CN108043239A - A kind of preparation method of the anion-exchange membrane with polysulfonate DOPA amine layer - Google Patents
A kind of preparation method of the anion-exchange membrane with polysulfonate DOPA amine layer Download PDFInfo
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- CN108043239A CN108043239A CN201711226075.1A CN201711226075A CN108043239A CN 108043239 A CN108043239 A CN 108043239A CN 201711226075 A CN201711226075 A CN 201711226075A CN 108043239 A CN108043239 A CN 108043239A
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- anion
- feed liquid
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- exchange membrane
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/44—Ion-selective electrodialysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/42—Ion-exchange membranes
Abstract
The invention discloses a kind of preparation methods of the anion-exchange membrane with polysulfonate DOPA amine layer, utilize dopamine auto polymerization principle, sulfonation dopamine is deposited into film surface by auto polymerization mode, obtain the modified anion exchange membrane of attachment sulfonation DOPA amine layer, so that anion-exchange membrane has a dianion selection separating property well, certain antifouling property is provided simultaneously with.Present invention process is simple, operates easy, preparation process asepsis environment-protecting.
Description
Technical field
The present invention relates to the methods that preparation has both Monovalent selectivity and resistance tocrocking anion-exchange membrane, particularly relate to one kind
The side for having both the anion-exchange membrane of Monovalent selectivity and resistance tocrocking with polysulfonate DOPA amine layer is prepared using auto polymerization deposition
Method.
Background technology
Electrodialytic technique as a kind of electric drive membrane separating process, is widely used in the place of saline-water reclamation and wastewater and sewage
Reason purification.Its core is amberplex, however because the complexity of raw water causes this technology to undergo huge challenge,
Including the F being harmful in removal underground water-And NO3 -And separation SO4 2-To avoid generation CaSO4Precipitation influences water treatment procedure, separately
Organic pollution in outer water body can also impact film properties.Anion-exchange membrane is important in amberplex one
Point, it can effectively solve the problems, such as this by improving its selective penetrated property and contamination resistance.In recent years improve and anion is selected
The method of permeability mainly by depositing a modified strata anionic species in anionic membrane surface, is handed over so as to improve anion
Change the Monovalent selectivity of film.Published electro-deposition method layer by layer on Journal of Membrane Science, commodity the moon from
Proton exchange surface is by applying electric field, alternating deposit polyanionic materials and range of polycationic substances so that Modified Membrane possesses list
Valency selective power.
However, the stability of above-mentioned electro-deposition method trivial operations layer by layer, ion selectivity and modified layer is not high.
Therefore, the present invention is intended to provide a kind of prepare the side for having both Monovalent selectivity and resistance tocrocking anion-exchange membrane
Method, the film prepared has good Monovalent selectivity energy, while also enhances the antifouling property of film.This method greatly enhances
Monovalent selectivity and modified layer stability.
The content of the invention
It is high to dianion selection separating property it is an object of the invention to solve commercialization anion-exchange membrane,
Existing to prepare the method with Monovalent selectivity anionic membrane cumbersome and the vulnerable to pollution during handling water the problem of, carries
The side of Monovalent selectivity and resistance tocrocking with polysulfonate DOPA amine layer anion-exchange membrane is had both for a kind of simply and easily prepare
Method.
The purpose of the present invention is what is be achieved through the following technical solutions：
It is a kind of to prepare the method for having both Monovalent selectivity and resistance tocrocking anion exchange film strips polysulfonate DOPA amine layer,
It is characterized in that：Using aggregation deposition method, sulfonation dopamine (SDA) is dissolved in Tris buffer solutions, is sunk by self-polymeric reaction
Product obtains being attached with SDA layers of modified anion exchange membrane in anion exchange film surface.
Further, method of the present invention is specifically prepared in accordance with the following steps：
(1) using anion-exchange membrane as basement membrane, successively with the NaOH solution of 0.2mol/L and the HCl solution of 0.2mol/L
Rinsed, then the basement membrane pre-processed with ultrapure water be soaked in the NaCl solution of 0.5mol/L 24 it is small when, for use；
(2) Dopamine hydrochloride is dissolved in absolute ethyl alcohol, is slowly added to the ammonium hydroxide and 1 of 20~30wt%, in 3-N-morpholinopropanesulfonic acid
When reaction 15~20 is small at 40~50 DEG C, gained reaction mixture is filtered for ester, and gained filter residue is done after being rinsed with absolute ethyl alcohol
It is dry, obtain sulfonation dopamine；The ratio between the Dopamine hydrochloride and the amount of substance of 1,3- propane sultones are 1：0.8
~1.2；The addition of the absolute ethyl alcohol is calculated as 80~140mL/g with the quality of the Dopamine hydrochloride；The ammonia
The addition of water is calculated as 0.35~0.45mL/g with the quality of the Dopamine hydrochloride；
(3) sulfonation dopamine is dissolved in the Tris buffer solutions that pH is 8.5~8.8, obtains mixed solution；The Tris
The concentration of buffer solution is 0.01mol/L；The addition of the sulfonation dopamine is with the volume of the Tris buffer solutions
It is calculated as 0.001~0.003g/mL；
(4) through hole being mounted on the basement membrane of the pretreatment on " two membranes and three chambers " device, the device include
First breather chamber, feed liquid room, the second breather chamber, electric mixer and gasing pump, first breather chamber, feed liquid room and second
For breather chamber by affixed three cell structures for forming sealing of long bolt, the feed liquid room is clipped in first breather chamber and described
The second breather chamber between；The two sides of the feed liquid room are equipped with the through hole connected with chamber in feed liquid room, the pretreatment
Basement membrane is mounted on the through hole for membrane, and first breather chamber, the second breather chamber are each via the pretreatment
Basement membrane is connected with the inner cavity of feed liquid room, is stirred after the mixed solution is added in feed liquid room, and 4~48 are stirred at 20~25 DEG C
Hour, reaction remains breather chamber and air communication simultaneously so that it is more that the membrane surface of pretreatment forms uniform polysulfonate
Bar amine layer, obtains the anion-exchange membrane with polysulfonate DOPA amine layer.
Further, in step (2), the preferably described reaction temperature is 50 DEG C, reaction time 18h.
Further, in step (4), the mixing speed is 150r/min.
Equipment used by preparation method according to the present invention specifically includes referring to CN201610124160.6
One breather chamber, feed liquid room, the second breather chamber, electric mixer and gasing pump, first breather chamber, feed liquid room and second are logical
Gas chamber is by affixed three cell structures for forming sealing of long bolt, wherein the feed liquid room is clipped in first breather chamber and institute
Between the second breather chamber stated；The two sides of the feed liquid room are equipped with the through hole connected with chamber in feed liquid room, the through hole
The basement membrane of place's installation pretreatment；The medial surface of first breather chamber and the medial surface of second breather chamber are respectively equipped with
Venthole corresponding with feed liquid room ipsilateral through hole, the air inlet of first breather chamber, second breather chamber into
The gas port gas outlet pipeline connection with the gasing pump respectively；The agitating paddle of the electric mixer stretches into the feed liquid
The inner cavity of room.
The first rubber ring for being useful for sealing is matched somebody with somebody at the through hole edge, is matched somebody with somebody in the groove of through hole circumferential direction and is useful for sealing
Second rubber ring.
The first row gas port connected with the first breather chamber is equipped at the top of first breather chamber.
The second exhaust port connected with the second breather chamber is equipped at the top of second breather chamber.
Compared with prior art, the beneficial effects of the present invention are：
(1) present invention is directly deposited by self-polymeric reaction in film surface, greatly reduces reaction step, realizes that a step is modified,
Greatly improve selectivity of the anion-exchange membrane to monovalent anion simultaneously.
(2) the sulfonation dopamine (SDA) that the present invention uses has the polymerizing power and adhesiveness of similar dopamine, and
Chemical property is stable, asepsis environment-protecting.
(3) present invention process is simple, operates easy, preparation process asepsis environment-protecting.
Description of the drawings
Fig. 1 is sulfonation dopamine synthetic route and chemical structural formula.
Fig. 2 is the schematic device that the present invention uses.
Fig. 3 is the signal that the selective penetrated property of the anion-exchange membrane with polysulfonate DOPA amine layer prepared by the present invention measures
Figure.
Fig. 4 is that the antifouling property of the anion-exchange membrane with polysulfonate DOPA amine layer prepared by the present invention measures signal
Figure.
Fig. 5 separates dianion selection with the anion-exchange membrane with polysulfonate DOPA amine layer for basement membrane of the present invention
Aptitude tests.
Fig. 6 is that anion-exchange membrane of the present invention with polysulfonate DOPA amine layer selects segregational stability test curve.
Fig. 7 is for basement membrane of the present invention with the anion-exchange membrane with polysulfonate DOPA amine layer to neopelex anti-pollution
Dye test.
Specific embodiment
Equipment used by the anion-exchange membrane of the present invention with polysulfonate DOPA amine layer is prepared, it is logical including first
Gas chamber 1, feed liquid room 2, the second breather chamber 3, electric mixer 4 and gasing pump 5, first breather chamber 1, feed liquid room 2 and
Two breather chambers 3 are by affixed three cell structures for forming sealing of long bolt, wherein the feed liquid room 2 is clipped in first ventilation
Between room 1 and second breather chamber 3；The two sides of the feed liquid room 2 are equipped with the through hole 21 connected with chamber in feed liquid room,
The basement membrane 6 of installation pretreatment at the through hole 21；The medial surface of first breather chamber 1 and second breather chamber 3
Medial surface be respectively equipped with venthole corresponding with 2 ipsilateral through hole of feed liquid room, the first air inlet of first breather chamber 1
11st, the second air inlet 31 of second breather chamber 3 gas outlet pipeline connection with the gasing pump 5 respectively；Described
The agitating paddle 41 of electric mixer 4 stretches into the inner cavity of the feed liquid room 2.
The first rubber ring 22 for being useful for sealing is matched somebody with somebody at 21 edge of through hole, and the groove of through hole circumferential direction is interior close with being useful for
Second rubber ring 23 of envelope.
First breather chamber, 1 top is equipped with the first row gas port 12 connected with the first breather chamber.
Second breather chamber, 3 top is equipped with the second exhaust port 32 connected with the second breather chamber.
First breather chamber, the second breather chamber and the feed liquid room be square structure, and the first breather chamber,
Second breather chamber and the vertex of feed liquid room four match somebody with somebody the mounting hole 24 for being useful for installation long bolt.
It is furnished with speed governing knob 42 and switch button 43 on the electric mixer 4.
The step of 1 autohemagglutination of embodiment deposition, modified anion exchange membrane
The preparation method of a kind of anion-exchange membrane with polysulfonate DOPA amine layer of the present invention, including walking as follows
Suddenly：
It is molten with 0.2MNaOH and 0.2M HCl using homogeneous Japanese FUJIFILM commercializations anion-exchange membrane as basement membrane
Liquid rinses former commercial membranes successively, washes away film surface impurity and the subsidiary Protective substances of business film surface, film is stored in 0.5M
In NaCl solution 24 it is small when.The sulfonation dopamine synthesis step and structural formula of autohemagglutination deposition are as shown in Figure 1.By 1.1376g
The Dopamine hydrochloride of (6mmol), which is dissolved in the absolute ethyl alcohol of 150mL, to be placed in 250mL flasks, is slowly added to 416 μ L (3mmol)
The 1,3-propane sultone of the ammonium hydroxide and 799mg (6.5mmol) of 28wt%, when reaction 18 is small at 50 DEG C, drag occurs
White depositions, will be rinsed with absolute ethyl alcohol after precipitation filtering be placed on for three times in 40 DEG C of vacuum drying chamber dry to get to
Sulfonation dopamine (SDA), autohemagglutination deposition prepare the schematic diagram such as Fig. 2 for having both Monovalent selectivity and resistance tocrocking anion-exchange membrane
It is shown.
Film to be modified is mounted on the through hole, the SDATris buffer solutions of 3g/L are poured into middle material liquid chamber, separately
Outer two chamber ventings room ensures both sides air flow.Film is placed vertically and one side is contacted with sulfonation dopamine solution, opposite side and sky
Oxygen contact in gas, aggregation deposition process holding temperature is 22 DEG C and electric mixer rotating speed is 150r/min, passes through control
Sedimentation time processed obtains the polysulfonate DOPA amine layer of different-thickness, with sedimentation time increase to 48 it is small when, polysulfonate dopamine
The thickness of layer reaches 0.53 μm, and the color at membrane surface modification position, which also gradually becomes, is deep to brownish black.
Embodiment 2 is deposited for autohemagglutination, making choice property of modified anion exchange membrane is tested
By taking the Modified Membrane of multiple autohemagglutinations deposition different time prepared in embodiment 1 as an example, film is placed in electrodialysis plant
In tested.The selectivity test schematic diagram of film is as shown in Figure 3.The volume of each room is 100mL, and effective area is
19.625cm2.Intermediate two Room are respectively light room and dense room, wherein adding in the Na of 100mL0.05M2SO4It is other with NaCl mixed solutions
The Na of 0.2M is added in the electrode chamber of two, side2SO4Solution is as electrolyte.In 5.1mAcm-2It is run under current density, electric osmose
Analysis time control is 120min, every 30min light room side feed liquid is taken to pass through its Cl of ion chromatography-And SO4 2-Concentration.Selection
Property size byIt represents, calculation formula is as follows：
Wherein JiFor object ion flux, unit molm-2·s-1；C be light room measured ion concentration, unit M.
It is as shown in Figure 5 to a dianion selectivity test.
The selectivity of the former film of business remains at 1 or so in electrodialytic process, shows Cl-And SO4 2-Ion indifference
Penetrate film, and be significantly improved by the selectivity of the Modified Membrane of polysulfonate depositing dopamine with the increase of sedimentation time.
When electrodialytic process proceeds to 90 minutes, Modified Membrane when deposition 4 is small is selectively 1.49, Modified Membrane when deposition 48 is small
Selectivity is even more to have reached 34.02, because the deposition of polysulfonate DOPA amine layer causes surface finer and close and with substantial amounts of
Bear is electrical, to SO4 2-Ion by there is the inhibition of bigger, it was demonstrated that polysulfonate depositing dopamine can effectively improve business
The selectivity of industry anionic membrane.
Embodiment 3 is deposited for autohemagglutination, modified anion exchange membrane making choice property steady testing
Exemplified by Modified Membrane when the autohemagglutination sedimentation time 48 prepared in embodiment 1 is small, film is placed in electrodialysis plant
It is tested, film to be tested preserves one month in 0.5M NaCl solutions before testing.Test schematic diagram is as shown in Figure 3.Each
The volume of room is 100mL, effective area 19.625cm2.Intermediate two Room are respectively light room and dense room, wherein adding in
The Na of 100mL0.05M2SO4With NaCl mixed solutions, the Na of 0.2M is added in the electrode chamber of two, side2SO4Solution is as electrolysis
Liquid.In 5.1mAcm-2Run under current density, the testing time in total 80 it is small when, taken when 2 is small light room side feed liquid by from
Sub- chromatographic determination Cl-And SO4 2-Concentration.Feed liquid is replaced after per sub-sampling.
It is as shown in Figure 6 to Modified Membrane selectivity steady testing.
Deposit 48 it is small when anion-exchange membrane light room in continuous electrodialytic process with polysulfonate DOPA amine layer Cl-
And SO4 2-Ion concentration near 0.01M and 0.04M, does not fluctuate significantly always, it was demonstrated that polysulfonate DOPA amine layer has good
Good stability and superpower Adhesion property.
Embodiment 4 is deposited for autohemagglutination, modified anion exchange membrane carries out antipollution test
Exemplified by Modified Membrane when the autohemagglutination sedimentation time 48 prepared in embodiment 1 is small, in 2mAcm-2Under current density
The antifouling property of film characterize as shown in Figure 4 using four electrode systems.Intermediate two feed liquid rooms for 0.05M NaCl and
0.174kg·m-3The mixed solution of neopelex (SDBS), two, side feed liquid room is 0.05M NaCl solutions, electric
The solution of pole room and feed liquid room is respectively with 1.2 × 10-3m3·min-1Flow 30 DEG C cycle, effective area 7.065cm2。
The variation of film both end voltage passes through Ag/AgCl electrodes and multitester measuring.In Contamination measurement, film both end voltage is dirty in film surface
It can be steeply risen during dye, the time at this time is the pollution time, is referred to as transformation time.
It is as shown in Figure 7 to the test of Modified Membrane antifouling property.
There is situation about polluting in the former film of business film surface when antipollution experiment proceeds to 76 minutes, and deposit 48 it is small when gather
The transformation time of the Modified Membrane of sulfonation dopamine is 112 minutes, and compared to former film, the contaminated time increases 36 minutes, shows
Polysulfonate depositing dopamine possesses certain effect for promoting the former film antifouling property of business.
Embodiment 5 is deposited for autohemagglutination, modified anion exchange membrane carries out film resistance measure
By taking the Modified Membrane of multiple autohemagglutinations deposition different time prepared in embodiment 1 as an example, it is placed in resistivity-measuring devices
It is tested, circulation fluid is 0.5M NaCl solutions.
Compare different autohemagglutination sedimentation time Modified Membrane sheet resistances, the former film of gained business and different autohemagglutination sedimentation time film tables
Surface resistance is as shown in table 1.
The film resistance of the former film of 1 business of table and modified anion exchange membrane
The film resistance of the former film of business is 1.02 Ω cm2, the resistance of Modified Membrane is with the increase of polysulfonate depositing dopamine time
And increase, by 1.34 Ω cms of the deposition 4 when small2Increase to deposition 48 it is small when 6.83 Ω cm2。
Claims (3)
1. a kind of preparation method of the anion-exchange membrane with polysulfonate DOPA amine layer, which is characterized in that the method is specific
It is prepared in accordance with the following steps：
(1) using anion-exchange membrane as basement membrane, carried out successively with the NaOH solution of 0.2mol/L and the HCl solution of 0.2mol/L
Rinsing, then the basement membrane pre-processed with ultrapure water；
(2) Dopamine hydrochloride is dissolved in absolute ethyl alcohol, is slowly added to the ammonium hydroxide and 1,3-propane sultone of 20-30wt%,
When reaction 15~20 is small at 40~50 DEG C, gained reaction mixture is filtered, gained filter residue is dry after being rinsed with absolute ethyl alcohol,
Obtain sulfonation dopamine；The ratio between the Dopamine hydrochloride and the amount of substance of 1,3- propane sultones are 1：0.8~
1.2；The addition of the absolute ethyl alcohol is calculated as 80~140mL/g with the quality of the Dopamine hydrochloride；The ammonium hydroxide
Addition 0.35~0.45mL/g is calculated as with the quality of the Dopamine hydrochloride；
(3) sulfonation dopamine is dissolved in the Tris buffer solutions that pH is 8.5~8.8, obtains mixed solution；The Tris bufferings
The concentration of solution is 0.01mol/L；The addition of the sulfonation dopamine is calculated as with the volume of the Tris buffer solutions
0.001~0.003g/mL；
(4) through hole being mounted on the basement membrane of the pretreatment on " two membranes and three chambers " device, the device include first
Breather chamber, feed liquid room, the second breather chamber, electric mixer and gasing pump, first breather chamber, feed liquid room and the second ventilation
By affixed three cell structures for forming sealing of long bolt, the feed liquid room is clipped in first breather chamber and described for room
Between two breather chambers；The two sides of the feed liquid room are equipped with the through hole connected with chamber in feed liquid room, the basement membrane of the pretreatment
For membrane be mounted on the through hole, first breather chamber, the second breather chamber each via the pretreatment basement membrane
It is connected with the inner cavity of feed liquid room, is stirred after the mixed solution is added in feed liquid room, it is small that 4~48 is stirred at 20~25 DEG C
When, reaction remains breather chamber and air communication simultaneously so that the membrane surface of pretreatment forms uniform polysulfonate DOPA
Amine layer obtains the anion-exchange membrane with polysulfonate DOPA amine layer.
2. preparation method as described in claim 1, it is characterised in that：In step (2), the reaction temperature is 50 DEG C, instead
When being 18 small between seasonable.
3. preparation method as described in claim 1, it is characterised in that：In step (4), the mixing speed is 150r/
min。
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| CN201711226075.1A CN108043239A (en) | 2017-11-29 | 2017-11-29 | A kind of preparation method of the anion-exchange membrane with polysulfonate DOPA amine layer |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110404419A (en) * | 2019-08-14 | 2019-11-05 | 东华大学 | A kind of sulfonation polyphenol nanofiltration membrane and preparation method thereof |
| CN112759041A (en) * | 2019-10-21 | 2021-05-07 | 中国石油化工股份有限公司 | Method for preparing anti-pollution ion exchange membrane |
| CN113019141A (en) * | 2021-04-02 | 2021-06-25 | 哈尔滨工业大学 | Preparation method of monovalent selective cation exchange membrane with charge Janus structure |
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| CN105709607A (en) * | 2016-03-04 | 2016-06-29 | 浙江工业大学 | Preparation method and equipment for ion exchange membrane with dopamine layer |
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2017
- 2017-11-29 CN CN201711226075.1A patent/CN108043239A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105709607A (en) * | 2016-03-04 | 2016-06-29 | 浙江工业大学 | Preparation method and equipment for ion exchange membrane with dopamine layer |
Non-Patent Citations (2)
| Title |
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| YAN ZHAO等: "Sulfonated reduced graphene oxide modification layers to improve monovalent anions selectivity and controllable resistance of anion exchange membrane", 《JOURNAL OF MEMBRANE SCIENCE》 * |
| YI-CHANG CHUNG等: "Water-borne composite coatings using nanoparticles modified with dopamine derivatives", 《THIN SOLID FILMS》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110404419A (en) * | 2019-08-14 | 2019-11-05 | 东华大学 | A kind of sulfonation polyphenol nanofiltration membrane and preparation method thereof |
| CN112759041A (en) * | 2019-10-21 | 2021-05-07 | 中国石油化工股份有限公司 | Method for preparing anti-pollution ion exchange membrane |
| CN113019141A (en) * | 2021-04-02 | 2021-06-25 | 哈尔滨工业大学 | Preparation method of monovalent selective cation exchange membrane with charge Janus structure |
| CN113019141B (en) * | 2021-04-02 | 2022-08-02 | 哈尔滨工业大学 | Preparation method of monovalent selective cation exchange membrane with charge Janus structure |
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