that permeable pressure head is driving force between each component, relies on each component in film, to dissolve and reach with diffusion rate difference to separate purpose.The outstanding advantage of this technology is low energy consumption, and simple to operate, process is pollution-free.At present, be tending towards ripe about the infiltration evaporation isolation technics of alcohol solutions such as ethanol, isopropyl alcohol, tentatively realized industrialization, but the infiltration evaporation of methanol aqueous solution separates and still be in laboratory stage, relevant research report both domestic and external is few.Reason is to compare with ethanol, isopropyl alcohol equimolecular, and the molecular structure of methyl alcohol, polarity are very similar with water, cause methyl alcohol to be competed mutually with the suction-operated of water in diffusion barrier, thereby makes methyl alcohol and shipwreck to separate.
The high flux sodium alginate that one Chinese patent application 200710071441.0 proposes and the preparation method of dimethyl-allyl-ammonium complex compound infiltrating and vaporizing membrane; Through sodium alginate and the hydrolysis again of dimethyldiallylammonium crosslinking, realize not only improving membrane separating property but also improved membrane flux.But shortcomings such as this method preparation is a kind of separating layer of pure organic polymer, in use, exists the film temperature tolerance relatively poor, and mechanical strength is not high, and service life is short, using value is limited in actual production.
One Chinese patent application 200710040764.3 discloses a kind of preparation method of organic and inorganic infiltration vaporization separation film; Through in the chemical vapour deposition (CVD) of macropore ceramic membrane surface, glycerol polymerization and ring-opening reaction, having prepared is the hydrophily compounding permeation vaporizing film of carrier with the inorganic ceramic membrane.This film is respond well when the separation of methanol aqueous solution, but this method prepares the process complicacy, and severe reaction conditions is with high costs, and needs to use the bigger organic solvent of toxicity in the preparation process.
One Chinese patent application 200610052633.2 discloses a kind of preparation method of doughnut osmosis vaporation permeable complex film, and polyvinyl alcohol and sodium alginate blended cross linking are made hollow fiber composite membrane.This method technology is simple, easy to operate, is suitable for and the separating of multiple alcohol solution.But hollow-fibre membrane in use is prone to the fracture of wire problem, and resistance tocrocking is poor, and system is difficult for operation steady in a long-term, and flat sheet membrane has greater advantage in this respect.
At present, do not see the research of sodium alginate hybridized film in the patent, sodium alginate is a kind of osmotic, evaporating and dewatering membrane material commonly used; Its wide material sources, cheap, and hydrophily is better; But pure sodium alginate film mechanical strength is not enough, can not satisfy the infiltration evaporation service condition.Phosphotungstic acid, silico-tungstic acid or heteropoly acid etc. belong to inorganic heteropoly acid; Has special discrete molecules structure; Hydrone there is very strong absorption property; Be introduced in the sodium alginate medium, not only can improve the not enough shortcoming of sodium alginate film dynamic performance, also significantly improved its Pervaporation Separation.
Summary of the invention
The purpose of this invention is to provide a kind of high selectivity, high flux, the preparation method of the hybrid organic-inorganic film that has good stability reaches in the Separate Efficiency Study to methanol aqueous solution.
One aspect of the present invention relates to a kind of infiltration evaporation hybridized film that is used for the separation of methanol aqueous solution; It is characterized in that; The raw material of preparation hybridized film comprises sodium alginate and inorganic acid, and the step of preparation hybridized film comprises: utilize sodium alginate and inorganic acid to carry out blend hydridization and obtain casting solution; Utilize solution casting method to process to be used for the sodium alginate infiltration evaporation hybridized film of the separation of methanol aqueous solution.
The present invention also relates to the preparation method of the infiltration evaporation hybridized film of the above-mentioned separation of methanol aqueous solution on the other hand, it is characterized in that, comprises the steps:
B) configuration of casting solution: the preparation sodium alginate aqueous solution, inorganic acid is mixed with the aqueous solution, inorganic acid solution is slowly joined in the sodium alginate soln, continue to stir formation homogeneous phase transparent solution;
B) basement membrane is handled: basement membrane is cut into certain size, is soaked in the organic solution of 2-5wt% polyacrylonitrile, keep 20-40min under the room temperature, then, dry under the room temperature successively in 25-35 ℃, 50-70 ℃ following water-bath 1-2h, and for use;
C) film: basement membrane is placed mould; With scraping hymenotome casting solution evenly is coated on membrane surface; Then more than 60-70 ℃ of following vacuum drying 12h, the gained film is soaked in the crosslinker solution crosslinked, remove unreacted impurity with the deionized water cyclic washing at last; Drying obtains the sodium alginate hybridized film.
In a preferred implementation of the present invention, it is characterized in that the mass fraction of inorganic acid is 0-8% among the described step a, does not comprise 0, is preferably 2-6%; The mass fraction of sodium alginate soln is 2-10%, is preferably 4-6%.
In a preferred implementation of the present invention, it is characterized in that the inorganic acid among the described step a is phosphotungstic acid, silico-tungstic acid or heteropoly acid, is preferably phosphotungstic acid.
In a preferred implementation of the present invention, it is characterized in that, also comprise the pH of the homogeneous phase solution of adjusting among the described step a, make it between 6-8.Gained solution is filtered through 2# sand mold funnel, remove insoluble matter, leave standstill, deaeration gets casting solution;
In a preferred implementation of the present invention, it is characterized in that the organic solvent that uses among the described step b is N, dinethylformamide, N, N-dimethylacetylamide or oxolane.
In a preferred implementation of the present invention, it is characterized in that mould is any in glass mold, the polytetrafluoroethylene (PTFE) mould among the described step c.
In a preferred implementation of the present invention, it is characterized in that, said crosslinking agent be in glutaraldehyde, phosphoric acid or the citric acid one or more, glutaraldehyde preferably.
The present invention also relates to the prepared infiltration evaporation hybridized film that is used for the separation of methanol aqueous solution that obtains of above-mentioned preparation method on the other hand.
The present invention also relates to the application of above-mentioned hybridized film in the separation of methanol aqueous solution on the other hand.
The hybrid organic-inorganic film that the present invention makes is a kind of infiltrating and vaporizing membrane of high-hydrophilic; Be applicable to the dehydration of organic solvent; Be difficult to realize that to other films the methanol aqueous solution that effectively separates has good separating effect; Simultaneously, the aqueous solution such as ethanol, isopropyl alcohol also there is separating effect preferably.
Description of drawings:
Fig. 1 is the surface scan Electronic Speculum figure of sodium alginate/phosphotungstic acid (6wt%) hybridized film of the present invention's preparation;
Fig. 2 is the section surface sweeping Electronic Speculum figure of sodium alginate/phosphotungstic acid (6wt%) hybridized film of the present invention's preparation.
The specific embodiment
Below in conjunction with accompanying drawing and specific embodiment the present invention is elaborated.
Embodiment 1:
Take by weighing the 4g sodium alginate and be dissolved in the 46g distilled water, stir down fully, take by weighing the 0.08g phosphotungstic acid until the sodium alginate dissolving at 70 ℃; 50g distilled water; Under the condition of supersonic frequency 50KHz, dissolve 30min, slowly join then in the sodium alginate soln, continue to stir 24h; Regulate pH between 6-8 with alkali, the mass percent of sodium alginate maintains 4% in the solution.Solution filters through sand core funnel, standing and defoaming.Nonwoven is placed the polyacrylonitrile solution 30min of mass fraction 2%, successively, dry under the room temperature in 30 ℃, 60 ℃ following water-bath 1-2h.The casting solution that configures evenly is coated in membrane surface with scraping hymenotome, and 60-70 ℃ of following vacuum drying 24h places crosslinker solution to carry out cross-linking reaction hybridized film; Crosslinker solution is the acetone-water solution (1: 2 of 100mL; V/v), 2.5mL hydrochloric acid, 2.5mL glutaraldehyde.Treat crosslinked fully after, remove unreacted impurity with the distilled water cyclic washing, drying under the room temperature.
The film of gained carries out the osmotic, evaporating and dewatering experiment of methanol aqueous solution; Feed liquid is the methanol aqueous solution of variable concentrations, places there-necked flask, and is heated by water-bath; Temperature maintenance is at 30 ℃; Feed liquid gets in the membrane module through peristaltic pump control flow velocity, refluxes then in there-necked flask, and the effective area of film is 12.56cm
2, treat the about 2h of whole system stable operation after, the vavuum pump of opening the film downstream vacuumizes, vacuum is 0.1MPa, penetrant is collected through cold-trap (liquid nitrogen, its fusing point be-196 ℃) cooling, lasting 5h.It is as shown in the table for its performance:
| Feed concentration (methyl alcohol wt%) | Permeation flux J (g/m 2h) | Separation factor alpha |
| 80 | 398 | 124 |
| 85 | 320 | 156 |
| 90 | 250 | 303 |
| 95 | 203 | 554 |
In the table, permeation flux
separation factor
In the formula, W is the weight of collecting in the cold-trap through thing (g), and A is membrane area (m
2), t is operating time (h), P
W, F
WBe respectively the content of water in per-meate side and the feed liquid, P
M, F
MBe respectively the content of alcohol in per-meate side and the feed liquid.
Embodiment 2:
Like the processing step of instance 1, wherein, the addition that only changes phosphotungstic acid is 0.16g, processes sodium alginate hybrid organic-inorganic film of the present invention, and its performance is as shown in the table:
| Feed concentration (methyl alcohol WT%) | Permeation flux J (g/m 2h) | Separation factor alpha |
| 80 | 459 | 137 |
| 85 | 345 | 202 |
| 90 | 284 | 344 |
| 95 | 266 | 571 |
Embodiment 3:
Like the processing step of instance 1, wherein, the addition that only changes phosphotungstic acid is 0.24g, processes sodium alginate hybrid organic-inorganic film of the present invention, and its performance is as shown in the table:
| Feed concentration (methyl alcohol wt%) | Permeation flux J (g/m 2h) | Separation factor alpha |
| 80 | 597 | 148 |
| 85 | 433 | 214 |
| 90 | 349 | 378 |
| 95 | 319 | 657 |
When being understood that; Specific embodiment of the present invention only is a property illustrative purposes presented for purpose of illustration; It limits protection scope of the present invention never in any form; Those skilled in the art can improve or conversion according to above-mentioned explanation, and all these improvement and conversion all should belong to the protection domain of accompanying claims of the present invention.
Claims (10)
1. an infiltration evaporation hybridized film that is used for the separation of methanol aqueous solution is characterized in that, the raw material of preparation hybridized film comprises sodium alginate and inorganic acid, and the step of preparation hybridized film comprises: utilize sodium alginate and inorganic acid to carry out blend hydridization and obtain casting solution; Utilize solution casting method to process to be used for the sodium alginate infiltration evaporation hybridized film of the separation of methanol aqueous solution.
2. the preparation method who is used for the infiltration evaporation hybridized film of the separation of methanol aqueous solution according to claim 1 is characterized in that, comprises the steps:
A) configuration of casting solution: the preparation sodium alginate aqueous solution, inorganic acid is mixed with the aqueous solution, inorganic acid solution is slowly joined in the sodium alginate soln, continue to stir formation homogeneous phase transparent solution;
B) basement membrane is handled: basement membrane is cut into certain size, is soaked in the organic solution of 2-5wt% polyacrylonitrile, keep 20-40min under the room temperature, then, dry under the room temperature successively in 25-35 ℃, 50-70 ℃ following water-bath 1-2h, and for use;
C) film: basement membrane is placed mould; With scraping hymenotome casting solution evenly is coated on membrane surface; Then more than 60-70 ℃ of following vacuum drying 12h, the gained film is soaked in the crosslinker solution crosslinked, remove unreacted impurity with the deionized water cyclic washing at last; Drying obtains the sodium alginate hybridized film.
3. the preparation method who is used for the infiltration evaporation hybridized film of the separation of methanol aqueous solution according to claim 2 is characterized in that the mass fraction of inorganic acid is 0-8% among the described step a, does not comprise 0, is preferably 2-6%; The mass fraction of sodium alginate soln is 2-10%, is preferably 4-6%.
4. the preparation method who is used for the infiltration evaporation hybridized film of the separation of methanol aqueous solution as claimed in claim 2 is characterized in that the inorganic acid among the described step a is phosphotungstic acid, silico-tungstic acid or heteropoly acid, is preferably phosphotungstic acid.
5. the preparation method who is used for the infiltration evaporation hybridized film of the separation of methanol aqueous solution as claimed in claim 2 is characterized in that, also comprises the pH of the homogeneous phase solution of adjusting among the described step a, makes it between 6-8.Gained solution is filtered through 2# sand mold funnel, remove insoluble matter, leave standstill, deaeration gets casting solution.
6. the preparation method who is used for the infiltration evaporation hybridized film of the separation of methanol aqueous solution as claimed in claim 2 is characterized in that the organic solvent that uses among the described step b is N, dinethylformamide, N, N-dimethylacetylamide or oxolane.
7. the preparation method who is used for the infiltration evaporation hybridized film of the separation of methanol aqueous solution as claimed in claim 2 is characterized in that, mould is any in glass mold, the polytetrafluoroethylene (PTFE) mould among the described step c.
8. the preparation method who is used for the infiltration evaporation hybridized film of the separation of methanol aqueous solution as claimed in claim 2 is characterized in that, said crosslinking agent be in glutaraldehyde, phosphoric acid or the citric acid one or more, glutaraldehyde preferably.
9. the prepared infiltration evaporation hybridized film that is used for the separation of methanol aqueous solution that obtains of any described preparation method of claim 2-8.
10. the application of the described hybridized film of claim 9 in the separation of methanol aqueous solution.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103028331A (en) * | 2013-01-03 | 2013-04-10 | 盐城工学院 | Preparation method of hydroxyethyl cellulose-silicon dioxide pervaporation hybrid membrane |
| CN103055717A (en) * | 2013-01-03 | 2013-04-24 | 盐城工学院 | Preparation method for cellulose ether-sodium alginate-tetraethylortho silicate pervaporation and hybrid membrane |
| CN103446899A (en) * | 2013-09-13 | 2013-12-18 | 天津工业大学 | Organic and inorganic surface chemically-crosslinked alginate-based hybrid hydrogel filter membrane, and preparation method thereof |
| CN103894074A (en) * | 2012-12-28 | 2014-07-02 | 中国科学院上海高等研究院 | Novel hybrid membrane as well as preparation method and application thereof |
| CN104190271A (en) * | 2014-08-19 | 2014-12-10 | 苏州君康医疗科技有限公司 | Polyether sulfone/alginate composite hollow fiber membrane and preparation method thereof |
| CN103446898B (en) * | 2013-09-13 | 2015-06-03 | 天津工业大学 | Alginate-base organic-inorganic composite hydrogel filtering membrane and preparation method thereof |
| CN104801208B (en) * | 2015-04-07 | 2017-04-19 | 天津大学 | Sodium alginate-flaky ZIF-8 hybrid composite membrane, and preparation and application thereof |
| CN106587903A (en) * | 2016-12-15 | 2017-04-26 | 苏州纽东精密制造科技有限公司 | Environment-friendly film for car roof |
| CN107376664A (en) * | 2017-08-09 | 2017-11-24 | 北京工业大学 | A kind of preparation method towards acid system selfreparing seperation film |
| CN108905642A (en) * | 2018-09-17 | 2018-11-30 | 北京林业大学 | A kind of sodium lignosulfonate being preferentially dehydrated/sodium alginate blending infiltrating and vaporizing membrane |
| CN109012220A (en) * | 2018-10-15 | 2018-12-18 | 北京林业大学 | A kind of preparation of New Two Dimensional material/sodium alginate infiltrating and vaporizing membrane |
| CN109534818A (en) * | 2017-09-22 | 2019-03-29 | 萍乡市普天高科实业有限公司 | Porous ceramics film preparation mold and method |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103894074A (en) * | 2012-12-28 | 2014-07-02 | 中国科学院上海高等研究院 | Novel hybrid membrane as well as preparation method and application thereof |
| CN103894074B (en) * | 2012-12-28 | 2017-09-29 | 中国科学院上海高等研究院 | Novel hybride film and its preparation and application |
| CN103028331A (en) * | 2013-01-03 | 2013-04-10 | 盐城工学院 | Preparation method of hydroxyethyl cellulose-silicon dioxide pervaporation hybrid membrane |
| CN103055717A (en) * | 2013-01-03 | 2013-04-24 | 盐城工学院 | Preparation method for cellulose ether-sodium alginate-tetraethylortho silicate pervaporation and hybrid membrane |
| CN103055717B (en) * | 2013-01-03 | 2014-11-26 | 盐城工学院 | Preparation method for cellulose ether-sodium alginate-tetraethylortho silicate pervaporation and hybrid membrane |
| CN103446899A (en) * | 2013-09-13 | 2013-12-18 | 天津工业大学 | Organic and inorganic surface chemically-crosslinked alginate-based hybrid hydrogel filter membrane, and preparation method thereof |
| CN103446899B (en) * | 2013-09-13 | 2015-05-06 | 天津工业大学 | Organic and inorganic surface chemically-crosslinked alginate-based hybrid hydrogel filter membrane, and preparation method thereof |
| CN103446898B (en) * | 2013-09-13 | 2015-06-03 | 天津工业大学 | Alginate-base organic-inorganic composite hydrogel filtering membrane and preparation method thereof |
| CN104190271B (en) * | 2014-08-19 | 2016-06-01 | 苏州君康医疗科技有限公司 | A kind of polyethersulfone/alginates composite hollow fiber membrane and its preparation method |
| CN104190271A (en) * | 2014-08-19 | 2014-12-10 | 苏州君康医疗科技有限公司 | Polyether sulfone/alginate composite hollow fiber membrane and preparation method thereof |
| CN104801208B (en) * | 2015-04-07 | 2017-04-19 | 天津大学 | Sodium alginate-flaky ZIF-8 hybrid composite membrane, and preparation and application thereof |
| CN106587903A (en) * | 2016-12-15 | 2017-04-26 | 苏州纽东精密制造科技有限公司 | Environment-friendly film for car roof |
| CN107376664A (en) * | 2017-08-09 | 2017-11-24 | 北京工业大学 | A kind of preparation method towards acid system selfreparing seperation film |
| CN109534818A (en) * | 2017-09-22 | 2019-03-29 | 萍乡市普天高科实业有限公司 | Porous ceramics film preparation mold and method |
| CN108905642A (en) * | 2018-09-17 | 2018-11-30 | 北京林业大学 | A kind of sodium lignosulfonate being preferentially dehydrated/sodium alginate blending infiltrating and vaporizing membrane |
| CN109012220A (en) * | 2018-10-15 | 2018-12-18 | 北京林业大学 | A kind of preparation of New Two Dimensional material/sodium alginate infiltrating and vaporizing membrane |
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