CN100540125C - Electric field driving polyelectrolyte is the preparation method of self assembly infiltrating and vaporizing membrane layer by layer - Google Patents
Electric field driving polyelectrolyte is the preparation method of self assembly infiltrating and vaporizing membrane layer by layer Download PDFInfo
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- 229920000867 polyelectrolyte Polymers 0.000 title claims abstract description 52
- 239000012528 membrane Substances 0.000 title claims abstract description 50
- 238000001338 self-assembly Methods 0.000 title claims abstract description 28
- 230000008016 vaporization Effects 0.000 title claims abstract description 28
- 230000005684 electric field Effects 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 230000004907 flux Effects 0.000 claims abstract description 41
- 125000002091 cationic group Chemical group 0.000 claims abstract description 16
- 229920001448 anionic polyelectrolyte Polymers 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 67
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 48
- 239000008367 deionised water Substances 0.000 claims description 40
- 229910052757 nitrogen Inorganic materials 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 229910002804 graphite Inorganic materials 0.000 claims description 16
- 239000010439 graphite Substances 0.000 claims description 16
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 15
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 14
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 9
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 9
- 235000019270 ammonium chloride Nutrition 0.000 claims description 8
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 6
- 229940059939 kayexalate Drugs 0.000 claims description 6
- 229940005550 sodium alginate Drugs 0.000 claims description 6
- 239000000661 sodium alginate Substances 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 5
- 235000010413 sodium alginate Nutrition 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 4
- -1 anionic ion Chemical class 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 14
- 150000001875 compounds Chemical class 0.000 abstract description 13
- 238000001035 drying Methods 0.000 abstract description 9
- 238000001704 evaporation Methods 0.000 abstract description 8
- 230000008595 infiltration Effects 0.000 abstract description 8
- 238000001764 infiltration Methods 0.000 abstract description 8
- 230000008020 evaporation Effects 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 70
- 239000000243 solution Substances 0.000 description 47
- 239000007788 liquid Substances 0.000 description 45
- 239000010410 layer Substances 0.000 description 32
- 230000018044 dehydration Effects 0.000 description 12
- 238000006297 dehydration reaction Methods 0.000 description 12
- 206010013786 Dry skin Diseases 0.000 description 8
- 230000007062 hydrolysis Effects 0.000 description 8
- 238000006460 hydrolysis reaction Methods 0.000 description 8
- 229920002873 Polyethylenimine Polymers 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
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- 230000010148 water-pollination Effects 0.000 description 3
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- MEYZYGMYMLNUHJ-UHFFFAOYSA-N tunicamycin Natural products CC(C)CCCCCCCCCC=CC(=O)NC1C(O)C(O)C(CC(O)C2OC(C(O)C2O)N3C=CC(=O)NC3=O)OC1OC4OC(CO)C(O)C(O)C4NC(=O)C MEYZYGMYMLNUHJ-UHFFFAOYSA-N 0.000 description 1
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- Separation Using Semi-Permeable Membranes (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention discloses a kind of in the electric field driving polyelectrolyte preparation method of self assembly infiltrating and vaporizing membrane layer by layer.(1) certain density cationic polyelectrolyte of preparation and anionic polyelectrolyte solution; (2), regulate in the assembling pond electric-field intensity between two electrodes by changing in the assembling pond distance and output voltage between positive and negative electrode; (3) with electronegative counterdie, the vertical electric field direction is inserted in the assembling pond of cationic polyelectrolyte solution, carries out the assembling of positive charge layer within a certain period of time, takes out the back cleaning-drying; The above-mentioned film that oneself is had positive charge inserts in the assembling pond of anionic polyelectrolyte solution, and the same negative electrical charge layer that carries out is assembled.So circulate repeatedly, until the polyelectrolyte self assembly osmosis vaporizing compound membrane that obtains the required number of plies.The present invention adopts the following self assembly infiltration evaporation membrane flux of electric field method preparation big, and good separating effect has overcome the essential assembling shortcoming that the number of plies is many, workload is big of self assembly infiltrating and vaporizing membrane under the non-electric field simultaneously.
Description
Technical field
The present invention relates to macromolecular material preparation and film separation field, relate in particular to a kind of electric field driving polyelectrolyte preparation method of self assembly infiltrating and vaporizing membrane layer by layer.
Background technology
Infiltration evaporation is a kind of novel film separation process of researching and developing out in recent decades, and under the liquid mixture steam pressure difference promoted, it utilized each component to realize separating feed liquid mixture with the different of diffusion rate by the dissolving of film.Compare with separating technologies such as traditional rectifying, absorption, extractions, it has separative efficiency height, simple, easy to operate, the low power consumption and other advantages of equipment.Separating nearly boiling point mixture, azeotropic mixture, during the high mixed system of temperature sensitivity, infiltration evaporation especially shows its special advantages.Nearly ten come, and commercial Application circle both domestic and external, academia continue to carry out to the research of infiltration evaporation especially organics dehydration, are all obtaining very big progress aspect theoretical and the practical application.
The hydrophily of the diffusion barrier that is used to dewater is quite important to its infiltration evaporation performance.Polyelectrolyte is owing to its superior hydrophily is widely used in osmotic, evaporating and dewatering research, comprising a series of natural polyelectrolyte such as shitosan, and sodium alginate, sodium cellulosate and synthetic polyelectrolyte such as Sodium Polyacrylate, SPSF etc.Traditional film-forming method is to adopt the method for scraping that is coated with, this method is at first a kind of polyelectrolyte casting solution to be scraped on supporter, treat that its little dried back scrapes the polyelectrolyte casting solution of another kind of oppositely charged on its surface, the polyelectrolyte that makes oppositely charged is compound generation compound polyelectrolyte film at the interface.But the thickness of the film that the method prepares is big, several microns in tens micrometer ranges, cause the flux of film to descend greatly; And filming technology is difficult to control, and the separation skin surface structure of the film that obtains is a heterogeneity, and is serious and influence the compactness of membrane structure, reduced the separating effect of film.The polyelectrolyte that new development is in recent years got up self assembly layer by layer (LbL) technology is a kind of novel masking technique.This technology is separated especially at film has very big application prospect (Regine v.Klitzing.Bernd Tieke.Adv Polym Sci (2004) 165:177-210) aspect the infiltration evaporation.This method is Electrostatic Absorption and the transition compensation principle that utilizes between positive and negative charge.Its basic process is: the positively charged polyelectrolyte of absorption on an electronegative counterdie, make the counterdie electric charge transition compensation of having adsorbed polyelectrolyte, and make the charge reversal of film become positive electricity like this; The film of the positively charged of charge reversal is adsorbed electronegative polyelectrolyte again, make film be inverted to negative electrical charge once more.The film that assembling so in layer forms is called self-assembled film layer by layer.The advantage of this method is: the hydrophily of the excellence of polyelectrolyte can extensively apply to organics dehydration; The self-assembled film surface texture is fine and close in order, has overcome to be coated with that knifing is separated or tomography defective uneven texture the separation factor height; The self-assembled film functional layer is thin, and thickness can be by the regulation and control of the assembling number of plies, and it is big to separate permeation flux.But, by the infiltrating and vaporizing membrane that obtains under this common assembling situation since every layer of adsorbance very little, each thickness in monolayer only is 0.5~3nm, generally needs assembling tens even hundreds of layer just certain separating effect can be arranged.Therefore, its major defect is time-consuming, and workload is big.A kind of electric field driving polyelectrolyte that the present invention proposes preparation method of self assembly infiltrating and vaporizing membrane layer by layer can effectively overcome above-mentioned shortcoming.
The separating property of water infiltration property infiltrating and vaporizing membrane passes to normal open amount (J) and separation factor (α
W/o) weigh.It is defined as follows:
Wherein permeate weight and obtain c ' by weight method
w, c '
oFor seeing through water and organic mass percentage concentration in the liquid, their value is determined by gas-chromatography or differential refractometer.c
w, c
oBe water in the feeding liquid and organic mass percentage concentration, its value is joined feeding liquid by experiment and is formed.
Summary of the invention
The purpose of this invention is to provide a kind of electric field driven high flux polyelectrolyte preparation method of self assembly infiltrating and vaporizing membrane layer by layer.
Comprise the steps:
1) 5~50 mass parts cationic polyelectrolytes are joined in the 10000 mass parts water, stir, 40~50 ℃ of following constant temperature 24~48 hours obtains cationic polyelectrolyte solution; 5~50 mass parts anionic polyelectrolytes join in the 10000 mass parts water, stir, and 40~50 ℃ of following constant temperature 24~48 hours obtains anionic polyelectrolyte solution;
2) the above-mentioned cationic polyelectrolyte solution of 1000~2000 mass parts is added in the cationic polyelectrolyte container, the battery lead plate that is connected both positive and negative polarity on the dc source is put into the cationic polyelectrolyte solution container respectively, fixed electrode, interelectrode distance is 5~20cm, output voltage range 1~50V; 1000~2000 mass parts anionic polyelectrolyte solution are added in the above-mentioned anionic polyelectrolyte container, put into the anionic polyelectrolyte solution container with being connected on the dc source battery lead plate of both positive and negative polarity, fixed electrode, interelectrode distance are 5~20cm, output voltage range 1~50V;
3) electronegative counterdie is put into the cationic solution container perpendicular to direction of an electric field, left standstill 5~30 minutes, electronegative counterdie charge reversal becomes the film of positively charged, and the film of the positively charged that takes out is soaked with deionized water, and it is dry down that nitrogen dries up 45~60 ℃ of backs; The desciccator diaphragm of positively charged is put into the anionic polyelectrolyte solution container, leave standstill 5~30 minutes after, the film of positively charged is inverted to electronegative film again, and electronegative film is taken out, and soaks with deionized water, it is dry down that nitrogen dries up 45~60 ℃ of backs; 1~20 time so repeatedly, prepare polyelectrolyte self assembly infiltrating and vaporizing membrane layer by layer.
Cationic polyelectrolyte is in the described step 1): poly-(dimethyl diallyl ammonium chloride), polymine, shitosan or polypropylene-base ammonium chloride.The anionic ion polyelectrolyte is in the step 1): kayexalate, sodium alginate or Sodium Polyacrylate.Step 2) voltage is preferably 2~20V in.Step 2) interelectrode distance in is preferably 8~15cm.Step 2) electrode in is graphite electrode, lead electrode or stainless steel electrode.The number of plies of assembling in the step 3) is preferably 5~10 layers.Counterdie in the step 3) is PA membrane or hydrolyzed polyacrylonitrile film.
The film of this method preparation can overcome traditional knifing legal system, and to be equipped with the polyelectrolyte membrane process restive, membrane structure heterogeneity and flux little and common " self-assembled film layer by layer " the assembling shortcoming that the number of plies is many, workload is big shows considerable flux and good selectivity and stability in infiltration evaporation.This method is utilized under extra electric field, and the effect of electric field force makes polyelectrolyte to the motion of counterdie direction on the one hand, accelerates the adsorption rate and the adsorbance that strengthens polyelectrolyte of polyelectrolyte; The orientation effect of electric field is orientated the polyelectrolyte polymer segment in solution on the other hand, make that the random coil of polyelectrolyte chain is arranged in parallel perpendicular to direction of an electric field in the presence of no electric field, parallel polyelectrolyte chain of unfolding is adsorbed onto on the counterdie more smooth, make the ordering more of function tunic, improve the separating effect of film.This method utilize electric field exist down the high-throughout polyelectrolyte of preparation layer by layer the self assembly infiltrating and vaporizing membrane at home and abroad do not appear in the newspapers as yet in the document, belong to first and propose.
The specific embodiment
Embodiment 1
20 mass parts poly-(dimethyl diallyl ammonium chloride) are dissolved in the 10000 mass parts deionized waters, 40 ℃ of following constant temperature 24 hours; 20 mass parts kayexalates are dissolved in the 10000 mass parts deionized waters, 40 ℃ of following constant temperature 24 hours.Poly-(dimethyl diallyl ammonium chloride) solution of 1000 mass parts is added in the container, graphite electrode plate is vertically put into solution, two interelectrode distances are 10cm, voltage is 5V, to immerse in the PA membrane in the solution of electric field existence, electronegative one side leaves standstill after 15 minutes and takes out towards the parallel placement of electrode anode, resulting film washed with de-ionized water, nitrogen dry up under back 45 ℃ dry; 1000 mass parts kayexalate solution are put into another container, and graphite electrode plate is vertically put into solution, and two interelectrode distances are 10cm, and voltage is 5V.The PA membrane that to assemble poly-(dimethyl diallyl ammonium chloride) immerses in the kayexalate solution of electric field existence, the one side of positively charged is towards the parallel placement of electrode negative pole, leave standstill after 15 minutes and take out, resulting film washed with de-ionized water, nitrogen dries up under back 45 ℃ dry.So circulation has obtained assembling 9 layers self-assembled film.This self assembly osmosis vaporizing compound membrane is used for isopropanol dehydration, finds that assembling film presents the water penetrated preferably.For the isopropanol feeding liquid that contains isopropyl alcohol 90wt%, 35 ℃ of following flux are 1.48kg/m
2H, seeing through liquid water content is 72.83% (α
W/o=24); 45 ℃ of following flux are 1.93kg/m
2H, seeing through liquid water content is 82.77% (α
W/o=43); 55 ℃ of following flux are 2.38kg/m
2H, seeing through liquid water content is 82.87% (α
W/o=44).
Embodiment 2
20 mass parts shitosans, 20 mass parts acetic acid are dissolved in the 10000 mass parts deionized waters, 50 ℃ of following constant temperature 48 hours; The poly-sodium alginate of 20 mass parts is dissolved in the 10000 mass parts deionized waters, 50 ℃ of following constant temperature 48 hours.1000 mass parts chitosan solutions are added in the container, and the lead electrode plate is vertically put into solution, and two interelectrode distances are 10cm, and voltage is 20V.In the solution that immerses in the PA membrane under the electric field existence, electronegative one side leaves standstill after 15 minutes and takes out towards the parallel placement of electrode anode, resulting film washed with de-ionized water, and nitrogen dries up under back 60 ℃ dry; 1000 mass parts sodium alginate solns are put into another container, and the lead electrode plate is vertically put into solution, and two interelectrode distances are 10cm, and voltage is 2V.The PA membrane of having assembled the positively charged of shitosan is immersed in the sodium alginate soln of electric field under existing, the one side of positively charged is towards the parallel placement of electrode negative pole, leave standstill after 15 minutes and take out, resulting film washed with de-ionized water, nitrogen dries up under back 60 ℃ dry.So circulation has obtained assembling 20 layers self-assembled film.Just this self assembly osmosis vaporizing compound membrane is used for isopropanol dehydration, finds that film presents the water penetrated preferably.For the isopropanol feeding liquid that contains isopropyl alcohol 95wt%, 35 ℃ of following flux are 0.78kg/m
2H, seeing through liquid water content is 81.77% (α
W/o=85); 45 ℃ of following flux are 0.91kg/m
2H, seeing through liquid water content is 84.82% (α
W/o=106); 55 ℃ of following flux are 1.35kg/m
2H, seeing through liquid water content is 85.77% (α
W/o=115).
Embodiment 3
50 mass parts polypropylene-base ammonium chlorides are dissolved in the 10000ml deionized water, 40 ℃ of following constant temperature 24 hours; 50 mass parts kayexalates are dissolved in the 10000ml deionized water, 40 ℃ of following constant temperature 24 hours.2000 mass parts polypropylene-base ammonium chloride solutions are added in the container, and the stainless steel electrode plate is vertically put into solution, and two interelectrode distances are 5cm, and voltage is 50V.The electronegative polyacrylonitrile film one side of hydrolysis is parallel towards electrode anode, takes out after leaving standstill 30min, and resulting film washed with de-ionized water, nitrogen dries up back 45 ℃ of dryings down.2000 mass parts kayexalate solution are put into another container, and the stainless steel electrode plate is vertically put into solution, and two interelectrode distances are 5cm, and voltage is 50V.One side charged in the polyacrylonitrile film of positively charged of polypropylene-base ammonium chloride polyelectrolyte is parallel towards the electrode negative pole with having assembled, take out after leaving standstill 30min, resulting film washed with de-ionized water, nitrogen dry up back 45 ℃ dry down.So circulation has obtained assembling 20 layers self-assembled film.Just this self assembly osmosis vaporizing compound membrane is used for isopropanol dehydration, finds that film presents the water penetrated preferably.For the isopropanol feeding liquid that contains isopropyl alcohol 90wt%, 35 ℃ of following flux are 0.53kg/m
2H, seeing through liquid water content is 95.21% (α
W/o=179); 45 ℃ of following flux are 0.75kg/m
2H, seeing through liquid water content is 95.38% (α
W/o=187); 55 ℃ of following flux are 1.03kg/m
2H, seeing through liquid water content is 95.93% (α
W/o=211).
Embodiment 4
5 mass parts polypropylene-base ammonium chlorides are dissolved in the 10000ml deionized water, 40 ℃ of following constant temperature 24 hours; 5 mass parts kayexalates are dissolved in the 10000ml deionized water, 40 ℃ of following constant temperature 24 hours.1000 mass parts polypropylene-base ammonium chloride solutions are added in the container, and the stainless steel electrode plate is vertically put into solution, and two interelectrode distances are 20cm, and voltage is 1V.The electronegative polyacrylonitrile film one side of hydrolysis is parallel towards electrode anode, takes out after leaving standstill 5min, and resulting film washed with de-ionized water, nitrogen dries up back 45 ℃ of dryings down.1000 mass parts kayexalate solution are put into another container, and the stainless steel electrode plate is vertically put into solution, and two interelectrode distances are 20cm, and voltage is 1V.One side charged in the polypropylene polynitriles film of positively charged of polypropylene-base ammonium chloride polyelectrolyte is parallel towards the electrode negative pole with having assembled, take out after leaving standstill 5min, resulting film washed with de-ionized water, nitrogen dry up back 45 ℃ dry down.So circulation has obtained assembling 1 layer self-assembled film.Just this self assembly osmosis vaporizing compound membrane is used for isopropanol dehydration, finds that film presents the water penetrated preferably.For the isopropanol feeding liquid that contains isopropyl alcohol 90wt%, 35 ℃ of following flux are 1.67kg/m
2H, seeing through liquid water content is 64.62% (α
W/o=16); 45 ℃ of following flux are 2.36kg/m
2H, seeing through liquid water content is 67.23% (α
W/o=18); 55 ℃ of following flux are 4.03kg/m
2H, seeing through liquid water content is 61.36% (α
W/o=14).
Embodiment 5
20 mass parts polymines are dissolved in the 10000ml deionized water, 40 ℃ of following constant temperature 24 hours; 10 mass parts Sodium Polyacrylates are dissolved in the 10000ml deionized water, 40 ℃ of following constant temperature 24 hours.1000 mass parts polyethyleneimine: amine aqueous solutions are added in the container, and graphite electrode plate is vertically put into solution, and two interelectrode distances are 10cm, and voltage is 20V.The electronegative PA membrane one side of hydrolysis is parallel towards electrode anode, takes out after leaving standstill 15min, and resulting film washed with de-ionized water, nitrogen dries up back 45 ℃ of dryings down.1000 mass parts sodium polyacrylate solution are put into another container, and graphite electrode plate is vertically put into solution, and two interelectrode distances are 10cm, and voltage is 20V.One side charged in the PA membrane of positively charged of polymine is parallel towards the electrode negative pole with having assembled, take out after leaving standstill 15min, resulting film washed with de-ionized water, nitrogen dry up back 45 ℃ dry down.So circulation has obtained assembling 10 layers self-assembled film.Just this self assembly osmosis vaporizing compound membrane is used for isopropanol dehydration, finds that film presents the water penetrated preferably.For the isopropanol feeding liquid that contains isopropyl alcohol 90wt%, 35 ℃ of following flux are 0.69kg/m
2H, seeing through liquid water content is 99.18% (α
W/o=1089); 45 ℃ of following flux are 1.23kg/m
2H, seeing through liquid water content is 99.27% (α
W/o=1198); 55 ℃ of following flux are 2.02kg/m
2H, seeing through liquid water content is 99.08% (α
W/o=979).
Embodiment 6
20 mass parts polymines are dissolved in the 10000ml deionized water, 40 ℃ of following constant temperature 24 hours; 10 mass parts Sodium Polyacrylates are dissolved in the 10000ml deionized water, 40 ℃ of following constant temperature 24 hours.1000 mass parts polyethyleneimine: amine aqueous solutions are added in the container, and graphite electrode plate is vertically put into solution, and two interelectrode distances are 10cm, and voltage is 5V.The electronegative PA membrane one side of hydrolysis is parallel towards electrode anode, takes out after leaving standstill 15min, and resulting film washed with de-ionized water, nitrogen dries up back 45 ℃ of dryings down.1000 mass parts sodium polyacrylate solution are put into another container, and graphite electrode plate is vertically put into solution, and two interelectrode distances are 10cm, and voltage is 5V.One side charged in the PA membrane of positively charged of polymine is parallel towards the electrode negative pole with having assembled, take out after leaving standstill 15min, resulting film washed with de-ionized water, nitrogen dry up back 45 ℃ dry down.So circulation has obtained assembling 9 layers self-assembled film.Just this self assembly osmosis vaporizing compound membrane is used for isopropanol dehydration, finds that film presents the water penetrated preferably.For the isopropanol feeding liquid that contains isopropyl alcohol 95wt%, 35 ℃ of following flux are 0.53kg/m
2H, seeing through liquid water content is 99.38% (α
W/o=3046); 45 ℃ of following flux are 0.89kg/m
2H, seeing through liquid water content is 99.47% (α
W/o=3566); 55 ℃ of following flux are 1.26kg/m
2H, seeing through liquid water content is 99.42% (α
W/o=3257).
Embodiment 7
20 mass parts polymines are dissolved in the 10000ml deionized water, 40 ℃ of following constant temperature 24 hours; 10 mass parts Sodium Polyacrylates are dissolved in the 10000ml deionized water, 40 ℃ of following constant temperature 24 hours.1000 mass parts polyethyleneimine: amine aqueous solutions are added in the container, and graphite electrode plate is vertically put into solution, and two interelectrode distances are 10cm, and voltage is 3V.The electronegative PA membrane one side of hydrolysis is parallel towards electrode anode, takes out after leaving standstill 15min, and resulting film washed with de-ionized water, nitrogen dries up back 45 ℃ of dryings down.1000 mass parts sodium polyacrylate solution are put into another container, and graphite electrode plate is vertically put into solution, and two interelectrode distances are 10cm, and voltage is 3V.One side charged in the PA membrane of positively charged of polymine is parallel towards the electrode negative pole with having assembled, take out after leaving standstill 15min, resulting film washed with de-ionized water, nitrogen dry up back 45 ℃ dry down.So circulation has obtained assembling 10 layers self-assembled film.Just this self assembly osmosis vaporizing compound membrane is used for isopropanol dehydration, finds that film presents the water penetrated preferably.For the isopropanol feeding liquid that contains isopropyl alcohol 90wt%, 35 ℃ of following flux are 0.78kg/m
2H, seeing through liquid water content is 98.38% (α
W/o=547); 45 ℃ of following flux are 1.78kg/m
2H, seeing through liquid water content is 98.32% (α
W/o=527); 55 ℃ of following flux are 2.97kg/m
2H, seeing through liquid water content is 97.91% (α
W/o=422).
Embodiment 8
20 mass parts polymines are dissolved in the 10000ml deionized water, 40 ℃ of following constant temperature 24 hours; 10 mass parts Sodium Polyacrylates are dissolved in the 10000ml deionized water, 40 ℃ of following constant temperature 24 hours.1000 mass parts polyethyleneimine: amine aqueous solutions are added in the container, and graphite electrode plate is vertically put into solution, and two interelectrode distances are 15cm, and voltage is 5V.The electronegative PA membrane one side of hydrolysis is parallel towards electrode anode, takes out after leaving standstill 15min, and resulting film washed with de-ionized water, nitrogen dries up back 45 ℃ of dryings down.1000 mass parts sodium polyacrylate solution are put into another container, and graphite electrode plate is vertically put into solution, and two interelectrode distances are 15cm, and voltage is 5V.One side charged in the PA membrane of positively charged of polymine is parallel towards the electrode negative pole with having assembled, take out after leaving standstill 15min, resulting film washed with de-ionized water, nitrogen dry up back 45 ℃ dry down.So circulation has obtained assembling 10 layers self-assembled film.Just this self assembly osmosis vaporizing compound membrane is used for isopropanol dehydration, finds that film presents the water penetrated preferably.For the isopropanol feeding liquid that contains isopropyl alcohol 80wt%, 35 ℃ of following flux are 0.92kg/m
2H, seeing through liquid water content is 98.77% (α
W/o=321); 45 ℃ of following flux are 1.52kg/m
2H, seeing through liquid water content is 98.64% (α
W/o=290); 55 ℃ of following flux are 2.35kg/m
2H, seeing through liquid water content is 98.42% (α
W/o=249).
Embodiment 9
20 mass parts polymines are dissolved in the 10000ml deionized water, 40 ℃ of following constant temperature 24 hours; 10 mass parts Sodium Polyacrylates are dissolved in the 10000ml deionized water, 40 ℃ of following constant temperature 24 hours.1000 mass parts polyethyleneimine: amine aqueous solutions are added in the container, and graphite electrode plate is vertically put into solution, and two interelectrode distances are 15cm, and voltage is 5V.The electronegative PA membrane one side of hydrolysis is parallel towards electrode anode, takes out after leaving standstill 15min, and resulting film washed with de-ionized water, nitrogen dries up back 45 ℃ of dryings down.1000 mass parts sodium polyacrylate solution are put into another container, and graphite electrode plate is vertically put into solution, and two interelectrode distances are 15cm, and voltage is 5V.One side charged in the PA membrane of positively charged of polymine is parallel towards the electrode negative pole with having assembled, take out after leaving standstill 15min, resulting film washed with de-ionized water, nitrogen dry up back 45 ℃ dry down.So circulation has obtained assembling 10 layers self-assembled film.Just this self assembly osmosis vaporizing compound membrane is used for isopropanol dehydration, finds that film presents the water penetrated preferably.For the isopropanol feeding liquid that contains isopropyl alcohol 70wt%, 35 ℃ of following flux are 1.23kg/m
2H, seeing through liquid water content is 97.78% (α
W/o=103); 45 ℃ of following flux are 1.92kg/m
2H, seeing through liquid water content is 97.51% (α
W/o=92); 55 ℃ of following flux are 2.98kg/m
2H, seeing through liquid water content is 97.85% (α
W/o=106).
Embodiment 10
20 mass parts polymines are dissolved in the 10000ml deionized water, 40 ℃ of following constant temperature 24 hours; 10 mass parts Sodium Polyacrylates are dissolved in the 10000ml deionized water, 40 ℃ of following constant temperature 24 hours.1000 mass parts polyethyleneimine: amine aqueous solutions are added in the container, and graphite electrode plate is vertically put into solution, and two interelectrode distances are 15cm, and voltage is 5V.The electronegative PA membrane one side of hydrolysis is parallel towards electrode anode, takes out after leaving standstill 15min, and resulting film washed with de-ionized water, nitrogen dries up back 45 ℃ of dryings down.1000 mass parts sodium polyacrylate solution are put into another container, and graphite electrode plate is vertically put into solution, and two interelectrode distances are 15cm, and voltage is 5V.One side charged in the PA membrane of positively charged of polymine is parallel towards the electrode negative pole with having assembled, take out after leaving standstill 15min, resulting film washed with de-ionized water, nitrogen dry up back 45 ℃ dry down.So circulation has obtained assembling 10 layers self-assembled film.Just this self assembly osmosis vaporizing compound membrane is used for isopropanol dehydration, finds that film presents the water penetrated preferably.For the isopropanol feeding liquid that contains isopropyl alcohol 50wt%, 35 ℃ of following flux are 1.87kg/m
2H, seeing through liquid water content is 96.25% (α
W/o=51); 45 ℃ of following flux are 2.75kg/m
2H, seeing through liquid water content is 96.46% (α
W/o=55); 55 ℃ of following flux are 4.03kg/m
2H, seeing through liquid water content is 95.72% (α
W/o=45).
Claims (5)
1. the electric field driven high flux polyelectrolyte preparation method of self assembly infiltrating and vaporizing membrane layer by layer is characterized in that comprising the steps:
1) 5~50 mass parts cationic polyelectrolytes are joined in the 10000 mass parts water, stir, 40~50 ℃ of following constant temperature 24~48 hours obtains cationic polyelectrolyte solution; 5~50 mass parts anionic polyelectrolytes join in the 10000 mass parts water, stir, and 40~50 ℃ of following constant temperature 24~48 hours obtains anionic polyelectrolyte solution;
2) the above-mentioned cationic polyelectrolyte solution of 1000~2000 mass parts is added in the cationic polyelectrolyte container, the battery lead plate that is connected both positive and negative polarity on the dc source is put into the cationic polyelectrolyte solution container respectively, fixed electrode, interelectrode distance is 5~20cm, output voltage range 1~50V; 1000~2000 mass parts anionic polyelectrolyte solution are added in the anionic polyelectrolyte container, put into the anionic polyelectrolyte solution container with being connected on the dc source battery lead plate of both positive and negative polarity, fixed electrode, interelectrode distance are 5~20cm, output voltage range 1~50V;
3) electronegative counterdie is put into the cationic solution container perpendicular to direction of an electric field, left standstill 5~30 minutes, electronegative counterdie charge reversal becomes the film of positively charged, and the film of the positively charged that takes out is soaked with deionized water, and it is dry down that nitrogen dries up 45~60 ℃ of backs; The desciccator diaphragm of positively charged is put into the anionic polyelectrolyte solution container, leave standstill 5~30 minutes after, the film of positively charged is inverted to electronegative film again, and electronegative film is taken out, and soaks with deionized water, it is dry down that nitrogen dries up 45~60 ℃ of backs; 1~20 time so repeatedly, prepare polyelectrolyte self assembly infiltrating and vaporizing membrane layer by layer;
Described cationic polyelectrolyte is: poly-(dimethyl diallyl ammonium chloride), polymine, shitosan or polypropylene-base ammonium chloride; The anionic ion polyelectrolyte is: kayexalate, sodium alginate or Sodium Polyacrylate; Counterdie is PA membrane or hydrolyzed polyacrylonitrile film.
2. according to the preparation method of self assembly infiltrating and vaporizing membrane layer by layer of a kind of electric field driven high flux polyelectrolyte described in the claim 1, it is characterized in that described step 2) in voltage be 2~20V.
3. according to the preparation method of self assembly infiltrating and vaporizing membrane layer by layer of a kind of electric field driven high flux polyelectrolyte described in the claim 1, it is characterized in that described step 2) in interelectrode distance be 8~15cm.
4. according to the preparation method of self assembly infiltrating and vaporizing membrane layer by layer of a kind of electric field driven high flux polyelectrolyte described in the claim 1, it is characterized in that described step 2) in electrode be graphite electrode, lead electrode or stainless steel electrode.
5. according to the preparation method of self assembly infiltrating and vaporizing membrane layer by layer of a kind of electric field driven high flux polyelectrolyte described in the claim 1, it is characterized in that the number of plies of assembling in the described step 3) is 5~10 layers.
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