CN201147677Y - Electric field aggrandizement assembly device for polyelectrolyte complex membrane - Google Patents
Electric field aggrandizement assembly device for polyelectrolyte complex membrane Download PDFInfo
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- CN201147677Y CN201147677Y CNU2007201699589U CN200720169958U CN201147677Y CN 201147677 Y CN201147677 Y CN 201147677Y CN U2007201699589 U CNU2007201699589 U CN U2007201699589U CN 200720169958 U CN200720169958 U CN 200720169958U CN 201147677 Y CN201147677 Y CN 201147677Y
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- 239000012528 membrane Substances 0.000 title claims abstract description 74
- 230000005684 electric field Effects 0.000 title claims abstract description 55
- 229920000867 polyelectrolyte Polymers 0.000 title claims abstract description 51
- 150000001875 compounds Chemical class 0.000 claims abstract description 43
- 238000007599 discharging Methods 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 abstract description 24
- 238000010521 absorption reaction Methods 0.000 abstract description 12
- 238000000926 separation method Methods 0.000 abstract description 7
- 230000003068 static effect Effects 0.000 abstract description 7
- 238000005728 strengthening Methods 0.000 abstract description 4
- 230000001351 cycling effect Effects 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 128
- 210000004379 membrane Anatomy 0.000 description 63
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 28
- 229920002239 polyacrylonitrile Polymers 0.000 description 26
- 229920000447 polyanionic polymer Polymers 0.000 description 24
- 239000008367 deionised water Substances 0.000 description 22
- 229910021641 deionized water Inorganic materials 0.000 description 22
- 229920002125 Sokalan® Polymers 0.000 description 17
- 239000000463 material Substances 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000000707 layer-by-layer assembly Methods 0.000 description 14
- 230000009471 action Effects 0.000 description 13
- 239000002131 composite material Substances 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 11
- 238000000108 ultra-filtration Methods 0.000 description 11
- 238000001704 evaporation Methods 0.000 description 10
- 230000008020 evaporation Effects 0.000 description 10
- 230000008595 infiltration Effects 0.000 description 10
- 238000001764 infiltration Methods 0.000 description 10
- 235000019441 ethanol Nutrition 0.000 description 9
- 239000004584 polyacrylic acid Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 230000004907 flux Effects 0.000 description 6
- 150000002466 imines Chemical class 0.000 description 6
- 229920000831 ionic polymer Polymers 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 210000002469 basement membrane Anatomy 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001471 micro-filtration Methods 0.000 description 2
- 238000001728 nano-filtration Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- MPDDTAJMJCESGV-CTUHWIOQSA-M (3r,5r)-7-[2-(4-fluorophenyl)-5-[methyl-[(1r)-1-phenylethyl]carbamoyl]-4-propan-2-ylpyrazol-3-yl]-3,5-dihydroxyheptanoate Chemical compound C1([C@@H](C)N(C)C(=O)C2=NN(C(CC[C@@H](O)C[C@@H](O)CC([O-])=O)=C2C(C)C)C=2C=CC(F)=CC=2)=CC=CC=C1 MPDDTAJMJCESGV-CTUHWIOQSA-M 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 241000826860 Trapezium Species 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
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- 238000006243 chemical reaction Methods 0.000 description 1
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- 238000004090 dissolution Methods 0.000 description 1
- 230000005685 electric field effect Effects 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- TVHALOSDPLTTSR-UHFFFAOYSA-H hexasodium;[oxido-[oxido(phosphonatooxy)phosphoryl]oxyphosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O TVHALOSDPLTTSR-UHFFFAOYSA-H 0.000 description 1
- 238000010406 interfacial reaction Methods 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- DWAYUNSAAKQFJZ-UHFFFAOYSA-G magnesium;dipotassium;trisodium;dihydrogen phosphate;hydrogen phosphate;dichloride;sulfate Chemical compound [Na+].[Na+].[Na+].[Mg+2].[Cl-].[Cl-].[K+].[K+].OP(O)([O-])=O.OP([O-])([O-])=O.[O-]S([O-])(=O)=O DWAYUNSAAKQFJZ-UHFFFAOYSA-G 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229920002627 poly(phosphazenes) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
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- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The utility model relates to an electric-field strengthening assembling device of a polyelectrolyte compound membrane, which belongs to the membrane separation field. The membrane production procedures of the traditional layer-upon-layer static absorption self-assembling method are complicated, and the period is long, and the membrane structure has poor adjustable and controllable performance. A tightening panel A (7), a polar plate A (3), a membrane chamber (4), a pervious supporting plate (5), a polar plate B (6) and a tightening panel B (8) are piled together in turn to be tightened to be a reactor (10); and a direct-current power source (21) is arranged at the two sides of the reactor (10). A feeding port (1) is connected with a pressure meter (11), a flowrate meter (12) and a cycling pump (13) through a pipeline, and then is connected with a polycation groove (16) through a valve A (14) and a valve B (15), and then passes through a valve C (18), a valve D (19) and a pressure meter (20) to return to a discharging port (2), thereby forming an electric-field strengthening device. The electric-field strengthening assembling device improves the membrane performance and the ordered performance of the compound membrane structure.
Description
Technical field
The utility model relates to a kind of electric field-enhanced apparatus for assembling of compound polyelectrolyte film, in order to strengthen assembling compound polyelectrolyte film and regulate and control its membrane structure under electric field action, belongs to the membrane separation technique field.
Background technology
Compound polyelectrolyte is a class purposes membrane material very widely, can be widely used in fields such as diffusion barrier, biology sensor, finishing, medical science.Polyelectrolyte claims polyion again, is meant the macromolecule that has many ionogenic ionic groups in main chain or side chain.The macromolecule that polyelectrolyte can be divided into polycation, polyanion and have the disassociation group of both positive and negative electric charge, i.e. Amphiphatic high polymer electrolyte.The compound polyelectrolyte film comprises not only that also the polyphosphazene polymer ion by two kinds of opposite charge forms, and also can be formed by the ionic surfactant of a kind of polyion and oppositely charged, Quadrafos, polysilicate etc.The preparation method that the compound polyelectrolyte film has roughly can be divided into following four classes: interfacial reaction method, dissolution with solvents method, original position complex method and layer-layer absorption method.
Since people such as Decher in 1991 propose first to utilize form the technology of multilayer film by the electrostatic interaction between the oppositely charged polyelectrolyte at the liquid-solid interface alternating deposit since, this layer upon layer electrostatic absorption (Layer-by-Layer adsorption, abbreviating LBL as) self assembly is considered to a kind of effective ways of constructing compound organic super thin film structure, shows application prospects.This legal system be equipped with mild condition, convenient and swift, nanoscale is controlled.The polyelectrolyte infiltrating and vaporizing membrane of layer upon layer electrostatic absorption method preparation generally all shows film properties preferably, but usually needs compound 50～60 layers of ability to obtain higher separation factor, system film program complexity, and the cycle is long.
We are according to the advantage separately that dynamically becomes embrane method and LBL method early stage, and a kind of new film build method of proposition is referred to as dynamic LBL method (Chinese patent application number: 200610012175.X).Its basic principle is: under the certain pressure effect forcibly with polyanion system coating materials liquid and polycation system coating materials liquid alternately at the membrane surface dynamic filtration, hold back on polyion and poly ion complexes (product of the reaction of polyanion and polycation) supported membrane surface, forms the compound polyelectrolyte layer with certain centrifugation.Dynamic LBL technology has been proved to be a kind of the synergy by applied force and has simplified the effective ways of film forming program, this method can promptly obtain high performance compound polyelectrolyte film in compound 2-5 layer, but no matter be static state or dynamic LBL technology, the performance of polyelectrolyte multilayer film and stratum boundary structure ordering are closely-related.In theory, owing to have Electrostatic Absorption gravitation between polycation and the polyanion, should form the ordered structure of static " contraposition " absorption between layer and the layer.But in fact because in the polyelectrolyte chain structure or have branching or have crosslinked or for inierpeneirating network structure or for trapezium structure, some macromolecule then exists side group and end group, these factors all can have a strong impact on complete " contraposition " Electrostatic Absorption between LBL process middle level and the layer, thereby the stratum boundary structure that forms not is the structure of complete orderingization.Therefore, static and dynamic its Modulatory character to membrane structure of LBL method is relatively poor, and film properties still has the space of further raising.
We adopt dynamic LBL technology to prepare the such fact of studies have shown that of polyelectrolyte multilayer film in earlier stage: the film forming motive force of the LBL technology of alternating deposit is not limited to the electrostatic force between polyion, also can be used as the motive force of reinforcement multilayer film assembling by the synergy of applied force.Compare simple dynamic pressurization, electric field force is more remarkable to the invigoration effect that the polyelectrolyte segment aligns and segment combines with substrate, be more conducive to form the multilayer film of compound with regular structure, and the Modulatory character of electric field force is stronger.Based on this, the utility model proposes a kind of electric field-enhanced apparatus for assembling of compound polyelectrolyte film, in order under electric field action, to strengthen assembling compound polyelectrolyte film and to regulate and control its membrane structure.
The utility model content
The purpose of this utility model is to provide a kind of electric field-enhanced apparatus for assembling of compound polyelectrolyte film, in order under electric field action, to strengthen assembling compound polyelectrolyte film, can effectively simplify the system film program of layer upon layer electrostatic absorption, further improve film properties, and realize effective regulation and control of membrane structure.
The technical solution of the utility model principle is: the DC electric field of the utmost point is introduced in the both sides at supporter, in the process of static state absorption or dynamic filtration said polycation solution, be controlled to be positive field, force to induce polycation to combine, and on the bed boundary, arrange more in an orderly manner with substrate.In like manner, when static state absorption or dynamic filtration polyanion, then be regulated to reversed electric field, force to induce polyanion to combine and form in order to arrange with substrate.Alternate repetition like this, can be implemented in the electric field-enhanced LBL assembling of polyelectrolyte film multilayer film under static state or the dynamic condition, and the order and the regularity of regulation and control multilayer film stratum boundary structure, prepare more orderly and complete high-performance infiltrating and vaporizing membrane, simultaneously can be by the electric field-enhanced further more compound number of plies that reduces.
The electric field-enhanced apparatus for assembling of compound polyelectrolyte film of the present utility model, it is characterized in that, on the basis of original dynamic Electrostatic Absorption method layer by layer, apply in the both sides of film can the commutation of falling the utmost point DC electric field, form the electric field-enhanced reactor of assembling compound polyelectrolyte film, in order under electric field action, to strengthen assembling compound polyelectrolyte film and to regulate and control its membrane structure.
The electric field-enhanced apparatus for assembling of compound polyelectrolyte film, this device comprise reactor 10, Pressure gauge 11, flowmeter 12, circulating pump 13, valve A14, valve B15, polycation hopper 16, polyanion hopper 17, valve C18, valve D19 and Pressure gauge 20 and the dc source 21 of the utmost point;
Be tightened to reactor 10 after wherein fasten panels A7, insulating pad A3, film chamber 4, permeable gripper shoe 5, insulating pad B6 and fasten panels B8 being stacked together successively in order; Support membrane is fixed on shape film forming room 4 on the permeable filter; Charging aperture 1 is opened the side in fasten panels A7, and penetrates into the surface of film chamber 4, and the opposite side of fasten panels A7 is established discharging opening 2, and discharging opening 2 penetrates into the surface of film chamber 4, forms a closed circuit; See through liquid outlet 9 and open one side, be used to collect solution through film in fasten panels B8;
10 liang of side joints of reactor are the dc source 21 of the utmost point; Charging aperture 1 is connected with Pressure gauge 11, flowmeter 12 and circulating pump 13 by pipeline, be connected with polyanion hopper 17 with polycation hopper 16 by valve A14, valve B15 respectively again, and then respectively by turning back to discharging opening 2 behind valve C18, valve D19 and the Pressure gauge 20, thereby form closed circuit and whole electric field-enhanced device.
Circulating pump in the poly-device of the electric field-enhanced assembling of pentalyte film is mainly used in the conveying polyelectrolyte solution, can arrive utmost point DC electric field and be used at film both sides formation electric field.Flow velocity and pressure are controlled by the valve in the pipeline, and measure concrete numerical value by flowmeter and Pressure gauge.By entering electric field-enhanced reactor, polyelectrolyte solution is entered by charging aperture 1 polyelectrolyte solution after the circulating pump pressurization, circulates on the film surface by discharging opening 2, sees through liquid on a small quantity and then is collected by seeing through liquid outlet 9.
Applying step of the present utility model:
(1) polycation and polyanion are dissolved in respectively in the solvent, are made into preparation liquid, standing and defoaming
(2) under the effect of 0.0～1.0MPa pressure, with polycation (or polyanion) solution at support membrane surface dynamic filtration, apply the DC electric field of 1～60 volt forward (or reverse) simultaneously in the support membrane both sides, act on 10～60 minutes, polycation (or polyanion) is trapped in film surface or hole, forms thin layer;
(3) film is immersed in the deionized water rinsing face and oven dry;
Also can after above-mentioned steps, further continue assembling again according to the following step
(4) under the effect of 0.0～1.0MPa pressure, forcibly with polyanion (or polycation) solution at support membrane surface dynamic filtration, apply the DC electric field of 1～60 volt reverse (or forward) simultaneously in support membrane film both sides, act on 10～60 minutes, polyanion and polycation are reacted, form the compound polyelectrolyte film;
(5) film is immersed in the deionized water rinsing face and oven dry;
Also can after above-mentioned steps, further continue assembling again according to the following step
(6) repeat (2)～(5) step, finally form the compound polyelectrolyte multilayer film.
Described layer upon layer electrostatic absorption method is meant at first basement membrane is carried out charged processing, immerses in the big molecular solution of poly-sun (the moon) ion, washs in pure water then, immerses in poly-cloudy (sun) ion solution again, forms ultra-thin separating layer after the repeated multiple times.
Described solvent can be water or organic alcohol.
In the utility model, described basement membrane is meant solution under pressure-driven, sees through a kind of segregation phenomenon of pellicle, can be NF membrane, milipore filter or micro-filtration membrane, and used material can be organic film, inoranic membrane or inorganic/organic hybrid films.The membrane aperture of described basement membrane is between 1 nanometer to 100 micron.
Below in conjunction with the drawings and specific embodiments embodiment and the strengthening effect that this is novel is described
Description of drawings:
The internal structural map of the electric field-enhanced reactor 10 of Fig. 1, assembling compound polyelectrolyte film
The electric field-enhanced apparatus for assembling figure of Fig. 2, compound polyelectrolyte film
The specific embodiment:
See also figure one and figure two.For form the electric capacity effect in the film both sides, at first pole plate A3 and pole plate B6 are wrapped up with insulating tape respectively, film to be assembled is positioned in the film chamber.With fasten panels A7, pole plate A3, film chamber 4, permeable gripper shoe 5, pole plate B6 and and fasten panels B8 be stacked together in order successively, be tightened to reactor 10 after penetrating fasten panels A7 and fasten panels B8 with bolt.10 liang of side joints of reactor are the dc source 21 of the utmost point.Charging aperture 1 is connected with Pressure gauge 11, flowmeter 12 and circulating pump 13 by pipeline, be connected with polyanion hopper 17 with polycation hopper 16 by valve A14, valve B15 respectively again, and then respectively by turning back to discharging opening 2 behind valve C18, valve D19 and the Pressure gauge 20, thereby form closed circuit and whole electric field-enhanced device.
Comparative Examples:
The employing support membrane is polyacrylonitrile (PAN) material, flat milipore filter, and molecular cut off 20000, membrane area are 79cm
2, used polycation material is Hi-fax imines (PEI, molecular weight are 60,000), the solvent of polymine is an absolute ethyl alcohol.
Assembling condition and method:
(1) with absolute ethyl alcohol polymine is made into the solution of 0.5wt%, standing and defoaming;
(2) for making polyacrylonitrile support membrane surface charged, adopt conventional hydrolyzed modified technology, at first when temperature is 65 ℃, polyacrylonitrile ultrafiltration film was immersed in the 2N NaOH solution 30 minutes, it is modified as the polyanion support membrane;
(3) film is immersed in the deionized water rinsing face and oven dry;
(4) film is placed the film chamber, be assembled into electric field-enhanced device according to above-mentioned embodiment, open valve A14 and valve C18, valve-off B15 and valve D19, start circulating pump 13, disconnect power supply 21, under 0.15MPa pressure, on polyacrylonitrile ultrafiltration film, filter 0.5wt%PEI solution time 30min, make the film surface form compound polyelectrolyte;
(5) film is taken out from the film chamber, be immersed in the deionized water, rinsing face and oven dry.
Above-mentioned assembling polyelectrolyte multilayer composite membrane is carried out the infiltration evaporation performance test in the infiltration evaporation membrane cisterna, test condition is: stoste is formed 95wt% ethanol/water system, 60 ℃ of experimental temperatures, film downstream pressure 100pa.
Recording the infiltration evaporation film properties is: permeation flux 429g.m
-2.h
-1, see through ethanol content 44.04wt% in the liquid, separation factor 24
The employing support membrane is polyacrylonitrile (PAN) material, flat milipore filter, and molecular cut off 20000, membrane area are 79cm
2, used polycation material is Hi-fax imines (PEI, molecular weight are 60,000), the solvent of polymine is an absolute ethyl alcohol.
Assembling condition and method:
(1) with absolute ethyl alcohol polymine is made into the solution of 0.5wt%, standing and defoaming;
(2) for making polyacrylonitrile support membrane surface charged, adopt conventional hydrolyzed modified technology, at first when temperature is 65 ℃, polyacrylonitrile ultrafiltration film was immersed in the 2N NaOH solution 30 minutes, it is modified as the polyanion support membrane;
(3) film is immersed in the deionized water rinsing face and oven dry;
(4) film is placed the film chamber, be assembled into electric field-enhanced device according to above-mentioned embodiment, open valve A14 and valve C18, valve-off B15 and valve D19 start circulating pump 13, connect power supply 21, be controlled to be 30 volts in forward dc electric field, under the 0.15MPa pressure, on polyacrylonitrile ultrafiltration film, filter 0.5wt%PEI solution, action time, 30min made the film surface form compound polyelectrolyte;
(5) film is taken out from the film chamber, be immersed in the deionized water, rinsing face and oven dry.
Above-mentioned assembling compound polyelectrolyte film is carried out the infiltration evaporation performance test in the infiltration evaporation membrane cisterna, test condition is: stoste is formed 95wt% ethanol/water system, 60 ℃ of experimental temperatures, film downstream pressure 100pa.
Recording the infiltration evaporation film properties is: permeation flux 357g.m
-2.h
-1, see through ethanol content 12.09wt% in the liquid, separation factor 138
AFM test before and after the electric field-enhanced LBL composite membrane, in 10 microns zones, it is 17.281nm that ethanol is done the mean roughness that solvent makes dynamic LBL composite membrane, electric field-enhanced LBL method film surface average roughness drops to 7.277nm, this explanation is under electric field-enhanced effect, the film surface is tending towards smooth, and the regularity of composite membrane and order improve.
The employing support membrane is polyacrylonitrile (PAN) material, flat milipore filter, and molecular cut off 20000, membrane area are 79cm
2, used polycation material is Hi-fax imines (PEI, molecular weight are 60,000), and polyanion is polyacrylic acid (PAA, molecular weight are 4,000,000), and polymine and polyacrylic solvent are water.
Assembling condition and method:
(1) with deionized water polyacrylic acid is made into the solution of 0.05wt%, polymine is made into the solution of 0.5wt%, standing and defoaming with isopropyl alcohol;
(2) for making polyacrylonitrile support membrane surface charged, adopt conventional hydrolyzed modified technology, at first when temperature is 65 ℃, polyacrylonitrile ultrafiltration film was immersed in the 2N NaOH solution 30 minutes, it is modified as the polyanion support membrane;
(3) film is immersed in the deionized water rinsing face and oven dry;
(4) film is placed the film chamber, be assembled into electric field-enhanced device according to above-mentioned embodiment, open valve A14 and valve C18, valve-off B15 and valve D19 start circulating pump 13, connect power supply 21, be controlled to be 15 volts in forward dc electric field, under the 0.15MPa pressure, on polyacrylonitrile ultrafiltration film, filter 0.5wt%PEI solution, action time, 15min made the film surface form compound polyelectrolyte;
(5) film is taken out from the film chamber, be immersed in the deionized water, rinsing face and oven dry;
(6) film is placed the film chamber, be assembled into electric field-enhanced device according to above-mentioned embodiment, open valve B15 and valve D19, valve-off A14 and valve C18 start circulating pump 13, connect power supply 21, be controlled to be 15 volts of reversed electric fields, under 0.15MPa pressure, filter 0.05wt%PAA solution, action time, 15min made it compound with the PEI layer;
(7) film is taken out from the film chamber, be immersed in the deionized water, rinsing face and oven dry.
(8) repeating step (4)-(5) is 1 time, can form the compound number of plies and be 1.5 layers polyelectrolyte composite membrane.
Above-mentioned assembling polyelectrolyte multilayer composite membrane is carried out the infiltration evaporation performance test in the infiltration evaporation membrane cisterna, test condition is: stoste is formed 95wt% ethanol/water system, 60 ℃ of experimental temperatures, film downstream pressure 100pa.
Recording the infiltration evaporation film properties is: permeation flux 543g.m
-2.h
-1, see through ethanol content 14.49wt% in the liquid, separation factor 112.
The employing support membrane is polyacrylonitrile (PAN) material, flat milipore filter, and molecular cut off 20000, membrane area are 79cm
2, used polycation material is Hi-fax imines (PEI, molecular weight are 60,000), polyanion is polyacrylic acid (PAA, molecular weight are 4,000,000).
Assembling condition and method:
(1) with deionized water polyacrylic acid is made into the solution of 0.05wt%, polymine is made into the solution of 0.5wt%, standing and defoaming with isopropyl alcohol
(2) for making polyacrylonitrile support membrane surface charged, adopt conventional hydrolyzed modified technology, at first when temperature is 65 ℃, polyacrylonitrile ultrafiltration film was immersed in the 2N NaOH solution 30 minutes, it is modified as the polyanion support membrane;
(3) film is immersed in the deionized water rinsing face and oven dry;
(4) film is placed the film chamber, be assembled into electric field-enhanced device according to above-mentioned embodiment, open valve A14 and valve C18, valve-off B15 and valve D19 start circulating pump 13, connect power supply 21, be controlled to be 15 volts in forward dc electric field, under the 0.15MPa pressure, on polyacrylonitrile ultrafiltration film, filter 0.5wt%PEI solution, action time, 15min made the film surface form compound polyelectrolyte;
(5) film is taken out from the film chamber, be immersed in the deionized water, rinsing face and oven dry;
(6) film is placed the film chamber, be assembled into electric field-enhanced device according to above-mentioned embodiment, open valve B15 and valve D19, valve-off A14 and valve C18 start circulating pump 13, connect power supply 21, be controlled to be 15 volts of reversed electric fields, under 0.15MPa pressure, filter 0.05wt%PAA solution, action time, 15min made it compound with the PEI layer;
(7) film is taken out from the film chamber, be immersed in the deionized water, rinsing face and oven dry.
(8) repeating step (4)-(7) is 5 times, can form the compound number of plies and be 5 layers polyelectrolyte composite membrane.
Recording the infiltration evaporation film properties is: permeation flux 268g.m
-2.h
-1, see through ethanol content 2.41wt% in the liquid, separation factor 769.
The employing support membrane is polyacrylonitrile (PAN) material, flat milipore filter, and molecular cut off 20000, membrane area are 79cm
2, used polycation material is Hi-fax imines (PEI, molecular weight are 60,000), polyanion is polyacrylic acid (PAA, molecular weight are 4,000,000).
Assembling condition and method:
(1) with deionized water polyacrylic acid is made into the solution of 0.05wt%, polymine is made into the solution of 0.5wt%, standing and defoaming with methyl alcohol
(2) for making polyacrylonitrile support membrane surface charged, adopt conventional hydrolyzed modified technology, at first when temperature is 65 ℃, polyacrylonitrile ultrafiltration film was immersed in the 2N NaOH solution 30 minutes, it is modified as the polyanion support membrane;
(3) film is immersed in the deionized water rinsing face and oven dry;
(4) film is placed the film chamber, be assembled into electric field-enhanced device according to above-mentioned embodiment, open valve A14 and valve C18, valve-off B15 and valve D19 start circulating pump 13, connect power supply 21, be controlled to be 60 volts in forward dc electric field, under the 0.15MPa pressure, on polyacrylonitrile ultrafiltration film, filter 0.5wt%PEI solution, action time, 15min made the film surface form compound polyelectrolyte;
(5) film is taken out from the film chamber, be immersed in the deionized water, rinsing face and oven dry;
(6) film is placed the film chamber, be assembled into electric field-enhanced device according to above-mentioned embodiment, open valve B15 and valve D19, valve-off A14 and valve C18 start circulating pump 13, connect power supply 21, be controlled to be 60 volts of reversed electric fields, under 0.15MPa pressure, filter 0.05wt%PAA solution, action time, 15min made it compound with the PEI layer;
(7) film is taken out from the film chamber, be immersed in the deionized water, rinsing face and oven dry.
(8) behind the repeating step (4)-(7) 2 times, repeat (4)-(5) 1 time again, can form the compound number of plies and be 2.5 layers polyelectrolyte composite membrane.Above-mentioned assembling polyelectrolyte multilayer composite membrane is carried out divalence Ni in the nanofiltration membrane cisterna
2+Separating property test, test condition is: Ni in the stoste
2+Content is 170mg/l, 25 ℃ of experimental temperatures, both sides differential pressure of membrane 0.25MPa.
Recording film properties is: membrane flux 26.0l.m
-2.h
-1, see through Ni in the liquid
2+Content 8.0mg/l is to Ni
2+Rejection be 95.3%.
The employing support membrane is Kynoar (PVDF) material, flat micro-filtration membrane, aperture (0.1 micron), membrane area is 79cm
2, used polycation material is Hi-fax imines (PEI, molecular weight are 60,000), polyanion is polyacrylic acid (PAA, molecular weight are 4,000,000).
Assembling condition and method:
(1) with deionized water polyacrylic acid is made into the solution of 0.05wt%, polymine is made into the solution of 0.5wt%, standing and defoaming with absolute ethyl alcohol
(2) for making the support membrane surface charged earlier, at first under 0.10MPa pressure, on support membrane, filter the polyacrylic acid solution 0.05wt%40min of 0.05wt%, and then filtration 0.5wt%PEI solution 40min, guaranteeing so has one deck compound polyelectrolyte on the film surface, make the film surface charged, and make the polyanion that combines with supporter be difficult for being stripped from down in the reversed electric field effect;
(3) film is immersed in the deionized water rinsing face and oven dry;
(4) film is placed the film chamber, be assembled into electric field-enhanced device according to above-mentioned embodiment, open valve A14 and valve C18, valve-off B15 and valve D19 start circulating pump 13, connect power supply 21, be controlled to be 1.0 volts in forward dc electric field, under the 0.10MPa pressure, on polyacrylonitrile ultrafiltration film, filter 0.5wt%PEI solution, action time, 15min made the film surface form compound polyelectrolyte;
(5) film is taken out from the film chamber, be immersed in the deionized water, rinsing face and oven dry;
(6) film is placed the film chamber, be assembled into electric field-enhanced device according to above-mentioned embodiment, open valve B15 and valve D19, valve-off A14 and valve C18 start circulating pump 13, connect power supply 21, be controlled to be 1.0 volts of reversed electric fields, under 0.10MPa pressure, filter 0.05wt%PAA solution, action time, 15min made it compound with the PEI layer;
(7) film is taken out from the film chamber, be immersed in the deionized water, rinsing face and oven dry.
(8) behind the repeating step (4)-(7) 3 times, repeat (4)-(5) 1 time again, can form the compound number of plies and be 3.5 layers polyelectrolyte composite membrane.
Above-mentioned assembling polyelectrolyte multilayer composite membrane is carried out divalence Cu in the nanofiltration membrane cisterna
2+Separating property test, test condition is: Cu in the stoste
2+Content is 100mg/l, 25 ℃ of experimental temperatures, both sides differential pressure of membrane 0.25MPa.Recording film properties is: membrane flux 32.0l.m
-2.h
-1, see through Cu in the liquid
2+Content 4.0mg/l is to Cu
2+Rejection be 96.0%.
Claims (1)
1, a kind of electric field-enhanced apparatus for assembling of compound polyelectrolyte film, this device comprise reactor (10), Pressure gauge (11), flowmeter (12), circulating pump (13), valve A (14), valve B (15), polycation hopper (16), polycation hopper (16), valve C (18), valve D (19) and Pressure gauge (20) and the dc source of the utmost point (21);
Be tightened to reactor (10) after wherein fasten panels A (7), insulating pad A (3), film chamber (4), permeable gripper shoe (5), insulating pad B (6) and fasten panels B (8) being stacked together successively in order; Support membrane is fixed on shape film forming room (4) on the permeable filter; Charging aperture (1) is opened in the side of fasten panels A (7), and penetrates into the surface of film chamber (4), and the opposite side of fasten panels A (7) is established discharging opening (2), and discharging opening (2) penetrates into the surface of film chamber (4), forms a closed circuit; See through liquid outlet (9) and open (8) one sides in fasten panels B;
Reactor (10) two side joints are the dc source of the utmost point (21); Charging aperture (1) is connected with Pressure gauge (11), flowmeter (12) and circulating pump (13) by pipeline, be connected with polycation hopper (16) with polycation hopper (16) by valve A (14), valve B (15) respectively again, and then respectively by turning back to discharging opening (2) behind valve C (18), valve D (19) and the Pressure gauge (20).
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101157010B (en) * | 2007-07-31 | 2010-06-02 | 北京工业大学 | Electric field ruggedization assembled method and apparatus of polyelectrolyte complexes membrane |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101157010B (en) * | 2007-07-31 | 2010-06-02 | 北京工业大学 | Electric field ruggedization assembled method and apparatus of polyelectrolyte complexes membrane |
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