CN102698617B - Acid-alkali polymer blend pervaporation membrane, and preparation method and application thereof - Google Patents
Acid-alkali polymer blend pervaporation membrane, and preparation method and application thereof Download PDFInfo
- Publication number
- CN102698617B CN102698617B CN201210190267.2A CN201210190267A CN102698617B CN 102698617 B CN102698617 B CN 102698617B CN 201210190267 A CN201210190267 A CN 201210190267A CN 102698617 B CN102698617 B CN 102698617B
- Authority
- CN
- China
- Prior art keywords
- acid
- solution
- polymer
- film
- infiltrating
- 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.)
- Expired - Fee Related
Links
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses an acid-alkali polymer blend pervaporation membrane, and a preparation method and application thereof, and relates to a polymer material film. The preparation method comprises the following steps: soaking an acid polymer in an alkaline solution, and converting the acid polymer into a polymer in a salt form; respectively dissolving the polymer in the salt form and polyethyleneimine in a polar aprotic solvent, filtering off undissolved substances, and respectively obtaining 6 to 12 mass percent salt-form polymer solution and polyethyleneimine solution; adding the polyethyleneimine solution into the salt-form polymer solution to obtain a salt-form polymer and polyethyleneimine cast solution, and defoaming for later use; performing film casting on the casting solution on a glass plate to form a membrane, drying, and removing the membrane; and soaking the membrane in an acid solution, washing off excessive acid by using deionized water, and annealing the membrane to obtain the acid-alkali polymer blend pervaporation membrane. The acid-alkali polymer blend pervaporation membrane can be used for separating a methanol/methyl tertiary butyl ether mixture.
Description
Technical field
The present invention relates to a kind of polymer material film, especially relate to a kind of Acid-Base polyblend infiltrating and vaporizing membrane and preparation method thereof and purposes.
Background technology
Methyl tertiary butyl ether(MTBE) is widely used in fine chemistry industry production and unleaded gas production field.In producing unleaded gas process, it can be used as dopes for gasoline.Methyl tertiary butyl ether(MTBE) is made by methyl alcohol and isobutene reaction.In course of reaction, people often add excessive methyl alcohol to improve reaction conversion ratio.Yet under atmospheric pressure, when methanol quality mark is 14.3%, methyl alcohol/methyl tertbutyl ether mixture forms azeotropic system.This causes the appearance of methyl alcohol/methyl tertbutyl ether mixture separation problem.In traditional chemical process, the separation of methyl alcohol/methyl tertiary butyl ether(MTBE) realizes by extraction-rectification technique: first water extracts methyl alcohol, isolate methyl tertiary butyl ether(MTBE), then, water/carbinol mixture enters rectification cell and realizes separation, and last isolated methyl alcohol enters reactor again and participates in reaction.But this technological process is more complicated, and rectification cell energy consumption is wherein large, and running cost is high.
Pervaporation Technology is a kind of novel membrane separation technique.Generally believe at present, its separation principle is that each component of liquid mixture difference due to their dissolvings in film and diffusion rate under steam pressure difference promotes realizes separated.Compare with traditional rectifying, extraction and absorbing process, have that separative efficiency is high, equipment is simple, environmental friendliness, good stability, easy to operate, energy consumption is low, be easy to the advantages such as amplification.It is mainly used in organics dehydration, and underwater micro-organic matter removes and the separated three large fields of organic mixture.Especially in nearly boiling point mixture, mixed system that azeotropic mixture is high with temperature sensitivity separated, more show the advantage that it is unique.It also can constantly remove reaction product with biology and chemical reaction coupling, and reaction conversion ratio is significantly improved.During the nearly last ten years, developing new membrane material, being modified into membrane technology and improving permeability of the membrane is the common focus of paying close attention to of domestic and international academia and industrial quarters.
For the research of infiltration evaporation separation of methanol/methyl tertiary butyl ether(MTBE) work the earliest, be several pieces of documents (the Cen Y. of late 1980s, Wesslein M., Lichtenthaler R.N., Proc.of Fourth Intern.Conf.on Pervap.Proc.in theChem.Ind.[C], 1989:522) and United States Patent (USP) (US4774365 and US4960519).Then in succession carried out the research work of this respect all over the world, mainly around to selective high, the membrane material that flux is large of methyl alcohol.Wherein most study comprise cellulose acetate, modification of chitosan and inorganic material film, polyimides in addition, the research of the materials such as polyvinyl alcohol is report to some extent also.
Phenolphthalein lateral group polyarylether sulfone and phenolphthalein lateral group polyarylether ketone all belong to novel engineering plastics, except having good mechanical performance, also have excellent high temperature resistant hydrolysis, chemical stability and dimensional stability.Due to the introducing of phenolphthalein side group in main chain, the degree of crystallinity of material decreases, and the dissolubility in polar organic solvent is also improved.In view of above characteristic, they are separated at gas, and ultrafiltration/nanofiltration and amberplex field are applied and study.In addition, under concentrated sulfuric acid effect, this bi-material can also be introduced sulfonic acid group and obtain acidic polymer on main chain phenyl ring.The introducing of sulfonic acid group, has further improved hydrophily and the polarity of material, makes it be more applicable for the separation of the polar/non-polar system as methyl alcohol/methyl tertiary butyl ether(MTBE).Although the made infiltrating and vaporizing membrane of sulfonation material is very high to the separation factor of methyl alcohol/methyl tertiary butyl ether(MTBE) system, permeation flux is lower, needs certain methods to improve the separating property of film.Polymine is a kind of alkaline branch polymer with primary amine, secondary amine and tertiary amine group.It can obtain polyion polymer with above-mentioned two kinds of sulfonation material generation ionomers.Being introduced in of appropriate polymine is not obvious when affecting separation factor, can effectively improve the permeation flux of film.
In order to weigh the index of infiltration evaporation membrane separating property, mainly contain two, i.e. the permeation flux of film (J) and separation factor (α).
In formula, the quality that Q is penetrating fluid (kg); L is thickness (μ m); A is effective separating area (m of film
2); T is operating time (h); J is permeation flux (kg μ mm
-2h
-1).
In formula, X and Y are the mass fraction (%) of methyl alcohol and methyl tertiary butyl ether(MTBE) in feed liquid and penetrant.
Summary of the invention
The object of this invention is to provide a kind of Acid-Base polyblend infiltrating and vaporizing membrane and preparation method thereof and purposes.
The preparation method of described Acid-Base polyblend infiltrating and vaporizing membrane comprises the following steps:
1) acidic polymer is put into aqueous slkali and soak, described acidic polymer is converted into the polymer existing with salt form;
2) polymer existing with salt form and the polymine that step 1) are obtained are dissolved in respectively in polar non-solute, remove by filter insoluble matter, obtain respectively mass fraction and be 6%～12% the polymer solution existing with salt form and polyethyleneimine: amine aqueous solution;
3) by step 2) the polyethyleneimine: amine aqueous solution that obtains adds in the polymer solution existing with salt form, the polymer that obtains existing with salt form and polymine casting solution, stand-by after deaeration;
4), by casting solution casting film-forming on glass plate, after being dried, film is taken off;
5) film step 4) being obtained is placed in after acid solution immersion, washes away excessive acid, then by film annealing in process, obtain Acid-Base polyblend infiltrating and vaporizing membrane by deionized water.
In step 1), described acidic polymer can be selected from sulphonated phenol phthalein lateral group polyarylether sulfone or sulfonation phenolphthalein lateral group polyarylether ketone etc.; Described aqueous slkali can be selected from a kind of in sodium hydroxide solution, potassium hydroxide solution, lithium hydroxide solution etc.; The molar concentration of described sodium hydroxide solution, potassium hydroxide solution, lithium hydroxide solution can be 1molL
-1; The time of described immersion can be 48h.
In step 2) in, described polar non-solute can be selected from a kind of in 1-Methyl-2-Pyrrolidone, DMF, DMA, dimethyl sulfoxide (DMSO) etc.
In step 3), the mass ratio of the described polymer existing with salt form and polymine can be (1～9): 1.
In step 4), described dry condition can be at 130～140 ℃ forced air drying 4～12h; Described film is taken off, can in deionized water, film be taken off.
In step 5), described acid solution can adopt hydrochloric acid or sulfuric acid etc.; The concentration of described acid solution can be 4%～10%; The temperature of described immersion can be 20～100 ℃, and the time of immersion can be 20～30h; Describedly by deionized water, wash away excessive sour temperature and can be 60～80 ℃; The condition of described annealing in process can be film is placed in to vacuum drying chamber annealing in process 12～24h at 60～100 ℃.
The thickness of prepared Acid-Base polyblend infiltrating and vaporizing membrane is 23 ± 1 μ m.
Prepared Acid-Base polyblend infiltrating and vaporizing membrane can be used for the separation of methyl alcohol/methyl tertbutyl ether mixture.
In laboratory, adopt performance evaluating apparatus to measure permeation flux and the separation factor of film.Wherein effective separating area of film is 62.31cm
2, feed liquid flow is 50～80Lh
-1.Membrane module sees through side and adopts the method vacuumizing to keep infiltration component low pressure, and pressure maintains 5 ± 1mbar.After per-meate side steam-condensation is collected, the calculating permeation flux of weighing, with its each constituent mass mark of gas chromatographic analysis and calculate separation factor.
The present invention has the following advantages: (1) adopts after the form first acidic polymer is changed to salify the method with alkaline polymer blend again, has solved two kinds of inconsistent problems of the direct blend of polymer; (2) the structure homogeneous of institute's masking and reproducible; (3) prepared Acid-Base polyblend infiltrating and vaporizing membrane, when keeping sulfonation phenolphthalein lateral group polyarylether sulfone and the high separation factor of sulfonation phenolphthalein lateral group polyarylether ketone, has improved the permeation flux of film largely.
Accompanying drawing explanation
Fig. 1 is phenolphthalein lateral group polyarylether sulfone infiltrating and vaporizing membrane, the infrared spectrogram of sulfonation phenolphthalein lateral group polyarylether sulfone infiltrating and vaporizing membrane and sulfonation phenolphthalein lateral group polyarylether sulfone/polymine Acid-Base polyblend infiltrating and vaporizing membrane.In Fig. 1, abscissa is wave number Wavenumber (cm
-1); Curve a is phenolphthalein lateral group polyarylether sulfone, and curve b is sulfonation phenolphthalein lateral group polyarylether sulfone, and curve c is sulfonation phenolphthalein lateral group polyarylether sulfone/polymine.
Fig. 2 be in embodiment 1 sulfonation phenolphthalein lateral group polyarylether sulfone/polymine Acid-Base polyblend infiltrating and vaporizing membrane in the time of 40 ℃ to the separating property containing the feed liquid of methyl alcohol 15% with operating time change curve.In Fig. 2, abscissa is operating time (h); Left ordinate is permeation flux (kg μ mm
-2h
-1); Right ordinate is separation factor.
Fig. 3 is phenolphthalein lateral group polyarylether ketone infiltrating and vaporizing membrane, the infrared spectrogram of sulfonation phenolphthalein lateral group polyarylether ketone infiltrating and vaporizing membrane and sulfonation phenolphthalein lateral group polyarylether ketone/polymine Acid-Base polyblend infiltrating and vaporizing membrane.In Fig. 3, abscissa is wave number Wavenumber (cm
-1); Curve a is phenolphthalein lateral group polyarylether sulfone, and curve b is sulfonation phenolphthalein lateral group polyarylether sulfone, and curve c is sulfonation phenolphthalein lateral group polyarylether sulfone/polymine.
Fig. 4 be in embodiment 4 sulfonation phenolphthalein lateral group polyarylether ketone/polymine Acid-Base polyblend infiltrating and vaporizing membrane in the time of 40 ℃ to the separating property containing the feed liquid of methyl alcohol 15% with operating time change curve.In Fig. 4, abscissa is operating time (h); Left ordinate is permeation flux (kg μ mm
-2h
-1); Right ordinate is separation factor.
The specific embodiment
Below in conjunction with specific embodiment, the invention will be further described.
Comparison example 1
Preparation and the separating property of sulfonation phenolphthalein lateral group polyarylether sulfone infiltrating and vaporizing membrane:
At nitrogen protection and 50 ℃, 10g phenolphthalein lateral group polyarylether sulfone is dissolved in the 150mL concentrated sulfuric acid.50 ℃ of holding temperatures, reaction continues 18h.After question response finishes, product is slowly poured in a large amount of deionized waters, and vigorous stirring leave heat, then standing over night.After filtration, with a large amount of deionized water washing sediments until the pH value of filtrate between 6-7.Then, sediment is vacuum drying 4h at 60 ℃, obtains sulfonation degree and be 0.71 sulfonation phenolphthalein lateral group polyarylether sulfone.
Sulfonation phenolphthalein lateral group polyarylether sulfone is dissolved in in 1-Methyl-2-Pyrrolidone, to obtain mass fraction be 6% casting solution, elimination insoluble matter, stand-by after standing and defoaming.With pipette, measure 9mL casting solution on the glass plate (15cm * 15cm) of dried and clean, casting film-forming, then moves in air dry oven and dry 4h at 130 ℃.Finally in deionized water, film is taken off gently and in vacuum drying chamber at 80 ℃ annealing in process 12h, obtain sulfonation phenolphthalein lateral group polyarylether sulfone infiltrating and vaporizing membrane, the thickness of gained film is 23.5 μ m.Infrared spectrogram is shown in Fig. 1, in Fig. 1, and 1024cm
-1peak correspondence-the SO at place
3the symmetrical stretching vibration of O=S=O key in H.Its Pervaporation Separation is: at 40 ℃, and the methyl alcohol/methyl tertiary butyl ether(MTBE) mixture feed liquid that is 15% to methanol quality mark, J=2.42kg μ mm
-2h
-1, α=532.4.
Comparison example 2
Preparation and the separating property of sulfonation phenolphthalein lateral group polyarylether ketone infiltrating and vaporizing membrane:
At nitrogen protection and 40 ℃, 10g phenolphthalein lateral group polyarylether ketone is dissolved in the 180mL concentrated sulfuric acid.40 ℃ of holding temperatures, reaction continues 30h.After question response finishes, product is slowly poured in a large amount of deionized waters, and vigorous stirring leave heat, then standing over night.After filtration, with a large amount of deionized water washing sediments until the pH value of filtrate between 6～7.Then, sediment is vacuum drying 4h at 60 ℃, obtains sulfonation degree and be 0.83 sulfonation phenolphthalein lateral group polyarylether ketone.
Sulfonation phenolphthalein lateral group polyarylether ketone is dissolved in in 1-Methyl-2-Pyrrolidone, to obtain mass fraction be 6% casting solution, elimination insoluble matter, stand-by after standing and defoaming.With pipette, measure 9mL casting solution on the glass plate (15cm * 15cm) of dried and clean, casting film-forming, then moves in air dry oven and dry 4h at 130 ℃.Finally in deionized water, film is taken off gently and in vacuum drying chamber at 80 ℃ annealing in process 12h, obtain sulfonation phenolphthalein lateral group polyarylether ketone infiltrating and vaporizing membrane, the thickness of gained film is 22.7 μ m.Infrared spectrogram is shown in Fig. 3, in Fig. 3, and 1025cm
-1peak correspondence-the SO at place
3the symmetrical stretching vibration of O=S=O key in H.Its Pervaporation Separation is: at 40 ℃, and the methyl alcohol/methyl tertiary butyl ether(MTBE) mixture feed liquid that is 15% to methanol quality mark, J=2.21kg μ mm
-2h
-1, α=331.6.
Embodiment 1
The preparation process of sulfonation phenolphthalein lateral group polyarylether sulfone is with comparison example 1.By sulfonation phenolphthalein lateral group polyarylether sulfone at 1molL
-1sodium hydroxide solution in soak 48h, by deionized water, wash away excessive NaOH, dry, obtain the sulfonation phenolphthalein lateral group polyarylether sulfone existing with sodium-salt form.
Sulfonation phenolphthalein lateral group polyarylether sulfone and 3g polymine that 3g is existed with sodium-salt form are dissolved in respectively in 47g 1-Methyl-2-Pyrrolidone, remove by filter insoluble matter, make mass fraction and be 6% solution.In 18g sulfonation phenolphthalein lateral group polyarylether sulfolane solution, add 2g polyethyleneimine: amine aqueous solution, standing and defoaming after stirring, obtains the casting solution that sulfonation phenolphthalein lateral group polyarylether sulfone and polymine mass ratio are 9:1.With pipette, measure 9mL casting solution on the glass plate (15cm * 15cm) of dried and clean, casting film-forming, then moves in air dry oven and dry 4h at 130 ℃.In deionized water, film is taken off gently, be then at room temperature placed in concentration and be 4% hydrochloric acid solution and soak 24h, then in temperature is the deionized water of 60 ℃, wash away excessive hydrochloric acid.Finally in vacuum drying chamber at 80 ℃ annealing in process 12h, obtain sulfonation phenolphthalein lateral group polyarylether sulfone/polymine Acid-Base polyblend infiltrating and vaporizing membrane, the thickness of film is 23.1 μ m.Infrared spectrogram is shown in Fig. 1, and in polymine, primary amine is at 1665cm
-1characteristic peak and sulfonation phenolphthalein lateral group polyarylether sulfone at 1682cm
-1characteristic peak overlap.In this example Acid-Base polyblend infiltrating and vaporizing membrane under different operating condition to the separating property of methyl alcohol/methyl tertbutyl ether mixture in Table 1, and in the time of 40 ℃, the separating property containing the feed liquid of methyl alcohol 15% is shown in to Fig. 2 with operating time change curve.
The separating property of Acid-Base polyblend infiltrating and vaporizing membrane in table 1 embodiment 1
Embodiment 2
The preparation of the sulfonation phenolphthalein lateral group polyarylether sulfone existing with sodium-salt form is with embodiment 1.
Sulfonation phenolphthalein lateral group polyarylether sulfone and 3g polymine that 3g is existed with sodium-salt form are dissolved in respectively in 47g DMF, remove by filter insoluble matter, make mass fraction and be 6% solution.In 21g sulfonation phenolphthalein lateral group polyarylether sulfolane solution, add 9g polyethyleneimine: amine aqueous solution, standing and defoaming after stirring, obtains the casting solution that sulfonation phenolphthalein lateral group polyarylether sulfone and polymine mass ratio are 7:3.With pipette, measure 9mL casting solution on the glass plate (15cm * 15cm) of dried and clean, casting film-forming, then moves in air dry oven and dry 4h at 130 ℃.In deionized water, film is taken off gently, be then at room temperature placed in concentration and be 4% hydrochloric acid solution and soak 24h, then in temperature is the deionized water of 60 ℃, wash away excessive hydrochloric acid.Finally in vacuum drying chamber at 80 ℃ annealing in process 12h, obtain sulfonation phenolphthalein lateral group polyarylether sulfone/polymine Acid-Base polyblend infiltrating and vaporizing membrane, the thickness of film is 23.6 μ m.In this example Acid-Base polyblend infiltrating and vaporizing membrane under different operating condition to the separating property of methyl alcohol/methyl tertbutyl ether mixture in Table 2.
The separating property of Acid-Base polyblend infiltrating and vaporizing membrane in table 2 embodiment 2
Embodiment 3
The preparation process of sulfonation phenolphthalein lateral group polyarylether ketone is with comparison example 2.By sulfonation phenolphthalein lateral group polyarylether ketone at 1molL
-1sodium hydroxide solution in soak 48h, by deionized water, wash away excessive NaOH, dry, obtain the sulfonation phenolphthalein lateral group polyarylether ketone existing with sodium-salt form.
Sulfonation phenolphthalein lateral group polyarylether ketone and 3g polymine that 3g is existed with sodium-salt form are dissolved in respectively in 47g 1-Methyl-2-Pyrrolidone amine, remove by filter insoluble matter, make mass fraction and be 6% solution.In 18g sulfonation phenolphthalein lateral group polyarylether ketone solution, add 2g polyethyleneimine: amine aqueous solution, standing and defoaming after stirring, obtains the casting solution that sulfonation phenolphthalein lateral group polyarylether ketone and polymine mass ratio are 9:1.With pipette, measure 9mL casting solution on the glass plate (15cm * 15cm) of dried and clean, casting film-forming, then moves in air dry oven and dry 8h at 130 ℃.In deionized water, film is taken off gently, be then at room temperature placed in concentration and be 4% sulfuric acid solution and soak 24h, then in temperature is the deionized water of 70 ℃, wash away excessive hydrochloric acid.Finally in vacuum drying chamber at 80 ℃ annealing in process 12h, obtain sulfonation phenolphthalein lateral group polyarylether ketone/polymine Acid-Base polyblend infiltrating and vaporizing membrane, the thickness of film is 23.4 μ m.In this example Acid-Base polyblend infiltrating and vaporizing membrane under different operating condition to the separating property of methyl alcohol/methyl tertbutyl ether mixture in Table 3.
The separating property of Acid-Base polyblend infiltrating and vaporizing membrane in table 3 embodiment 3
Embodiment 4
The preparation of the sulfonation phenolphthalein lateral group polyarylether ketone existing with sodium-salt form is with embodiment 3.
Sulfonation phenolphthalein lateral group polyarylether ketone and 3g polymine that 3g is existed with sodium-salt form are dissolved in respectively 47gN, in dinethylformamide, remove by filter insoluble matter, make mass fraction and be 6% solution.In 18g sulfonation phenolphthalein lateral group polyarylether ketone solution, add 12g polyethyleneimine: amine aqueous solution, standing and defoaming after stirring, obtains the casting solution that sulfonation phenolphthalein lateral group polyarylether ketone and polymine mass ratio are 6:4.With pipette, measure 9mL casting solution on the glass plate (15cm * 15cm) of dried and clean, casting film-forming, then moves in air dry oven and dry 8h at 130 ℃.In deionized water, film is taken off gently, be then at room temperature placed in concentration and be 4% sulfuric acid solution and soak 24h, then in temperature is the deionized water of 70 ℃, wash away excessive hydrochloric acid.Finally in vacuum drying chamber at 80 ℃ annealing in process 12h, obtain sulfonation phenolphthalein lateral group polyarylether ketone/polymine Acid-Base polyblend infiltrating and vaporizing membrane, the thickness of film is 23.6 μ m.Infrared spectrogram is shown in Fig. 3,1025cm in figure
-1peak correspondence-the SO at place
3the symmetrical stretching vibration of O=S=O key in H, 1570cm
-1the corresponding polymine in peak in the characteristic peak of secondary amine.In this example Acid-Base polyblend infiltrating and vaporizing membrane under different operating condition to the separating property of methyl alcohol/methyl tertbutyl ether mixture in Table 4.
The separating property of Acid-Base polyblend infiltrating and vaporizing membrane in table 4 embodiment 4
And in the time of 40 ℃, the separating property of the feed liquid containing methyl alcohol 15% is shown in to Fig. 4 with operating time change curve.
Claims (5)
1. for separating of a preparation method for the Acid-Base polyblend infiltrating and vaporizing membrane of methyl alcohol/methyl tertbutyl ether mixture, it is characterized in that comprising the following steps:
1) acidic polymer is put into aqueous slkali and soak, described acidic polymer is converted into the polymer existing with salt form; Described acidic polymer is selected from sulfonation phenolphthalein lateral group polyarylether sulfone or sulfonation phenolphthalein lateral group polyarylether ketone;
2) by step 1) polymer existing with salt form and the polymine that obtain be dissolved in respectively in polar non-solute, remove by filter insoluble matter, obtain respectively mass fraction and be 6%～12% the polymer solution existing with salt form and polyethyleneimine: amine aqueous solution; Described polar non-solute is selected from a kind of in 1-Methyl-2-Pyrrolidone, DMF, DMA, dimethyl sulfoxide (DMSO); Described aqueous slkali is selected from a kind of in sodium hydroxide solution, potassium hydroxide solution, lithium hydroxide solution; The molar concentration of described sodium hydroxide solution, potassium hydroxide solution, lithium hydroxide solution is 1molL
-1;
3) by step 2) the polyethyleneimine: amine aqueous solution that obtains adds in the polymer solution existing with salt form, the polymer that obtains existing with salt form and polymine casting solution, stand-by after deaeration; It is described that to take polymer that salt form exists and the mass ratio of polymine be 1～9: 1;
4), by casting solution casting film-forming on glass plate, after being dried, film is taken off;
5) by step 4) after the film that obtains is placed in acid solution and soaks, by deionized water, wash away excessive acid, then by film annealing in process, obtain Acid-Base polyblend infiltrating and vaporizing membrane; Described acid solution adopts hydrochloric acid or sulfuric acid; The concentration of described acid solution is 4%～10%; The temperature of described immersion is 20～100 ℃, and the time of immersion is 20～30h; It is described that by deionized water, to wash away excessive sour temperature be 60～80 ℃; The condition of described annealing in process is for to be placed in vacuum drying chamber annealing in process 12～24h at 60～100 ℃ by film.
2. a kind of preparation method of the Acid-Base polyblend infiltrating and vaporizing membrane for separating of methyl alcohol/methyl tertbutyl ether mixture as claimed in claim 1, is characterized in that in step 1) in, the time of described immersion is 48h.
3. a kind of preparation method of the Acid-Base polyblend infiltrating and vaporizing membrane for separating of methyl alcohol/methyl tertbutyl ether mixture as claimed in claim 1, is characterized in that in step 4) in, described dry condition forced air drying 4～12h at 130～140 ℃; Described film being taken off, is in deionized water, film to be taken off.
4. the Acid-Base polyblend infiltrating and vaporizing membrane that as described in any one in claim 1～3 prepared by preparation method.
5. the application of the Acid-Base polyblend infiltrating and vaporizing membrane that as described in any one in claim 1～3 prepared by preparation method in separation of methanol/methyl tertbutyl ether mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210190267.2A CN102698617B (en) | 2012-06-08 | 2012-06-08 | Acid-alkali polymer blend pervaporation membrane, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210190267.2A CN102698617B (en) | 2012-06-08 | 2012-06-08 | Acid-alkali polymer blend pervaporation membrane, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102698617A CN102698617A (en) | 2012-10-03 |
| CN102698617B true CN102698617B (en) | 2014-10-08 |
Family
ID=46891841
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210190267.2A Expired - Fee Related CN102698617B (en) | 2012-06-08 | 2012-06-08 | Acid-alkali polymer blend pervaporation membrane, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102698617B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103386255B (en) * | 2013-08-15 | 2015-08-05 | 中国科学院长春应用化学研究所 | A kind of milipore filter or NF membrane and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1071100A (en) * | 1991-09-27 | 1993-04-21 | 中国科学院大连化学物理研究所 | The preparation of sulfonated polyary-ether-sulfone nanometer filter film |
| CN101724165A (en) * | 2009-11-20 | 2010-06-09 | 清华大学 | Epoxy crosslinking sulfonated polyaryletherketone proton exchange membrane material and preparation method thereof |
| CN101721926A (en) * | 2009-12-01 | 2010-06-09 | 大连理工大学 | Sulfonated copolymerized arylene ether ketone compound nano filtration membrane containing Chinazolin ketone and preparation method thereof |
| CN101875722A (en) * | 2009-11-27 | 2010-11-03 | 清华大学 | Method for preparing polybenzimidazole/sulfonated polymer composite proton exchange membrane material |
-
2012
- 2012-06-08 CN CN201210190267.2A patent/CN102698617B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1071100A (en) * | 1991-09-27 | 1993-04-21 | 中国科学院大连化学物理研究所 | The preparation of sulfonated polyary-ether-sulfone nanometer filter film |
| CN101724165A (en) * | 2009-11-20 | 2010-06-09 | 清华大学 | Epoxy crosslinking sulfonated polyaryletherketone proton exchange membrane material and preparation method thereof |
| CN101875722A (en) * | 2009-11-27 | 2010-11-03 | 清华大学 | Method for preparing polybenzimidazole/sulfonated polymer composite proton exchange membrane material |
| CN101721926A (en) * | 2009-12-01 | 2010-06-09 | 大连理工大学 | Sulfonated copolymerized arylene ether ketone compound nano filtration membrane containing Chinazolin ketone and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| "改性酚酞侧基聚芳醚酮渗透蒸发膜的制备及其醋酸脱水性能研究";陈建华;《中国博士学位论文全文数据库 工程科技Ⅰ辑》;20090721(第08期);第57页第3段-第58页第2段,图4-1（c） * |
| 陈建华."改性酚酞侧基聚芳醚酮渗透蒸发膜的制备及其醋酸脱水性能研究".《中国博士学位论文全文数据库 工程科技Ⅰ辑》.2009,(第08期),第57-60页. |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102698617A (en) | 2012-10-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105169970A (en) | Preparation method for polydopamine-modified polyamide composite forward osmosis membrane | |
| CN102773024B (en) | Method for preparing hollow fiber type forward osmotic membrane | |
| CN104785121A (en) | Three-layer composite membrane of sodium alginate, polydopamine-polyethyleneimine and polyacrylonitrile, and preparation and application of three-layer composite membrane | |
| CN110479102A (en) | Pervaporation desalination anisotropic membrane and preparation method thereof | |
| CN101721927B (en) | Ultrafiltration membrane copoly(phthalazinone aryl ether sulfone) and preparation method thereof | |
| CN103342631A (en) | Process for separating propylene glycol monomethyl ether aqueous solution by using double membrane coupling technology | |
| CN103464006A (en) | Preparation of PDMS/PVDF (polydimethylsiloxane/polyvinylidene fluoride) blended microporous film | |
| CN102516654B (en) | Out-phase ion exchange composite film and preparation method thereof | |
| CN102489178B (en) | Method for preparing molybdenum disulfide pervaporation membrane for separating alcohol-containing wastewater | |
| CN104209024A (en) | Polyarylenesulfidesulfone/sulfonated polymer composite separation membrane and preparation method thereof | |
| CN102921307B (en) | Preparation method of high-performance forward osmosis membrane | |
| CN110975619B (en) | Reverse osmosis membrane rinsing system and rinsing method thereof | |
| CN102698617B (en) | Acid-alkali polymer blend pervaporation membrane, and preparation method and application thereof | |
| CN105435645B (en) | A kind of composite nanometer filtering film and preparation method thereof | |
| CN103788364A (en) | Carboxyl-containing polyethersulfone, ultrafiltration membrane, and preparation methods of the carboxyl-containing polyethersulfone and the ultrafiltration membrane | |
| CN103642063A (en) | Preparation method of mythyl p-hydroxybenzoate molecular imprinting composite membrane and application thereof | |
| CN103263858A (en) | Cross-linking hyperbranched polymer composite nano filtration membrane prepared by one step method in water phase, preparation method and application | |
| CN110813107A (en) | High-flux low-pressure composite reverse osmosis membrane and preparation method thereof | |
| CN102701327B (en) | Application of hydrophilic Ge-ZSM-5 molecular sieve membrane to separation of organics/water system | |
| CN100551505C (en) | A kind of diffusion barrier that is used for separation of methanol/dimethyl carbonate azeotrope and preparation method thereof | |
| CN103191652A (en) | Preparation method and application of composite ultrafiltration membrane for separating salicylic acid in aspirin | |
| CN111249909A (en) | Modification method of reverse osmosis membrane for drinking water purification | |
| CN103848718A (en) | Method for preparing electronic-grade isopropanol by virtue of ion exchange fibers and microporous membrane coupling columns | |
| CN107441953B (en) | Preparation method and application of negative charge polyelectrolyte/molecular sieve composite membrane | |
| CN109382005B (en) | Composite nano filtering boron film and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20141008 Termination date: 20200608 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |