CN108905645B - Ion exchange membrane with high molecular protection film and preparation method thereof - Google Patents

Ion exchange membrane with high molecular protection film and preparation method thereof Download PDF

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Publication number
CN108905645B
CN108905645B CN201810991995.0A CN201810991995A CN108905645B CN 108905645 B CN108905645 B CN 108905645B CN 201810991995 A CN201810991995 A CN 201810991995A CN 108905645 B CN108905645 B CN 108905645B
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ion exchange
exchange membrane
film
protective film
polymer protective
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CN108905645A (en
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卜毅男
陈白杨
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Shenzhen Hehe Environmental Technology Co ltd
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Shenzhen Hehe Environmental Technology Co ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D71/00Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06Organic material
    • B01D71/28Polymers of vinyl aromatic compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D67/00Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002Organic membrane manufacture
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D69/00Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12Composite membranes; Ultra-thin membranes
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/42Treatment of water, waste water, or sewage by ion-exchange
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2311/00Details relating to membrane separation process operations and control
    • B01D2311/26Further operations combined with membrane separation processes
    • B01D2311/2623Ion-Exchange
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/36Organic compounds containing halogen

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

The invention discloses an ion exchange membrane with a high polymer protective film and a preparation method thereof. The ion exchange membrane comprises: the ion exchange membrane comprises a high polymer protection film and an ion exchange film, wherein the high polymer protection film is formed on the surface of the ion exchange film, the high polymer protection film is a film which is made of high polymer materials and has a porous structure, the average pore diameter of the high polymer protection film is smaller than 100 daltons, the ion exchange film is a styrene heterogeneous ion exchange film, the material of the high polymer protection film is chitosan or a chitosan derivative, the high polymer protection film is formed on the surface of the ion exchange film by adopting a phase molecular conversion method or is formed on the surface of the ion exchange film by adopting a coating film forming method, and one side of the high polymer protection film is provided with a flow guiding structure. The ion exchange membrane with the high-molecular protective film and the preparation method thereof provided by the invention have the characteristics of high retention rate of organic matters and good deionization effect.

Description

Ion exchange membrane with high molecular protection film and preparation method thereof
Technical Field
The invention relates to the field of water treatment, in particular to an ion exchange membrane with a high molecular protection membrane and a preparation method thereof.
Background
Various organic matters in a water sample are indexes which are frequently required to be detected in water treatment research, and the existing analysis and detection method has larger interference when inorganic ions exist in a large amount. In order to avoid the interference of inorganic ions, solid-liquid extraction, liquid-liquid extraction and other modes are usually adopted for pretreatment before, so as to extract organic matters in water. However, for practical water samples, the organic components are very complex, and hydrophilic organic matters are difficult to be efficiently recovered through an extraction process, so that the organic matters have larger loss.
Inorganic ions in the water sample are removed by adopting an electrodialysis mode, organic matters in the water sample are reserved, and the organic matters in the water sample can be recovered more efficiently, so that the subsequent detection is convenient. However, in the detection of some practical water samples, it is found that a series of interactions between the organic matters and the ion exchange membrane occur, for example, ionic organic matters are also removed, and organic matters with strong adsorptivity are also adsorbed. These effects all cause loss of organics and cause detection errors of organics.
In addition, in the prior art, a partition plate is arranged between two ion exchange membranes in the electrodialyzer, so that on one hand, short circuit caused by direct contact of the anion exchange membrane and the cation exchange membrane is avoided, and on the other hand, turbulent flow and uniform concentration distribution of sample liquid are promoted. The pore space of the baffle plate is smaller, and liquid is easy to remain after cleaning, so that the concentration of a subsequent sample can be influenced; in addition, when the electrodialysis is used for treating liquid, the thinner the thickness of the water sample in the sample chamber is, the better the treatment effect is, in order to pursue the treatment effect, the distance between the two ion exchange membranes of the electrodialysis device for detection is often smaller, and after the separation plate is placed, the separation plate thickness can limit the distance between the two ion exchange membranes.
Disclosure of Invention
The invention aims to provide an ion exchange membrane with a high polymer protective film and a preparation method thereof, and the ion exchange membrane has the characteristics of high retention rate of organic matters and good deionization effect.
In order to achieve the above object, the present invention provides the following solutions:
An ion exchange membrane having a polymeric protective film comprising: the ion exchange membrane comprises a high polymer protective film and an ion exchange membrane, wherein the high polymer protective film is formed on the surface of the ion exchange membrane, and the high polymer protective film is a film which is made of high polymer materials and has a porous structure.
Optionally, the polymer protective film has an average pore size of less than 100 daltons.
Optionally, the ion exchange membrane is a styrene heterogeneous ion exchange membrane.
Optionally, the material of the polymer protective film is chitosan or a derivative of chitosan.
Optionally, the polymer protective film is a film formed on the surface of the ion exchange film by adopting a phase molecular conversion method.
Optionally, the polymer protective film is a film formed on the surface of the ion exchange film by a coating film forming method.
Optionally, one side of the polymer protection film is attached to the ion exchange film, and the other side is provided with a flow guiding structure.
Optionally, the flow guiding structure is a plurality of strings with the diameter smaller than 1mm.
The invention also provides a preparation method of the ion exchange membrane with the polymer protective film, which comprises the following steps:
preparing a heterogeneous ion exchange membrane taking styrene as a framework;
preparing a solution containing chitosan or a derivative thereof;
Immersing the ion exchange membrane into the solution containing chitosan or the derivative thereof after fixing the ion exchange membrane by using a clamp, so that only one side of the ion exchange membrane contacts the solution for 20min;
taking out the ion exchange membrane and airing at a place protected from light at normal temperature.
Optionally, the method further comprises: and repeatedly immersing the dried ion exchange membrane into a solution containing chitosan or derivatives thereof for 20min, and taking out the ion exchange membrane and drying the ion exchange membrane in a place protected from light at normal temperature.
According to the specific embodiment provided by the invention, the invention discloses the following technical effects: according to the ion exchange membrane with the high polymer protective film and the preparation method thereof, organic matters in the solution can be effectively blocked by the high polymer protective film in the electrodialysis process, so that the contact between the high polymer protective film and the ion exchange membrane can not be reduced or greatly reduced, and the retention of the organic matters can be improved. In addition, the compact microporous structure of the polymer protective film ensures that water molecules and ions in the solution can smoothly pass through the polymer protective film, but can block most of organic matters from directly contacting with the ion exchange film, so that the influence of the organic matters on the ion exchange groups can be reduced, and the ion exchange function of the ion exchange film is protected. In addition, the ion exchange membrane with the high polymer protective film provided by the invention has the advantages that the high polymer protective film is formed on the surface of the ion exchange membrane, a gap between the films does not exist, a water layer is not formed, the influence on the change of the volume of a water sample in the electrodialysis process is smaller, and in addition, the high polymer protective film is provided with the flow guiding structure, so that the water sample can be uniformly treated in the electrodialysis process; the use of a baffle is avoided, and the space between two ion exchange membranes is shortened; the influence of residual liquid in the gap of the partition board on the concentration of the sample after the cleaning process is avoided.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions of the prior art, the drawings that are needed in the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of an ion exchange membrane with a polymer protective film according to an embodiment of the present invention;
FIG. 2 is a schematic diagram of an ion exchange membrane flow guiding structure with a polymer protective film according to an embodiment of the present invention;
FIG. 3 is a flow chart of a method for preparing an ion exchange membrane with a polymer protective film according to an embodiment of the invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the invention, are within the scope of the invention based on the embodiments of the invention.
The invention aims to provide an ion exchange membrane with a high polymer protective film and a preparation method thereof, and the ion exchange membrane has the characteristics of high retention rate of organic matters and good deionization effect.
In order that the above-recited objects, features and advantages of the present invention will become more readily apparent, a more particular description of the invention will be rendered by reference to the appended drawings and appended detailed description.
Fig. 1 is a schematic structural diagram of an ion exchange membrane with a polymer protective film according to an embodiment of the present invention, and as shown in fig. 1, the ion exchange membrane with a polymer protective film provided by the present invention includes: the ion exchange membrane comprises an ion exchange membrane 1 and a polymer protective film 2, wherein the polymer protective film 2 is formed on the surface of the ion exchange membrane 1, and the polymer protective film 2 is a film which is composed of polymer materials and has a porous structure. The average pore size is less than 100 daltons.
The ion exchange membrane 1 may be a styrene heterogeneous ion exchange membrane. The surface of the film is relatively rough, and the polymer film material is easy to be adhered to the ion exchange film during the subsequent polymer protective film forming.
The material of the polymer protective film 2 is chitosan or chitosan derivatives. The chitosan or the derivative thereof is easy to form a film, and the polymer film prepared from the material has higher acid and alkali tolerance (can work in a wider pH range) and stronger tolerance to organic matters.
The polymer protective film 2 can be formed on the surface of the ion exchange film by adopting a phase molecular conversion method; the ion exchange membrane may be formed on the surface of the ion exchange membrane by a coating film forming method.
One side of the polymer protective film 2 is attached to the ion exchange film 1, and the other side is provided with a flow guiding structure 3, as shown in fig. 2. The flow guiding structure can be a plurality of strings with the diameter smaller than 1 mm. The string can be made of non-conductive and corrosion-resistant materials such as polytetrafluoroethylene, PEEK and the like.
The invention also provides a preparation method of the ion exchange membrane with the polymer protective film, as shown in fig. 3, the preparation method provided by the invention comprises the following steps:
Step 301: preparing a heterogeneous ion exchange membrane taking styrene as a framework;
step 302: preparing a solution containing chitosan or a derivative thereof;
Step 303: immersing the ion exchange membrane in the solution in step 202 after fixing the ion exchange membrane by using a clamp, and enabling only one side of the ion exchange membrane to contact the solution for 20min;
Step 304: taking out the ion exchange membrane and airing at a place protected from light at normal temperature.
In order to obtain a polymer protective film with compact aperture, the coating process can be repeated, namely, the dried ion exchange film is immersed into a solution containing chitosan or derivatives thereof for 20min, and then taken out to be dried in a place with light shielding at normal temperature.
The following test and verification are carried out on the effect of the ion exchange membrane with the polymer protective film provided by the invention:
Example 1
In the method, common halogenated organic matters are selected as samples, and the effect of organic matter retention after deionization operation by using different membranes is verified. The sample was prepared with ultrapure water, and contained 100. Mu.g/L of chloroform, 100. Mu.g/L of bromomethane, 100. Mu.g/L of chloral, 100. Mu.g/L of trichloroacetonitrile, 100. Mu.g/L of trichloroacetic acid, 100. Mu.g/L of monochloroacetic acid, and 10mg/L of chloride ions. In the experiment, the interval between the anion exchange membrane and the cation exchange membrane is 1mm, the voltage between the two electrode plates is direct current 20V, and tap water is introduced into a sample chamber; the sample injection flow rate is 0.5mL/min, sodium bicarbonate solution is introduced into the two electrode chambers, and the flow rate is 1mL/min.
The initial water quality index and the index after pretreatment are shown in Table one:
List one
The composite membrane in the table I refers to the ion exchange membrane with the polymer protective membrane provided by the invention, and the result shows that electrodialysis equipment adopting the composite membrane has good removal of chloride ions, and the removal rate is more than 99%; the recovery rate of the two membranes to chloroform, bromoform, chloral and trichloroacetonitrile is ideal and is more than 95%. However, for substances such as trichloroacetic acid and monochloroacetic acid which are easy to ionize in water, common ion exchange membranes cannot recover the substances, and the recovery rate is 0; and after the composite membrane is adopted, the recovery rate of the two substances is 76% and 54%, and the recovery rate is greatly improved.
Example two
Tap water is selected as a water sample to be tested in the example, and the treatment effect is verified. In the experiment, the interval between the anion exchange membrane and the cation exchange membrane is 1mm, the voltage between the two electrode plates is direct current 20V, and tap water is introduced into a sample chamber; the sample injection flow rate of tap water is 0.5mL/min, sodium bicarbonate solution is introduced into the two electrode chambers, and the flow rate is 1mL/min. The initial water quality index and the index after pretreatment are shown in Table II:
Watch II
From the results, the electrodialysis device adopting the composite membrane has good removal of chloride ions, and the removal rate is more than 98.9%. After the tap water sample is treated by the composite membrane electrodialysis device, the retention rate of Total Organic Carbon (TOC) is 89.3%, and the retention rate of TOC of the sample treated by the common ion exchange membrane electrodialysis device is 62.9%. The retention rate of the total organic matters is improved, and the accuracy of the improvement detection method is significant for applying electrodialysis equipment to the detection field.
According to the ion exchange membrane with the high polymer protective film and the preparation method thereof, organic matters in the solution can be effectively blocked by the high polymer protective film in the electrodialysis process, so that the contact between the high polymer protective film and the ion exchange membrane can not be reduced or greatly reduced, and the retention of the organic matters can be improved. In addition, the compact microporous structure of the polymer protective film ensures that water molecules and ions in the solution can smoothly pass through the polymer protective film, but can block most of organic matters from directly contacting with the ion exchange film, so that the influence of the organic matters on the ion exchange groups can be reduced, and the ion exchange function of the ion exchange film is protected. In addition, the ion exchange membrane with the high polymer protective film provided by the invention has the advantages that the high polymer protective film is formed on the surface of the ion exchange membrane, a gap between the films does not exist, a water layer is not formed, the influence on the change of the volume of a water sample in the electrodialysis process is smaller, and in addition, the high polymer protective film is provided with the flow guiding structure, so that the water sample can be uniformly treated in the electrodialysis process; the use of a baffle is avoided, and the space between two ion exchange membranes is shortened; the influence of the liquid remained in the gap of the partition board after each cleaning on the concentration of the sample is avoided.
In the present specification, each embodiment is described in a progressive manner, and each embodiment is mainly described in a different point from other embodiments, and identical and similar parts between the embodiments are all enough to refer to each other.
The principles and embodiments of the present invention have been described herein with reference to specific examples, the description of which is intended only to assist in understanding the methods of the present invention and the core ideas thereof; also, it is within the scope of the present invention to be modified by those of ordinary skill in the art in light of the present teachings. In view of the foregoing, this description should not be construed as limiting the invention.

Claims (9)

1. An ion exchange membrane having a polymer protective film, comprising: the ion exchange membrane comprises a high polymer protective film and an ion exchange membrane, wherein the high polymer protective film is formed on the surface of the ion exchange membrane, and the high polymer protective film is a film which is made of a high polymer material and has a porous structure;
the preparation method of the ion exchange membrane with the polymer protective film comprises the following steps:
preparing a heterogeneous ion exchange membrane taking styrene as a framework;
preparing a solution containing chitosan or a derivative thereof;
Immersing the ion exchange membrane into the solution containing chitosan or the derivative thereof after fixing the ion exchange membrane by using a clamp, so that only one side of the ion exchange membrane contacts the solution for 20min;
taking out the ion exchange membrane and airing at a place protected from light at normal temperature.
2. The ion exchange membrane of claim 1, wherein the polymeric protective membrane has an average pore size of less than 100 daltons.
3. The ion exchange membrane of claim 1, wherein the ion exchange membrane is a styrenic heterogeneous ion exchange membrane.
4. The ion exchange membrane according to claim 1, wherein the material of the polymer protective film is chitosan or a chitosan derivative.
5. The ion exchange membrane according to claim 1, wherein the polymer protective film is a film formed on a surface of the ion exchange membrane by a phase-inversion method.
6. The ion exchange membrane according to claim 1, wherein the polymer protective film is a film formed on a surface of the ion exchange membrane by a coating film forming method.
7. The ion exchange membrane according to any one of claims 1 to 6, wherein one side of the polymeric protective membrane is attached to the ion exchange membrane, and the other side is provided with a flow guiding structure.
8. The ion exchange membrane of claim 7, wherein the flow directing structure is a plurality of strings having a diameter of less than 1 mm.
9. A method for producing an ion exchange membrane with a polymer protective film according to any one of claims 1 to 8, comprising:
preparing a heterogeneous ion exchange membrane taking styrene as a framework;
preparing a solution containing chitosan or a derivative thereof;
Immersing the ion exchange membrane into the solution containing chitosan or the derivative thereof after fixing the ion exchange membrane by using a clamp, so that only one side of the ion exchange membrane contacts the solution for 20min;
Taking out the ion exchange membrane, and airing at a place protected from light at normal temperature;
The method further comprises the steps of: and repeatedly immersing the dried ion exchange membrane into a solution containing chitosan or derivatives thereof for 20min, and taking out the ion exchange membrane and drying the ion exchange membrane in a place protected from light at normal temperature.
CN201810991995.0A 2018-08-29 2018-08-29 Ion exchange membrane with high molecular protection film and preparation method thereof Active CN108905645B (en)

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JP2001157823A (en) * 1999-12-03 2001-06-12 Tokuyama Corp Ion exchange membrane and method of manufacturing the same
JP2004149586A (en) * 2002-10-29 2004-05-27 Tokuyama Corp Method for manufacturing ion-exchange membrane
JP2004269681A (en) * 2003-03-07 2004-09-30 Nippon Muki Co Ltd Ion-exchange-functional membrane and method for producing the same
CN103762375A (en) * 2014-01-10 2014-04-30 清华大学深圳研究生院 Polyfluortetraethylene sandwich layer protective ion exchange membrane, preparation method of membrane and liquid flow battery
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JP2004149586A (en) * 2002-10-29 2004-05-27 Tokuyama Corp Method for manufacturing ion-exchange membrane
JP2004269681A (en) * 2003-03-07 2004-09-30 Nippon Muki Co Ltd Ion-exchange-functional membrane and method for producing the same
CN103762375A (en) * 2014-01-10 2014-04-30 清华大学深圳研究生院 Polyfluortetraethylene sandwich layer protective ion exchange membrane, preparation method of membrane and liquid flow battery
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