CN1704151A - Bipolar film and preparation method thereof - Google Patents
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Abstract
The invention relates to a two-pore film and it's preparing technique. The said two-pore film comprises anion exchange layer, cation exchange layer and inter boundary layer, wherein inter boundary layer catalyst is formed by branch polymer of organic manipulation which has molecule structure's repetitive unit contains nitrogen atom and outmost amino, or end amino modifying substance of the polymers. Its preparing method is that first preparing anion exchange layer, and preparing anther anion exchange layer solution with opposite electricity, then preparing catalyst weak solution of inter boundary layer and fixes its catalyst on anion exchange layer by absorbing and blanketing modes, or mixes the catalyst with anion exchange layer solution and then preparing it by slobbering mode.
Description
Technical field:
The present invention relates to the Bipolar Membrane technology of preparing in the separation membrane in the field of chemical engineering, particularly electrodialytic water is separated separating process.
Background technology:
The function of Bipolar Membrane was known already, and under the driving of reverse biased electric field, it can become water decomposition hydrogen ion and hydroxide ion, and this water decomposition has advantages such as simple, efficient, energy-conservation; Based on the electrodialytic technique of Bipolar Membrane pollute, reclaim in control have reality in resource and the chemical process or potential widespread use (" Bipolar Membrane technical manual " (Handbook on Bipolar Membrane Technology, ISBN9036515203) 17-46 page or leaf) of A.J.B.Kemperman chief editor.Reported Bipolar Membrane in the document already by prepared in various methods, for example, United States Patent (USP) 4024043 and 4057481 has been reported the method for preparing the monolithic type Bipolar Membrane, promptly introduces the yin, yang ion-exchange group and makes Bipolar Membrane with chemical process respectively in the polymer-based film both sides.The Bipolar Membrane of this method preparation can not add the catalytic specie that promotes water decomposition between two retes, film both sides volts lost height, thereby rarely found in commercial Bipolar Membrane at present.For the material that will have katalysis more easily is added in the intermediate layer of Bipolar Membrane, most commodity Bipolar Membrane all are to be composited by two opposite electrically ion-exchange membrane layer.In United States Patent (USP) 4355116 and 4776161, and the 159th volume 395-404 page or leaf of the technical journal " colloid and surfaces A are collected " (Colloidsand Surfaces A) of Dutch Elsevier Science Press (Elsevier Science Publishers) has reported that the anion-exchange membrane that forms with the aminating agent amination that contains tertiary amine group and primary amine, secondary amine group simultaneously prepares Bipolar Membrane.The intermediate layer of the Bipolar Membrane of this method preparation contains non-quaternary ammonium group, according to " Chemical Reaction Model " (technical journal " nature " of London nature Publishing Group (NaturePublishing Group) is the 280th volume 824-826 page or leaf (Nature)) of Bipolar Membrane water decomposition, these groups can promote water decomposition; But yet this be the quantity of the amination point of limited amount on the anion-exchange membrane matrix of catalytic activity point of intermediate layer of the Bipolar Membrane of catalytic specie with weak solution from group, the quantity of catalytic activity point is insufficient, makes that the volts lost of film both sides is inadequately little.Another kind of catalytic specie commonly used is a metal ion.Reported at technical journal " electrochemistry journal " (Electrochimica Acta) the 31st volume 1175-1176 of Britain Pergamon-Elsevier science company limited (Pergamon-Elsevier Science LTD) page or leaf and to have used inorganic electrolyte, such as sodium wolframate, chromium nitrate, ruthenium trichloride, indium sulfate etc., the pre-treatment ion-exchange membrane, and then compound two opposite electrical ion-exchange membrane layer are made Bipolar Membrane.The certain catalysis of metal ion that is added in this Bipolar Membrane water decomposition of Bipolar Membrane, but metal ion is very easy to loss in the water decomposition process, causes the performance of Bipolar Membrane stable inadequately, work-ing life is very short.In order to address this problem, according to technical journal " membrane science magazine " (Journal of Membrane Science) the 78th volume 13-23 page or leaf of United States Patent (USP) 5227040 and Dutch Elsevier Science Press (Elsevier SciencePublisher), can there be two kinds of methods to fix metal ion, the one, the ion-exchange membrane elder generation of having adsorbed metal ion handles through hot alkaline solution and is used for preparing Bipolar Membrane again, and the Bipolar Membrane that perhaps also intermediate layer can be adsorbed with metal ion is handled with hot alkaline solution.Yet the method for this fixing metal ions and to prepare the method for this Bipolar Membrane comparatively loaded down with trivial details, and raise in the volts lost of using long period film both sides, film properties descends.Another kind of catalytic specie commonly used is an ion exchange resin, report as United States Patent (USP) 4253900, the ion exchange resin that these are crosslinked is dispersed in the polymers soln, is deposited in the middle of two retes by methods such as coating, cast, injection, silk screen printings, and then the preparation Bipolar Membrane.These ion exchange resin require particle diameter little (less than 1 micron), narrowly distributing, be distributed in evenly, at random, the intermediate layer of Bipolar Membrane single pearl layer, thereby this Bipolar Membrane preparation is very difficult and loaded down with trivial details, but and the charged group of the limited amount of the catalytic activity point of intermediate layer in resin, this makes that the volts lost of Bipolar Membrane both sides is higher.In the Chinese patent 99125066.4, disclosing a kind of intermediate layer is Bipolar Membrane Zeo-karb, that contain the cross-linked structure of quaternary ammonium group and tertiary amine groups that is scattered here and there, this PREPARATIOM OF BIPOLAR MEMBRANE method can realize ultra-thinization of intermediate layer easily, but has comparatively small amt, the higher shortcoming of film both sides volts lost of catalytic activity point equally.
Summary of the invention:
The objective of the invention is to, overcome deficiency of the prior art, the composition of the intermediate layer of existing Bipolar Membrane is made improvements, obtain stable performance, long service life, the little Bipolar Membrane of film both sides volts lost, and this Bipolar Membrane is easy to preparation.
Bipolar Membrane of the present invention, comprise anionresin layer, cationic exchange layer and intermediate layer, it is characterized in that, the catalytic specie that constitutes described intermediate layer is to contain nitrogen-atoms in the repeating unit by molecular structure and outermost layer is the dendritic polymer of the organic backbone of amido, or the end amido modifier of these polymkeric substance constitutes.
The dendritic polymer of described formation intermediate layer, the algebraically that preferably contains nitrogen-atoms and outermost layer in the repeating unit and be amido is the dendritic polymer of 2-10, its initial initiated core is ammonia, quadrol or other polyamines preferably, dendriform polymine (poly (ethyleneimine) dendrimer for example, abbreviation PEI), dendriform polypropylene imines (poly (propyleneimine) dendrimer, be called for short PPI) and dendriform daiamid (poly (amidoamine) dendrimer is called for short PAMAM).
Described dendritic polymer is that molecular weight distribution width (ratio of weight-average molecular weight and number-average molecular weight) is the dendritic polymer of 1.0-3.0, and preferably the molecular weight distribution width approaches 1.0 dendritic polymer.
Described end amido modifier is meant that the outermost layer end group is the dendritic polymer of hydroxyl, sulfydryl, carboxyl, carboxylate radical, phosphate radical, sulfate radical, inferior sulfate radical, quaternary ammonium group.
PREPARATIOM OF BIPOLAR MEMBRANE method of the present invention comprises: [1] prepares the anionresin layer earlier and prepares cationic exchange layer solution, perhaps prepare the cationic exchange layer earlier and prepare anionresin layer solution, [2] dilute solution of catalytic specie of preparation intermediate layer, with adsorb, the mode of coating is fixed on the catalytic specie in the dilute solution on negatively charged ion or the cationic exchange layer; The catalytic specie that perhaps will constitute intermediate layer is blended in positively charged ion or the anionresin layer solution, [3] with hydrostomia cationic exchange layer solution on the anionresin layer or on the cationic exchange layer mode of hydrostomia anionresin layer solution prepare Bipolar Membrane, it is characterized in that, contain nitrogen-atoms in the repeating unit that the described catalytic specie that is blended in positively charged ion or the anionresin layer solution is a molecular structure and outermost layer is the dendritic polymer of the organic backbone of amido, or the end amido modifier of these polymkeric substance; The heavy ratio of the matter of described quality that is blended in the intermediate layer catalytic specie in positively charged ion or the anionresin layer solution and ion exchange resin is 10
-5-0.1, preferably 10
-4-0.01; The dilute solution of the catalytic specie of described intermediate layer, its solvent are water or other organic solvent, and its solute is above-mentioned dendritic polymer or its end amido modifier, and the mass concentration of solution is 10
-4-1.0mg/mL, preferably 10
-3-0.1mg/mL.
The dendritic polymer of described formation intermediate layer, the algebraically that preferably contains nitrogen-atoms and outermost layer in the repeating unit and be amido is the dendritic polymer of 2-10, its initial initiated core is ammonia, quadrol or other polyamines preferably, for example dendriform polymine, dendriform polypropylene imines and dendriform daiamid.
Described dendritic polymer is that molecular weight distribution width (ratio of weight-average molecular weight and number-average molecular weight) is the dendritic polymer of 1.0-3.0, and preferably the molecular weight distribution width approaches 1.0 dendritic polymer.
Described end amido modifier is meant that the outermost layer end group is the dendritic polymer of hydroxyl, sulfydryl, carboxyl, carboxylate radical, phosphate radical, sulfate radical, inferior sulfate radical, quaternary ammonium group.
In the prior art, the closely adjacent or institute that is bonded together constitutes Bipolar Membrane by two electrically opposite ion exchange layers, because the interaction between two retes, junction at two retes forms zone of transition, the removable ionic concn in this zone reduces, and has the fixed charge that is not compensated, and this zone is exactly the intermediate layer of Bipolar Membrane, be the zone of Bipolar Membrane water decomposition, critical influence arranged for the performance of Bipolar Membrane.Film is positioned in the electrolyte solution, and under the effect of DC electric field, water can directly be dissociated into hydrogen ion and hydroxide ion, and enters contiguous compartment by the positive and negative ion-exchange membrane layer respectively and obtain corresponding bronsted lowry acids and bases bronsted lowry solution.
With the Bipolar Membrane of the inventive method preparation, contain the dendritic polymer that nitrogen-atoms and outermost layer are amido or the end amido modifier of these polymkeric substance in the repeating unit that its intermediate layer material is a molecular structure.Because this dendritic polymer is highly branched, highly symmetry and end group density are more much higher than common polymkeric substance, therefore the quantity of the water decomposition catalytic site of the intermediate layer of this Bipolar Membrane is also just than the Bipolar Membrane of making the intermediate layer material with common ion-exchanger or much higher with the Bipolar Membrane of small molecules amination agent amination anionresin layer refabrication, on the other hand, this dendritic polymer molecular memory is hydrophilic at cavity and end group, function with suction water storage, thereby make the intermediate layer of Bipolar Membrane more hydrophilic, help the water decomposition of Bipolar Membrane.And because catalytic specie molecule rank ground is dispersed in and becomes dilute solution in the solvent or be dispersed in the solution of ion exchange layer, so the intermediate layer of formed Bipolar Membrane is thinner, and catalytic specie is evenly distributed.Owing to above reason, the water decomposition ability of Bipolar Membrane of the present invention is strong, and the volts lost of film both sides is little.Because the large size of dendritic polymer in use can not be lost through the yin, yang ion exchange layer, the Bipolar Membrane performance that therefore this dendritic polymer is modified is very stable, and long service life simultaneously.
Among the Bipolar Membrane preparation method of the present invention, catalytic specie adsorbs in the formation of intermediate layer only needs ion-exchange membrane is immersed in the solution of catalytic specie, the perhaps solution of coating catalytic specie on ion-exchange membrane, perhaps catalytic specie is blended in the ion exchange layer solution, preparation process is simple.
By the test shows to the Bipolar Membrane of many groups embodiment preparation, the volts lost of these film both sides is starkly lower than the volts lost of the Bipolar Membrane that does not add any catalytic specie, and film properties is stable, long service life.
Embodiment
Embodiment 1:
Dissolving is that in distilled water, concentration is 0.01mg/mL for the dendriform daiamid (PAMAM, U.S. Dendritech company produce) in the 2nd generation of nuclear with the quadrol; Under the room temperature with out-phase anion-exchange membrane (Chinese Shanghai chemical plant company limited, model 3362BW, thickness 0.42mm, water content 35%, loading capacity (doing) 1.8mmol/g, face resistance 12 Ω .cm
2, permselective property 89%) be immersed in this aqueous solution, treat that fully (24 hours) are taken out in the absorption back, at room temperature dry in the shade naturally; On this anion-exchange membrane, be coated with one deck sulfonated poly (phenylene oxide) (SulphonatedPoly (phenylene oxide) then, SPPO) dimethyl formamide solution (concentration is 1g/4ml) is as the anode membrane layer, in 60 ℃ of baking ovens, placed 6 hours, take out and promptly get Bipolar Membrane.
This film is at 0.5mol/L Na
2SO
4In the aqueous solution, current density 1000A/m
2Under the volts lost of film both sides less than 2.6V, and film properties is very stable, long service life.
According to testing with the Bipolar Membrane of quadrat method preparation, the result is that both sides voltage is reduced to 3.5V to the anion-exchange membrane of adsorption catalysis material not.
Embodiment 2:
The PREPARATIOM OF BIPOLAR MEMBRANE process is similar to Example 1, just the out-phase anion-exchange membrane is changed into homogeneous-phase anion exchange film (the thickness 0.2mm that Shandong marine chemical industry research institute produces, water content 40%, loading capacity (doing) 1.8mmol/g, face resistance 4 Ω .cm
2, permselective property 92%).
This film is at 0.5mol/L Na
2SO
4In the aqueous solution, current density 1000A/m
2Under the volts lost of film both sides less than 2.0V, and film properties is very stable, long service life.
According to testing with the Bipolar Membrane of quadrat method preparation, the result is that both sides voltage is reduced to 3.2V to the anion-exchange membrane of adsorption catalysis material not.
Embodiment 3:
The PREPARATIOM OF BIPOLAR MEMBRANE process is similar to Example 1, just will replace with as the material sulfonated poly (phenylene oxide) of anode membrane layer sulfonated polyether-ether-ketone (Sulphonated Poly (ether ether ketone), S-PEEK).
This film is at 0.5mol/L Na
2SO
4In the aqueous solution, current density 1000A/m
2Under the volts lost of film both sides less than 2.5V, and film properties is very stable, long service life.
According to testing with the Bipolar Membrane of quadrat method preparation, the result is that both sides voltage is reduced to 3.6V to the anion-exchange membrane of adsorption catalysis material not.
Embodiment 4:
The PREPARATIOM OF BIPOLAR MEMBRANE process is similar to Example 1, just be with concentration 0.01mg/mL with the quadrol be the dendriform daiamid aqueous solution in the 2nd generation of nuclear change into concentration be 0.001mg/mL be dendriform daiamid (the being similarly U.S. Dendritech company produces) aqueous solution in the 5th generation of nuclear with the quadrol.
This film is at 0.5mol/L Na
2SO
4In the aqueous solution, current density 1000A/m
2Under the volts lost of film both sides less than 2.9V, and film properties is very stable, long service life.
According to testing with the Bipolar Membrane of quadrat method preparation, the result is that both sides voltage is reduced to 3.5V to the anion-exchange membrane of adsorption catalysis material not.
Embodiment 5:
The PREPARATIOM OF BIPOLAR MEMBRANE process is similar to Example 1, just changes the dendriform daiamid into dendriform daiamid that terminal groups modification is the same algebraically of same initiated core of quaternary ammonium group, and its concentration of aqueous solution is 0.01mg/mL.
This film is at 0.5mol/L Na
2SO
4In the aqueous solution, current density 1000A/m
2Under the volts lost of film both sides less than 2.4V, and film properties is very stable, long service life.
According to testing with the Bipolar Membrane of quadrat method preparation, the result is that both sides voltage is reduced to 3.5V to the anion-exchange membrane of adsorption catalysis material not.
Embodiment 6:
The PREPARATIOM OF BIPOLAR MEMBRANE process is similar to Example 2, just be with concentration 0.01mg/mL with the quadrol be the dendriform daiamid aqueous solution in the 2nd generation of nuclear change into concentration be 0.01mg/mL be the dendriform polypropylene imines aqueous solution (Dutch DSM (DSM) company) in the 3rd generation of nuclear with ammonia.
This film is at 0.5mol/L Na
2SO
4In the aqueous solution, current density i000A/m
2Under the volts lost of film both sides less than 1.8V, and film properties is very stable, long service life.
According to testing with the Bipolar Membrane of quadrat method preparation, the result is that both sides voltage is reduced to 3.2V to the anion-exchange membrane of adsorption catalysis material not.
Embodiment 7:
The PREPARATIOM OF BIPOLAR MEMBRANE process is similar to Example 6, just will be that to change concentration into be the 0.1mg/mL aqueous solution for the aqueous solution of dendriform polypropylene imines concentration 0.01mg/mL in the 3rd generation of nuclear with ammonia.
This film is at 0.5mol/L Na
2SO
4In the aqueous solution, current density 1000A/m
2Under the volts lost of film both sides less than 2.6V, and film properties is very stable, long service life.
According to testing with the Bipolar Membrane of quadrat method preparation, the result is that both sides voltage is reduced to 3.2V to the anion-exchange membrane of adsorption catalysis material not.
Embodiment 8:
Concentration is that to add with the quadrol in the dimethyl formamide solution of sulfonated poly (phenylene oxide) of 1g/4ml be that the dendriform daiamid (production of U.S. Dendritech company) in the 2nd generation of nuclear is as cationic exchange layer solution; making the quality of dendriform daiamid and the mass ratio of sulfonated poly (phenylene oxide) is 0.005; then in out-phase anion-exchange membrane (Shanghai Chemical Plant Co., Ltd.; model 3362BW) is coated with this cationic exchange layer solution of one deck on; in 60 ℃ of baking ovens, placed 6 hours, take out and promptly get Bipolar Membrane.
This film is at 0.5mol/L Na
2SO
4In the aqueous solution, current density 1000A/m
2Under the volts lost of film both sides less than 2.2V, and film properties is very stable, long service life.
According to testing with the Bipolar Membrane of quadrat method preparation, the result is that both sides voltage is reduced to 3.5V to the anion-exchange membrane of adsorption catalysis material not.
Embodiment 9:
The PREPARATIOM OF BIPOLAR MEMBRANE process is similar to Example 8, and what just add in cationic exchange layer solution is that the dendriform daiamid in the 2nd generation of nuclear and the mass ratio of sulfonated poly (phenylene oxide) are 0.01 with the quadrol.
This film is at 0.5mol/L Na
2SO
4In the aqueous solution, current density 1000A/m
2Under the volts lost of film both sides less than 2.3V, and film properties is very stable, long service life.
According to testing with the Bipolar Membrane of quadrat method preparation, the result is that both sides voltage is reduced to 3.5V to the anion-exchange membrane of adsorption catalysis material not.
Embodiment 10:
The PREPARATIOM OF BIPOLAR MEMBRANE process is similar to Example 8, and what just add in cationic exchange layer solution is that the dendriform daiamid in the 2nd generation of nuclear and the mass ratio of sulfonated poly (phenylene oxide) are 10 with the quadrol
-4
This film is at 0.5mol/L Na
2SO
4In the aqueous solution, current density 1000A/m
2Under the volts lost of film both sides less than 3.0V, and film properties is very stable, long service life.
According to testing with the Bipolar Membrane of quadrat method preparation, the result is that both sides voltage is reduced to 3.5V to the anion-exchange membrane of adsorption catalysis material not.
Claims (8)
1. Bipolar Membrane, comprise anionresin layer, cationic exchange layer and intermediate layer, it is characterized in that, the catalytic specie that constitutes described intermediate layer is to contain nitrogen-atoms in the repeating unit by molecular structure and outermost layer is the dendritic polymer of the organic backbone of amido, or the end amido modifier of these polymkeric substance constitutes.
2. Bipolar Membrane as claimed in claim 1 is characterized in that, the dendritic polymer of described formation intermediate layer is that to contain nitrogen-atoms and outermost layer in the repeating unit be that the algebraically of amido is the dendritic polymer of 2-10,
3. Bipolar Membrane as claimed in claim 1 is characterized in that, the initial initiated core of described dendritic polymer is ammonia, quadrol or other polyamines.
4. Bipolar Membrane as claimed in claim 1 is characterized in that, described dendritic polymer is that the molecular weight distribution width is the dendritic polymer of 1.0-3.0.
5. Bipolar Membrane as claimed in claim 1 is characterized in that, described " end amido modifier " is meant that the outermost layer end group is the dendritic polymer of hydroxyl, sulfydryl, carboxyl, carboxylate radical, phosphate radical, sulfate radical, inferior sulfate radical, quaternary ammonium group.
6. PREPARATIOM OF BIPOLAR MEMBRANE method comprises: [1] preparation anionresin layer earlier also prepares cationic exchange layer solution, and perhaps preparation cationic exchange layer is also prepared anionresin layer solution earlier; [2] dilute solution of catalytic specie of preparation intermediate layer, with adsorb, the mode of coating is fixed on the catalytic specie in the dilute solution on negatively charged ion or the cationic exchange layer; The catalytic specie that perhaps will constitute intermediate layer is blended in positively charged ion or the anionresin layer solution; [3] with hydrostomia cationic exchange layer solution on the anionresin layer or on the cationic exchange layer mode of hydrostomia anionresin layer solution prepare Bipolar Membrane, it is characterized in that, contain nitrogen-atoms in the repeating unit that the described catalytic specie that is blended in positively charged ion or the anionresin layer solution is a molecular structure and outermost layer is the dendritic polymer of the organic backbone of amido, or the end amido modifier of these polymkeric substance; The heavy ratio of the matter of described quality that is blended in the intermediate layer catalytic specie in positively charged ion or the anionresin layer solution and ion exchange resin is 10
-5-0.1; The dilute solution of the catalytic specie of described intermediate layer, its solvent are water or other organic solvent, and its solute is above-mentioned dendritic polymer or its end amido modifier, and the mass concentration of solution is 10
-4-1.0mg/mL.
7. PREPARATIOM OF BIPOLAR MEMBRANE method as claimed in claim 6 is characterized in that, the heavy ratio of the matter of described quality that is blended in the intermediate layer catalytic specie in positively charged ion or the anionresin layer solution and ion exchange resin is 10
-4-0.01.
8. PREPARATIOM OF BIPOLAR MEMBRANE method as claimed in claim 6 is characterized in that, the mass concentration of the dilute solution of the catalytic specie of described intermediate layer is 10
-3-0.1mg/mL.
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| CN101949032A (en) * | 2010-09-21 | 2011-01-19 | 福建师范大学 | Preparation method for modified bipolar membrane doped with nano SiO2 |
| CN102304723A (en) * | 2011-09-20 | 2012-01-04 | 福建师范大学 | Three-membrane four-chamber chlorine-free alkali-producing electrolytic tank consisting of anion and cation exchange membranes and bipolar membrane |
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| CN104593819A (en) * | 2015-01-06 | 2015-05-06 | 山东天维膜技术有限公司 | Bipolar membrane and preparation method thereof |
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|---|---|---|---|---|
| CA2043583C (en) * | 1990-05-31 | 1999-01-05 | Fumio Hanada | Bipolar membrane and method for its production |
| CN1101254C (en) * | 1999-11-26 | 2003-02-12 | 清华大学 | Bipolar film and its preparing process |
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| CN101949032A (en) * | 2010-09-21 | 2011-01-19 | 福建师范大学 | Preparation method for modified bipolar membrane doped with nano SiO2 |
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| CN104593819A (en) * | 2015-01-06 | 2015-05-06 | 山东天维膜技术有限公司 | Bipolar membrane and preparation method thereof |
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| CN108568219A (en) * | 2017-03-08 | 2018-09-25 | 财团法人工业技术研究院 | Composite structure |
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| CN106968108A (en) * | 2017-05-03 | 2017-07-21 | 厦门大学 | A kind of application of monolithic type Bipolar Membrane in flow battery |
| CN110756055A (en) * | 2019-05-15 | 2020-02-07 | 北京化工大学 | Bipolar membrane and preparation method thereof |
| CN110898861A (en) * | 2019-12-09 | 2020-03-24 | 中国科学技术大学先进技术研究院 | Preparation method of bipolar membrane and bipolar membrane |
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