CN102600732A - Method for preparing bipolar membrane modified by solar photocatalyst - Google Patents
Method for preparing bipolar membrane modified by solar photocatalyst Download PDFInfo
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- CN102600732A CN102600732A CN2012101010177A CN201210101017A CN102600732A CN 102600732 A CN102600732 A CN 102600732A CN 2012101010177 A CN2012101010177 A CN 2012101010177A CN 201210101017 A CN201210101017 A CN 201210101017A CN 102600732 A CN102600732 A CN 102600732A
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Abstract
The invention relates to a method for preparing a bipolar membrane. The method comprises the following steps of: firstly mixing carboxymethylcellulose and polyving alcohol to prepare a PVA-CMC (Polyving Alcohol-Carboxymethylcellulose) cation exchange membrane, mixing chitosan and acetic acid aqueous solution to dissolve and prepare a chitosan acetic acid aqueous solution, dipping a glutaraldehyde solution, and carrying out curtain coating on the PVA-CMC cation exchange membrane. The method is characterized by comprising the following steps of adding a solar photocatalyst before dipping the glutaraldehyde solution after preparing the chitosan acetic acid aqueous solution. The solar photocatalyst is Co2<+>-TiO2, Fe3<+>-TiO2, Cr3<+>-TiO2, N-TiO2, S-TiO2, P-TiO2 or C-TiO2, and according to the addition amount of the solar photocatalyst, the ratio of the chitosan to the solar photocatalyst is equal to (3.0-6.0g):(0.001-0.1g). According to the method for preparing the bipolar membrane, disclosed by the invention, the solar photocatalyst is guided into an intermediate interface layer of the bipolar membrane, the catalyst intermediate interface layer is hydrolyzed, the hydrolysis efficiency is improved, and the membrane impedance and slot voltage are reduced.
Description
Technical field
The present invention relates to a kind of PREPARATIOM OF BIPOLAR MEMBRANE method, is the PREPARATIOM OF BIPOLAR MEMBRANE method that the sunlight catalytic agent is incorporated into intermediate layer specifically.
Background technology
(Bipolar Membrane's Bipolar Membrane BPM) normally is composited by anion exchange membrane facing (AM) and cation exchange rete (CM), and the yin, yang two rete inboards and the adjacent domain thereof that will constitute Bipolar Membrane usually are called intermediate layer.When placing Bipolar Membrane between electric groove yin, yang the two poles of the earth; Under the effect of DC electric field; Water in the Bipolar Membrane intermediate layer is with dissociating; Generate hydrogen ion and hydroxide ion, hydrogen ion sees through the cation exchange rete and gets into cathode chamber, and hydroxide ion sees through anion exchange membrane facing and gets into the anode chamber.
Bipolar Membrane and water decomposition technology thereof have very extensively and important use in fields such as Chemical Manufacture, separation, twice laid, resource recovery and environmental protection.
Promote Bipolar Membrane intermediate layer water decomposition, improve water decomposition efficient, reduce the membrane impedance and the tank voltage of Bipolar Membrane, reduce the generation of electroxidation reduction side reaction in the electric groove, become the focus of current Bipolar Membrane research.
T.Jeevananda etc. introduce the Bipolar Membrane intermediate layer with iron hydroxide, and water decomposition efficient obtains to improve; Guo Zhenzhen etc. as the anode membrane layer, promote the Bipolar Membrane water in intermediate layer to dissociate after the Fe3+ modification carboxymethyl cellulose phosphorylation; Employing nanometer, composite semiconductor photocatalysts such as Chen Riyao carry out modification to Bipolar Membrane, catalysis intermediate layer water decomposition, and under UV-irradiation, the water decomposition efficient of Bipolar Membrane obviously improves, and membrane impedance and tank voltage reduce greatly.
The present invention proposes the sunlight catalytic agent is added in the Bipolar Membrane, utilizes sunlight catalytic Bipolar Membrane intermediate layer water decomposition, and then reduces membrane impedance and tank voltage.
Summary of the invention
The purpose of this invention is to provide the Bipolar Membrane preparation method that a kind of intermediate layer contains the sunlight catalytic agent, it can make full use of solar energy, photocatalysis Bipolar Membrane intermediate layer water decomposition, and then reduce membrane impedance and tank voltage.
The objective of the invention is to realize through following technical scheme:
Accurately take by weighing 3.0g～6.0g carboxymethyl cellulose (CMC), be mixed with mass fraction and be 3.0%～6.0% the CMC aqueous solution; Other gets 6.0g～9.0g polyvinyl alcohol (PVA), with the dissolving of distilled water heated and stirred, joins in the CMC aqueous solution of above-mentioned preparation.Stir, vacuum deaerator obtains thickness film liquid, curtain coating in smooth culture dish, the at room temperature air-dry dry film that becomes a common practice.The first use of air-dry film mass fraction is 7.0%～10.0% the crosslinked 15～40min of FeCl3 solution soaking, and the back is clean with distilled water flushing, and natural air drying promptly gets the PVA-CMC cation-exchange membrane.
Accurately take by weighing 3.0g～6.0g shitosan (CS), using mass fraction is 2.0%～4.0% acetic acid aqueous solution stirring and dissolving, is mixed with mass fraction and is 3.0%～6.0% shitosan acetic acid aqueous solution.Take by weighing 0.001～0.1g sunlight catalytic agent powder, add adequate amount of ethanol, stir, and use ultrasonic oscillation, make it to be uniformly dispersed.Join then in the shitosan acetic acid aqueous solution of above-mentioned preparation; Quicken to stir, slowly dripping volume fraction while stirring is 3～6mL, 0.25% glutaraldehyde solution, vacuum deaerator; Obtain thickness film liquid; Curtain coating makes on the PVA-CMC cation-exchange membrane in above-mentioned, and is at room temperature air-dry, the Bipolar Membrane after the promptly handy sunlight catalytic agent modification.
Described sunlight catalytic agent is meant Co2+-TiO2, Fe3+-TiO2, Cr3+-TiO2, N-TiO2, S-TiO2, P-TiO2 or C-TiO2.
The agent of described interpolation sunlight catalytic, addition are that the mass ratio of shitosan and sunlight catalytic agent is 3.0g～6.0g: 0.001g～0.1g.
The specific embodiment
Embodiment 1
Accurately take by weighing 3.0g CMC, be mixed with 3.0% (mass fraction) CMC aqueous solution.Other gets 6.0g PVA, with the dissolving of distilled water heated and stirred, joins in the CMC aqueous solution of above-mentioned preparation.Stir, vacuum deaerator obtains thickness film liquid, curtain coating in smooth culture dish, the at room temperature air-dry dry film that becomes a common practice.With the crosslinked 15min of FeCl3 solution soaking of 7.0% (mass fraction), the back is clean with distilled water flushing earlier for air-dry film, and natural air drying promptly gets the PVA-CMC cation-exchange membrane.
Accurately take by weighing 3.0g CS,, be mixed with 3.0% (mass fraction) shitosan acetic acid aqueous solution with the acetic acid aqueous solution stirring and dissolving of 2.0% (mass fraction).Take by weighing 0.001g sunlight catalytic agent Fe3+-TiO2 powder, add adequate amount of ethanol, stir, and use ultrasonic oscillation, make it to be uniformly dispersed.Join then in the shitosan acetic acid aqueous solution of above-mentioned preparation; Quicken to stir, slowly drip 3mL0.25% (volume fraction) glutaraldehyde solution while stirring, vacuum deaerator; Obtain thickness film liquid; Curtain coating makes on the PVA-CMC cation-exchange membrane in above-mentioned, and is at room temperature air-dry, promptly gets the PVA-CMC/Fe3+-TiO2-CS Bipolar Membrane.
The PVA-CMC/Fe3+-TiO2-CS Bipolar Membrane bath voltage (V) under different electric current density (mA/cm2) that at room temperature records is as shown in the table:
Embodiment 2
Accurately take by weighing 3gCMC, be mixed with 3.5% (mass fraction) CMC aqueous solution.Other gets 9g PVA, with the dissolving of distilled water heated and stirred, joins in the CMC aqueous solution of above-mentioned preparation.Stir, vacuum deaerator obtains thickness film liquid, curtain coating in smooth culture dish, the at room temperature air-dry dry film that becomes a common practice.With the crosslinked 20min of FeCl3 solution soaking of 7.5% (mass fraction), the back is clean with distilled water flushing earlier for air-dry film, and natural air drying promptly gets the PVA-CMC cation-exchange membrane.
Accurately take by weighing 3gCS,, be mixed with 3.5% (mass fraction) shitosan acetic acid aqueous solution with the acetic acid aqueous solution stirring and dissolving of 2.5% (mass fraction).Take by weighing 0.1g sunlight catalytic agent Co2+-TiO2 powder, add adequate amount of ethanol, stir, and use ultrasonic oscillation, make it to be uniformly dispersed.Join then in the shitosan acetic acid aqueous solution of above-mentioned preparation; Quicken to stir, slowly drip 6mL0.25% (volume fraction) glutaraldehyde solution while stirring, vacuum deaerator; Obtain thickness film liquid; Curtain coating makes on the PVA-CMC cation-exchange membrane in above-mentioned, and is at room temperature air-dry, promptly gets the PVA-CMC/Co2+-TiO2-CS Bipolar Membrane.
The PVA-CMC/Co2+-TiO2-CS Bipolar Membrane bath voltage (V) under different electric current density (mA/cm2) that at room temperature records is as shown in the table:
Embodiment 3
Accurately take by weighing 4.0gCMC, be mixed with 4.0% (mass fraction) CMC aqueous solution.Other gets 8.0g PVA, with the dissolving of distilled water heated and stirred, joins in the CMC aqueous solution of above-mentioned preparation.Stir, vacuum deaerator obtains thickness film liquid, curtain coating in smooth culture dish, the at room temperature air-dry dry film that becomes a common practice.With the crosslinked 40min of FeCl3 solution soaking of 10% (mass fraction), the back is clean with distilled water flushing earlier for air-dry film, and natural air drying promptly gets the PVA-CMC cation-exchange membrane.
Accurately take by weighing 4.0gCS,, be mixed with 4.0% (mass fraction) shitosan acetic acid aqueous solution with the acetic acid aqueous solution stirring and dissolving of 2.5% (mass fraction).Take by weighing 0.05g sunlight catalytic agent Cr3+-TiO2 powder, add adequate amount of ethanol, stir, and use ultrasonic oscillation, make it to be uniformly dispersed.Join then in the shitosan acetic acid aqueous solution of above-mentioned preparation; Quicken to stir slow while stirring Dropwise 5 mL0.25% (volume fraction) glutaraldehyde solution, vacuum deaerator; Obtain thickness film liquid; Curtain coating makes on the PVA-CMC cation-exchange membrane in above-mentioned, and is at room temperature air-dry, promptly gets the PVA-CMC/Cr3+-TiO2-CS Bipolar Membrane.
The PVA-CMC/Cr3+-TiO2-CS Bipolar Membrane bath voltage (V) under different electric current density (mA/cm2) that at room temperature records is as shown in the table:
Embodiment 4
Accurately take by weighing 4.5g CMC, be mixed with 4.5% (mass fraction) CMC aqueous solution.Other gets 7.5g PVA, with the dissolving of distilled water heated and stirred, joins in the CMC aqueous solution of above-mentioned preparation.Stir, vacuum deaerator obtains thickness film liquid, curtain coating in smooth culture dish, the at room temperature air-dry dry film that becomes a common practice.With the crosslinked 35min of FeCl3 solution soaking of 8.5% (mass fraction), the back is clean with distilled water flushing earlier for air-dry film, and natural air drying promptly gets the PVA-CMC cation-exchange membrane.
Accurately take by weighing 4.5g CS,, be mixed with 4.5% (mass fraction) shitosan acetic acid aqueous solution with the acetic acid aqueous solution stirring and dissolving of 3.0% (mass fraction).Take by weighing 0.01g sunlight catalytic agent N-TiO2 powder, add adequate amount of ethanol, stir, and use ultrasonic oscillation, make it to be uniformly dispersed.Join then in the shitosan acetic acid aqueous solution of above-mentioned preparation; Quicken to stir, slowly drip 4.5mL0.25% (volume fraction) glutaraldehyde solution while stirring, vacuum deaerator; Obtain thickness film liquid; Curtain coating makes on the PVA-CMC cation-exchange membrane in above-mentioned, and is at room temperature air-dry, promptly gets the PVA-CMC/N-TiO2-CS Bipolar Membrane.
The PVA-CMC/N-TiO2-CS Bipolar Membrane bath voltage (V) under different electric current density (mA/cm2) that at room temperature records is as shown in the table:
Embodiment 5
Accurately take by weighing 5.0g CMC, be mixed with 5.0% (mass fraction) CMC aqueous solution.Other gets 6.5g PVA, with the dissolving of distilled water heated and stirred, joins in the CMC aqueous solution of above-mentioned preparation.Stir, vacuum deaerator obtains thickness film liquid, curtain coating in smooth culture dish, the at room temperature air-dry dry film that becomes a common practice.With the crosslinked 40min of FeCl3 solution soaking of 9.0% (mass fraction), the back is clean with distilled water flushing earlier for air-dry film, and natural air drying promptly gets the PVA-CMC cation-exchange membrane.
Accurately take by weighing 5.0gCS,, be mixed with 5.0% (mass fraction) shitosan acetic acid aqueous solution with the acetic acid aqueous solution stirring and dissolving of 4.0% (mass fraction).Take by weighing 0.06g sunlight catalytic agent P-TiO2 powder, add adequate amount of ethanol, stir, and use ultrasonic oscillation, make it to be uniformly dispersed.Join then in the shitosan acetic acid aqueous solution of above-mentioned preparation; Quicken to stir slow while stirring Dropwise 5 mL0.25% (volume fraction) glutaraldehyde solution, vacuum deaerator; Obtain thickness film liquid; Curtain coating makes on the PVA-CMC cation-exchange membrane in above-mentioned, and is at room temperature air-dry, promptly gets the PVA-CMC/P-TiO2-CS Bipolar Membrane.
The PVA-CMC/P-TiO2-CS Bipolar Membrane bath voltage (V) under different electric current density (mA/cm2) that at room temperature records is as shown in the table:
Embodiment 6
Accurately take by weighing 6.0gCMC, be mixed with 6.0% (mass fraction) CMC aqueous solution.Other gets 6.0g PVA, with the dissolving of distilled water heated and stirred, joins in the CMC aqueous solution of above-mentioned preparation.Stir, vacuum deaerator obtains thickness film liquid, curtain coating in smooth culture dish, the at room temperature air-dry dry film that becomes a common practice.With the crosslinked 15mm of FeCl3 solution soaking of 10.0% (mass fraction), the back is clean with distilled water flushing earlier for air-dry film, and natural air drying promptly gets the PVA-CMC cation-exchange membrane.
Accurately take by weighing 6.0gCS,, be mixed with 6.0% (mass fraction) shitosan acetic acid aqueous solution with the acetic acid aqueous solution stirring and dissolving of 4.0% (mass fraction).Take by weighing 0.001g sunlight catalytic agent S-TiO2 powder, add adequate amount of ethanol, stir, and use ultrasonic oscillation, make it to be uniformly dispersed.Join then in the shitosan acetic acid aqueous solution of above-mentioned preparation; Quicken to stir, slowly drip 6mL0.25% (volume fraction) glutaraldehyde solution while stirring, vacuum deaerator; Obtain thickness film liquid; Curtain coating makes on the PVA-CMC cation-exchange membrane in above-mentioned, and is at room temperature air-dry, promptly gets the PVA-CMC/S-TiO2-CS Bipolar Membrane.
The PVA-CMC/S-TiO2-CS Bipolar Membrane bath voltage (V) under different electric current density (mA/cm2) that at room temperature records is as shown in the table:
Claims (4)
1. one kind with sunlight catalytic agent modification PREPARATIOM OF BIPOLAR MEMBRANE method; At first getting carboxymethyl cellulose mixes with polyvinyl alcohol and processes PVA-CMC cation exchange rete; Then get shitosan and be mixed with the shitosan acetic acid aqueous solution with the acetic acid aqueous solution stirring and dissolving; Curtain coating is on the PVA-CMC cation-exchange membrane after dripping glutaraldehyde solution, it is characterized in that described be mixed with the shitosan acetic acid aqueous solution after, added the sunlight catalytic agent before dripping glutaraldehyde solution.
2. according to claim 1ly a kind ofly it is characterized in that the agent of described interpolation sunlight catalytic, at first take by weighing sunlight catalytic agent powder with sunlight catalytic agent modification PREPARATIOM OF BIPOLAR MEMBRANE method; Add adequate amount of ethanol, stir, and use ultrasonic oscillation; Make it to be uniformly dispersed, join then in the shitosan acetic acid aqueous solution, quicken to stir; Slowly dripping volume fraction while stirring is 3～6mL, 0.25% glutaraldehyde solution, and vacuum deaerator obtains thickness film liquid; Thickness film flow is prolonged on the PVA-CMC cation-exchange membrane that has made, and is at room temperature air-dry.
3. described a kind of with sunlight catalytic agent modification PREPARATIOM OF BIPOLAR MEMBRANE method with 3 according to claim 1; It is characterized in that the agent of described interpolation sunlight catalytic, sunlight catalytic agent addition is a shitosan: sunlight catalytic agent=3.0g～6.0g: 0.001g～0.1g.
4. according to claim 1 a kind of with sunlight catalytic agent modification PREPARATIOM OF BIPOLAR MEMBRANE method, it is characterized in that described sunlight catalytic agent is Co
2+-TiO2, Fe
3+-TiO2, Cr
3+-TiO
2, N-TiO
2, S-TiO
2, P-TiO
2Or C-TiO
2
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103657731A (en) * | 2013-09-12 | 2014-03-26 | 江苏科技大学 | Preparation method of photocatalytic composite nano-particles and application of photocatalytic composite nano-particles in acid orange dye wastewater treatment |
| CN106865844A (en) * | 2017-03-01 | 2017-06-20 | 太原理工大学 | A kind of photoelectrocatalysis recycling and processing device for high-concentration phenol ammonia waste water |
| CN107096572A (en) * | 2017-04-24 | 2017-08-29 | 太原师范学院 | A kind of method for preparing Bipolar Membrane surface powder state photochemical catalyst |
| US10843138B1 (en) | 2019-10-07 | 2020-11-24 | King Abdulaziz University | Cellulose acetate V/ZN photocatalytic material |
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| CN1865509A (en) * | 2006-04-07 | 2006-11-22 | 福建师范大学 | Novel dipolar membrane and use thereof in electrolysis preparation of ferrate |
| CN101613483A (en) * | 2009-08-05 | 2009-12-30 | 福建师范大学 | With photosensitizers or photocatalytic semiconductor material is the Bipolar Membrane in middle layer and preparation method thereof |
| CN102336916A (en) * | 2011-09-13 | 2012-02-01 | 福建师范大学 | Method for preparing modified bipolar membrane taking poly(vinyl alcohol)-chitosan as interface layer |
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2012
- 2012-04-06 CN CN2012101010177A patent/CN102600732A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1865509A (en) * | 2006-04-07 | 2006-11-22 | 福建师范大学 | Novel dipolar membrane and use thereof in electrolysis preparation of ferrate |
| CN101613483A (en) * | 2009-08-05 | 2009-12-30 | 福建师范大学 | With photosensitizers or photocatalytic semiconductor material is the Bipolar Membrane in middle layer and preparation method thereof |
| CN102336916A (en) * | 2011-09-13 | 2012-02-01 | 福建师范大学 | Method for preparing modified bipolar membrane taking poly(vinyl alcohol)-chitosan as interface layer |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103657731A (en) * | 2013-09-12 | 2014-03-26 | 江苏科技大学 | Preparation method of photocatalytic composite nano-particles and application of photocatalytic composite nano-particles in acid orange dye wastewater treatment |
| CN106865844A (en) * | 2017-03-01 | 2017-06-20 | 太原理工大学 | A kind of photoelectrocatalysis recycling and processing device for high-concentration phenol ammonia waste water |
| CN107096572A (en) * | 2017-04-24 | 2017-08-29 | 太原师范学院 | A kind of method for preparing Bipolar Membrane surface powder state photochemical catalyst |
| US10843138B1 (en) | 2019-10-07 | 2020-11-24 | King Abdulaziz University | Cellulose acetate V/ZN photocatalytic material |
| US10870088B1 (en) | 2019-10-07 | 2020-12-22 | King Abdulaziz University | Composite photocatalysts embedded in microporous membranes |
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Application publication date: 20120725 |