CN111111794A - Preparation method of out-of-phase bipolar membrane not easy to fall off - Google Patents
Preparation method of out-of-phase bipolar membrane not easy to fall off Download PDFInfo
- Publication number
- CN111111794A CN111111794A CN201911424479.0A CN201911424479A CN111111794A CN 111111794 A CN111111794 A CN 111111794A CN 201911424479 A CN201911424479 A CN 201911424479A CN 111111794 A CN111111794 A CN 111111794A
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- Prior art keywords
- membrane
- bipolar membrane
- mesh cloth
- exchange membrane
- cation exchange
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- 239000012528 membrane Substances 0.000 title claims abstract description 122
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000004744 fabric Substances 0.000 claims abstract description 49
- 238000005341 cation exchange Methods 0.000 claims abstract description 46
- 239000003011 anion exchange membrane Substances 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 32
- 238000003825 pressing Methods 0.000 claims abstract description 24
- 238000003466 welding Methods 0.000 claims abstract description 14
- 229920001169 thermoplastic Polymers 0.000 claims description 11
- 238000007731 hot pressing Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000003957 anion exchange resin Substances 0.000 claims description 4
- 239000003729 cation exchange resin Substances 0.000 claims description 4
- 238000005342 ion exchange Methods 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 238000005096 rolling process Methods 0.000 claims description 3
- 210000004379 membrane Anatomy 0.000 description 60
- 239000010410 layer Substances 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000004416 thermosoftening plastic Substances 0.000 description 7
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 239000003014 ion exchange membrane Substances 0.000 description 4
- 238000005349 anion exchange Methods 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 210000002469 basement membrane Anatomy 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 210000003934 vacuole Anatomy 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- B01J47/00—Ion-exchange processes in general; Apparatus therefor
- B01J47/12—Ion-exchange processes in general; Apparatus therefor characterised by the use of ion-exchange material in the form of ribbons, filaments, fibres or sheets, e.g. membranes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The preparation method of the heterogeneous bipolar membrane difficult to fall off comprises the following steps: (1) attaching the anion exchange membrane only with the mesh cloth on one side and the cation exchange membrane only with the mesh cloth on one side without two sides of the mesh cloth to prepare a bipolar membrane, or attaching the anion exchange membrane only with the mesh cloth on one side without one side of the mesh cloth and the cation exchange membrane with the double-sided mesh cloth to prepare a bipolar membrane, or attaching the cation exchange membrane only with the mesh cloth on one side without one side of the mesh cloth and the anion exchange membrane with the double-sided mesh cloth to prepare a bipolar membrane; (2) and (2) putting the bipolar membrane prepared in the step (1) into a high-temperature and high-pressure environment for pressing and welding. The method has the advantages of simple process and convenient operation, and the prepared bipolar membrane has strong stability and is not easy to peel off. In addition, the bipolar membrane prepared by the method still has mesh support, the mechanical property is still good, and the bipolar membrane cannot be curled and deformed.
Description
Technical Field
The invention relates to the field of bipolar membrane preparation, in particular to a preparation method of a heterogeneous bipolar membrane which is not easy to fall off.
Background
The polar membrane is also called bipolar membrane, and is an anion-cation exchange composite membrane prepared by compounding a cation exchange membrane and an anion exchange membrane. The membrane is characterized in that under the action of a direct current electric field, water between the anion exchange membrane and the cation exchange membrane is dissociated into H + and OH-which selectively pass through the anion exchange membrane and the cation exchange membrane respectively, so that the membrane is an H + and OH-ion source. The bipolar membranes are divided into two types, namely heterogeneous membranes and homogeneous membranes, and the preparation methods of the bipolar membranes in the prior art generally comprise the following methods: (1) the hot pressing formation process of anion and cation exchange film includes superposing dried anion and cation exchange film inside stainless steel plate covered with PTFE film, eliminating inner bubble, heating and pressurizing to obtain bipolar film. (2) The method for adhering and forming the anion-cation exchange membrane layer is to coat the inner sides of the anion-cation exchange membrane layer and the cation-cation exchange membrane layer with adhesives respectively, then to superpose, to remove the air bubbles and vacuoles inside, and to obtain the bipolar membrane after drying. (3) And (3) a casting forming method, namely covering a layer of polymer solution dispersed with cation exchange resin on the anion exchange membrane layer, or covering a layer of polymer solution dispersed with anion exchange resin on the cation exchange membrane layer, and drying to obtain the bipolar membrane. (4) The method is to introduce anion and cation exchange groups on both sides of the polymer basement membrane by chemical reaction method to prepare bipolar membrane. (5) The formation method of one film layer on another film layer by electrodeposition is that an ion exchange membrane is assembled in an electrolytic bath, ion exchange resin powder with opposite electric properties is suspended in an electrolyte, and direct current is supplied to deposit resin particles on the surface of the membrane to form the bipolar membrane.
In a plurality of preparation methods, the hot pressing method of the anion-cation exchange membrane layer does not need any additional chemical reagent and complex electrical equipment, and is environment-friendly and safe. However, the two layers of the anion exchange membrane and the cation exchange membrane are easy to separate in the use process of the bipolar membrane directly thermally pressed by the method, and scale is easy to deposit in a stripped gap, so that the performance of the membrane is attenuated, the hydrolysis voltage is increased, and even the membrane loses the effect.
Therefore, it is necessary to provide a method for preparing a heterogeneous bipolar membrane with less tendency to fall off in order to overcome the deficiencies of the prior art.
Disclosure of Invention
The invention aims to avoid the defects of the prior art and provides a preparation method of a heterogeneous bipolar membrane which is not easy to fall off.
The object of the invention is achieved by the following technical measures.
Provided is a method for producing a heterogeneous bipolar membrane which is less likely to fall off, 1. A method for producing a heterogeneous bipolar membrane which is less likely to fall off, comprising the steps of: (1) attaching the anion exchange membrane only with the mesh cloth on one side and the cation exchange membrane only with the mesh cloth on one side without two sides of the mesh cloth to prepare a bipolar membrane, or attaching the anion exchange membrane only with the mesh cloth on one side without one side of the mesh cloth and the cation exchange membrane with the double-sided mesh cloth to prepare a bipolar membrane, or attaching the cation exchange membrane only with the mesh cloth on one side without one side of the mesh cloth and the anion exchange membrane with the double-sided mesh cloth to prepare a bipolar membrane; (2) and (2) putting the bipolar membrane prepared in the step (1) into a high-temperature and high-pressure environment for pressing and welding.
Preferably, the anion exchange membrane and the cation exchange membrane in step (1) have the same or different ion exchange capacities.
Preferably, the anion exchange membrane and the cation exchange membrane in step (1) have the same or different thicknesses.
Preferably, the anion exchange membrane is formed by mixing an anion exchange resin and a thermoplastic, and the cation exchange membrane is formed by mixing a cation exchange resin and a thermoplastic.
Preferably, the pressing process in the step (2) is hot pressing, IMD hot press molding, high frequency welding, ultrasonic welding or rolling.
Preferably, the pressing temperature in the step (2) is 60-250 ℃.
Preferably, the pressing temperature in the step (2) is 120-150 ℃.
Preferably, the pressing temperature in the step (2) is 80-100 ℃.
Preferably, the pressure in step (2) is 0.5-50 MPa.
Preferably, the pressure in step (2) is 30-50 MPa.
The preparation method of the heterogeneous bipolar membrane difficult to fall off comprises the following steps: (1) attaching the anion exchange membrane only with the mesh cloth on one side and the cation exchange membrane only with the mesh cloth on one side without two sides of the mesh cloth to prepare a bipolar membrane, or attaching the anion exchange membrane only with the mesh cloth on one side without one side of the mesh cloth and the cation exchange membrane with the double-sided mesh cloth to prepare a bipolar membrane, or attaching the cation exchange membrane only with the mesh cloth on one side without one side of the mesh cloth and the anion exchange membrane with the double-sided mesh cloth to prepare a bipolar membrane; (2) and (2) putting the bipolar membrane prepared in the step (1) into a high-temperature and high-pressure environment for pressing and welding. The method has the advantages of simple process and convenient operation, and the prepared bipolar membrane has strong stability and is not easy to peel off. In addition, the bipolar membrane prepared by the method still has mesh support, the mechanical property is still good, and the bipolar membrane cannot be curled and deformed.
Detailed Description
The invention is further illustrated by the following examples.
Example 1.
A method for producing a hetero-bipolar membrane which is less likely to fall off, there is provided a method for producing a hetero-bipolar membrane which is less likely to fall off, 1. a method for producing a hetero-bipolar membrane which is less likely to fall off, comprising the steps of: (1) attaching the anion exchange membrane only with the mesh cloth on one side and the cation exchange membrane only with the mesh cloth on one side without the mesh cloth on two sides to prepare a bipolar membrane; (2) and (2) putting the bipolar membrane prepared in the step (1) into a high-temperature and high-pressure environment for pressing and welding.
In this example, the anion exchange membrane and the cation exchange membrane in step (1) have the same or different ion exchange capacities. In the step (1), the thicknesses of the anion exchange membrane and the cation exchange membrane are the same or different. The use of anion exchange membranes or cation exchange membranes with different properties can improve the selection diversity of the bipolar membrane, and can adjust the hydrolysis voltage on the two sides of the bipolar membrane and the concentration of generated acid and alkali.
In this example, the anion exchange membrane is formed by mixing an anion exchange resin and a thermoplastic, and the cation exchange membrane is formed by mixing a cation exchange resin and a thermoplastic. The thermoplastic plastic has the characteristics of heating, melting, cooling and solidifying, so that the thermoplastic plastic can be used as a binding agent for an anion exchange membrane and a cation exchange membrane.
In this embodiment, the pressing process in step (2) is hot pressing with a hot plate, hot pressing, IMD hot press molding, high frequency welding, ultrasonic welding, or rolling. No matter which pressing process is adopted, the anion exchange membrane and the cation exchange membrane are ensured to be attached and aligned before pressing.
In this embodiment, the pressing temperature in the step (2) is 60 ℃ to 250 ℃, and the pressing pressure is 25 MPa. At high temperature, the thermoplastics in the thermoplastic box cation exchange membranes in the anion exchange membranes are melted and then mixed with each other, so that the two surfaces of the anion exchange membranes and the two surfaces of the cation exchange membranes, which are attached to each other, are fully welded. In a high pressure environment, the flow of the molten thermoplastic is accelerated, and the welding can be accelerated.
The preparation method of the out-of-phase bipolar membrane not easy to fall off has the advantages of simple process, convenient operation and high welding speed, and the prepared bipolar membrane has strong stability and is not easy to fall off. In addition, the bipolar membrane prepared by the method still has mesh support, the mechanical property is still good, and the bipolar membrane cannot be curled and deformed.
Example 2.
A method for producing a bipolar membrane which is less likely to fall off, and which is otherwise the same as in example 1 except that: and (1) attaching the surface of the anion exchange membrane with the mesh cloth on the single surface without the mesh cloth and the cation exchange membrane with the mesh cloth on the double surfaces together to prepare the bipolar membrane. The pressing temperature in the step (2) is 150 ℃, and the pressing pressure in the step (2) is 35 MPa. The one-layer screen cloth is arranged between the middle of the bipolar membrane anion exchange membrane and the middle of the cation exchange membrane, the adhesiveness of the bipolar membrane is not influenced, the welding can be very firm, the single-layer screen cloth can control the thickness of the two layers of membranes of the ion exchange membrane and the cation exchange membrane, which are mutually permeated, not too deep, and the influence on the hydrolysis voltage is avoided.
Example 3.
A method for producing a bipolar membrane which is less likely to fall off, and which is otherwise the same as in example 1 except that: step (1), attaching one surface of a cation exchange membrane with a mesh cloth on only one side without the mesh cloth and an anion exchange membrane with a double-sided mesh cloth together to prepare a bipolar membrane; the pressing temperature in the step (2) is 90 ℃, and the pressing pressure is 50 MPa. Have one deck screen cloth between bipolar membrane anion exchange membrane and the middle of the cation exchange membrane not to influence the cohesiveness of bipolar membrane, equally can the butt fusion very firm, the thickness that the two-layer membrane of single-deck screen cloth can also control and should ion exchange membrane and cation exchange membrane interpenetration can not be too dark, has avoided the influence to hydrolysis voltage, and the butt fusion can also avoid the ion exchange membrane to decompose under this temperature.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. A preparation method of a heterogeneous bipolar membrane which is not easy to fall off is characterized by comprising the following steps:
(1) attaching the anion exchange membrane only with the mesh cloth on one side and the cation exchange membrane only with the mesh cloth on one side without two sides of the mesh cloth to prepare a bipolar membrane, or attaching the anion exchange membrane only with the mesh cloth on one side without one side of the mesh cloth and the cation exchange membrane with the double-sided mesh cloth to prepare a bipolar membrane, or attaching the cation exchange membrane only with the mesh cloth on one side without one side of the mesh cloth and the anion exchange membrane with the double-sided mesh cloth to prepare a bipolar membrane;
(2) and (2) putting the bipolar membrane prepared in the step (1) into a high-temperature and high-pressure environment for pressing and welding.
2. The method for preparing a bipolar membrane with low tendency to fall off according to claim 1, wherein: in the step (1), the anion exchange membrane and the cation exchange membrane have the same or different ion exchange capacities.
3. The method for preparing a bipolar membrane with low probability of shedding according to claim 2, wherein: in the step (1), the thicknesses of the anion exchange membrane and the cation exchange membrane are the same or different.
4. The method for preparing a bipolar membrane with low probability of shedding according to claim 2, wherein: the anion exchange membrane in the step (1) is formed by mixing anion exchange resin and thermoplastic plastics;
the cation exchange membrane is formed by mixing cation exchange resin and thermoplastic plastics.
5. The method for preparing a bipolar membrane with low probability of shedding according to claim 2, wherein: and (3) the pressing process in the step (2) is hot pressing by a hot plate, hot pressing, IMD hot press molding, high-frequency welding, ultrasonic welding or rolling.
6. The method for preparing a bipolar membrane with low probability of shedding according to claim 2, wherein: the pressing temperature in the step (2) is 60-250 ℃.
7. The method for preparing a bipolar membrane with low tendency to fall off according to claim 1, wherein: the pressing temperature in the step (2) is 120-150 ℃.
8. The method for preparing a bipolar membrane with low tendency to fall off according to claim 1, wherein: the pressing temperature in the step (2) is 80-100 ℃.
9. The method for preparing a bipolar membrane with low tendency to fall off according to claim 1, wherein: the pressing pressure in the step (2) is 0.5MPa-50 MPa.
10. The method for preparing a bipolar membrane with low tendency to fall off according to claim 1, wherein: in the step (2), the pressing pressure is 30-50 Mpa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911424479.0A CN111111794A (en) | 2019-12-31 | 2019-12-31 | Preparation method of out-of-phase bipolar membrane not easy to fall off |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201911424479.0A CN111111794A (en) | 2019-12-31 | 2019-12-31 | Preparation method of out-of-phase bipolar membrane not easy to fall off |
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| CN111111794A true CN111111794A (en) | 2020-05-08 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6217733B1 (en) * | 1994-07-05 | 2001-04-17 | Solvay (Societe Anonyme) | Bipolar membrane and method for fabricating such bipolar membrane |
| CN2732339Y (en) * | 2004-10-21 | 2005-10-12 | 浙江欧美环境工程有限公司 | Heterophase ion exchange membrane reinforced by employing conductive ion reticular cloth |
| CN106999925A (en) * | 2014-11-19 | 2017-08-01 | 豪威株式会社 | The two poles of the earth ion exchange plate and its manufacture method |
| CN107171010A (en) * | 2017-05-11 | 2017-09-15 | 厦门大学 | A kind of compound Bipolar Membrane and preparation method thereof |
| CN107706435A (en) * | 2017-10-09 | 2018-02-16 | 太原理工大学 | A kind of bipolar film type direct borohydride fuel cell |
-
2019
- 2019-12-31 CN CN201911424479.0A patent/CN111111794A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6217733B1 (en) * | 1994-07-05 | 2001-04-17 | Solvay (Societe Anonyme) | Bipolar membrane and method for fabricating such bipolar membrane |
| CN2732339Y (en) * | 2004-10-21 | 2005-10-12 | 浙江欧美环境工程有限公司 | Heterophase ion exchange membrane reinforced by employing conductive ion reticular cloth |
| CN106999925A (en) * | 2014-11-19 | 2017-08-01 | 豪威株式会社 | The two poles of the earth ion exchange plate and its manufacture method |
| CN107171010A (en) * | 2017-05-11 | 2017-09-15 | 厦门大学 | A kind of compound Bipolar Membrane and preparation method thereof |
| CN107706435A (en) * | 2017-10-09 | 2018-02-16 | 太原理工大学 | A kind of bipolar film type direct borohydride fuel cell |
Non-Patent Citations (4)
| Title |
|---|
| 刘颖等: "双极膜制备及改性研究进展", 《化工进展》 * |
| 时钧等: "《膜技术手册》", 31 January 2001, 北京：化学工业出版社 * |
| 杨座国: "《膜科学技术过程与原理》", 31 August 2009, 上海：华东理工大学出版社 * |
| 王湛等: "《膜分离技术基础》", 31 August 2006, 北京：化学工业出版社 * |
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Application publication date: 20200508 |