CN108905645A - A kind of amberplex and preparation method thereof with polymer protective film - Google Patents
A kind of amberplex and preparation method thereof with polymer protective film Download PDFInfo
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- CN108905645A CN108905645A CN201810991995.0A CN201810991995A CN108905645A CN 108905645 A CN108905645 A CN 108905645A CN 201810991995 A CN201810991995 A CN 201810991995A CN 108905645 A CN108905645 A CN 108905645A
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- amberplex
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- 230000001681 protective effect Effects 0.000 title claims abstract description 65
- 229920000642 polymer Polymers 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000005342 ion exchange Methods 0.000 claims abstract description 18
- 229920001661 Chitosan Polymers 0.000 claims abstract description 17
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 11
- 239000003014 ion exchange membrane Substances 0.000 claims abstract description 9
- 239000011248 coating agent Substances 0.000 claims abstract description 5
- 238000000576 coating method Methods 0.000 claims abstract description 5
- 239000011148 porous material Substances 0.000 claims abstract description 4
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 239000005416 organic matter Substances 0.000 abstract description 21
- 239000012528 membrane Substances 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 8
- 230000014759 maintenance of location Effects 0.000 abstract description 6
- 238000002242 deionisation method Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 238000000909 electrodialysis Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000005192 partition Methods 0.000 description 7
- 238000001514 detection method Methods 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- DIKBFYAXUHHXCS-UHFFFAOYSA-N bromoform Chemical compound BrC(Br)Br DIKBFYAXUHHXCS-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000008399 tap water Substances 0.000 description 4
- 235000020679 tap water Nutrition 0.000 description 4
- HFFLGKNGCAIQMO-UHFFFAOYSA-N trichloroacetaldehyde Chemical compound ClC(Cl)(Cl)C=O HFFLGKNGCAIQMO-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229910001410 inorganic ion Inorganic materials 0.000 description 3
- 238000012795 verification Methods 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- DRUIESSIVFYOMK-UHFFFAOYSA-N Trichloroacetonitrile Chemical compound ClC(Cl)(Cl)C#N DRUIESSIVFYOMK-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 229950005228 bromoform Drugs 0.000 description 2
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 2
- 229940106681 chloroacetic acid Drugs 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229940029273 trichloroacetaldehyde Drugs 0.000 description 2
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000001172 liquid--solid extraction Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/28—Polymers of vinyl aromatic compounds
-
- 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
- B01D67/0002—Organic membrane manufacture
-
- 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
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2311/00—Details relating to membrane separation process operations and control
- B01D2311/26—Further operations combined with membrane separation processes
- B01D2311/2623—Ion-Exchange
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
Landscapes
- 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 a kind of amberplex and preparation method thereof with polymer protective film.The amberplex includes：Polymer protective film and amberplex, polymer protective film is formed in ion exchange film surface, polymer protective film is high molecular material composition, film with cavernous structure, the average pore size of polymer protective film is less than 100 dalton, amberplex is styrene heterogeneous ion-exchange membrane, the material of polymer protective film is the derivative of chitosan or chitosan, polymer protective film is formed in the ion exchange film surface using phase molecule conversion method or is formed in the ion exchange film surface using coating membrane formation process, polymer protective film side is provided with flow-guiding structure.Amberplex and preparation method thereof provided by the invention with polymer protective film has the characteristics that high to organic matter retention rate, deionization effect is good.
Description
Technical field
The present invention relates to water treatment fields, more particularly to a kind of amberplex and its system with polymer protective film
Preparation Method.
Background technique
Various organic matters are the indexs that detection is frequently necessary in water process research in water sample, and current analyzing detecting method exists
Inorganic ions is be disturbed larger when there are a lot.In order to avoid the interference of inorganic ions, liquid-solid extraction, liquid are usually taken before
The modes such as liquid extraction are pre-processed, and Organic substance in water is extracted.But for actual water sample, organic components are sufficiently complex,
It is difficult to recycle hydrophilic organic efficient by extraction process, causes organic matter to be lost larger.
Inorganic ions in water sample is removed using electrodialysis mode, retains the organic matter in water sample, can be more efficient return
Organic matter in water sample is received, subsequent detection is facilitated.But it is found in the detection of certain actual water samples, organic matter is the same as amberplex meeting
A series of interaction is generated, if ionic state organic matter is also removed, the organic matter of strong adsorption is also adsorbed.These are made
With the loss that can all cause organic matter, cause the detection error of organic matter.
Moreover, in the prior art, partition being placed in electric dialyzator among two amberplexes, on the one hand avoids yin, yang
Amberplex directly contacts generation short circuit, on the other hand sample liquids is promoted to generate turbulent flow, uniform concentration distribution.And partition
Hole is smaller, after cleaning, is easy to retain liquid, can have an impact to subsequent sample concentration；And because electrodialysis process liquid
When, the thinner treatment effect of the thickness of sample room water sample is better, in order to pursue treatment effect, often detects and uses two ion of electric dialyzator
Exchange membrane spacing is smaller, and after placing partition, block board thickness will limit two amberplex spacing.
Summary of the invention
The object of the present invention is to provide a kind of amberplex and preparation method thereof with polymer protective film, has pair
The feature that organic matter retention rate is high, deionization effect is good.
To achieve the above object, the present invention provides following schemes：
A kind of amberplex with polymer protective film, including：Polymer protective film and amberplex, the height
Molecule protective film is formed in the ion exchange film surface, the polymer protective film be high molecular material composition, have
The film of cavernous structure.
Optionally, the average pore size of the polymer protective film is less than 100 dalton.
Optionally, the amberplex is styrene heterogeneous ion-exchange membrane.
Optionally, the material of the polymer protective film is the derivative of chitosan or chitosan.
Optionally, the polymer protective film is formed in the ion exchange film surface using phase molecule conversion method
Film.
Optionally, the polymer protective film is formed in the ion exchange film surface using coating membrane formation process
Film.
Optionally, the polymer protective film side is attached on the amberplex, and the other side is provided with water conservancy diversion knot
Structure.
Optionally, the flow-guiding structure is the cord that a plurality of diameter is less than 1mm.
The present invention also provides a kind of preparation method of amberplex with polymer protective film, the method packets
It includes：
Preparation is using styrene as the heterogeneous ion-exchange membrane of skeleton；
Prepare the solution of chitosan-containing or derivatives thereof；
Amberplex is immersed in after fixed to the solution of described chitosan-containing or derivatives thereof using fixture, hands over ion
It changes film and there was only solution 20min described in a side contacts；
It is dried after taking out amberplex in the place that room temperature is protected from light.
Optionally, the method also includes：Amberplex after repetition will dry immerses chitosan-containing or derivatives thereof
Solution 20min after, take out and in the place that room temperature is protected from light dry step.
The specific embodiment provided according to the present invention, the invention discloses following technical effects：It is provided by the invention to have
Amberplex of polymer protective film and preparation method thereof, polymer protective film can will be in solution in electrodialytic process
Organic matter effectively obstructs, and makes it that it can not or be greatly decreased with the contact of amberplex, so that the reservation of organic matter can be improved.
Moreover, the dense micro-hole structure of polymer protective film, allows hydrone and ion in solution to pass through polymer protective film,
But direct contact of most of organic matter with amberplex has been obstructed, therefore, organic matter can have been reduced to ion-exchange group
It influences, to protect the ion exchanging function of amberplex.In addition, the ion provided by the invention with polymer protective film
Exchange membrane is since polymer protective film is formed in ion exchange film surface, and there is no the gaps between film and film, not will form water
Layer, so that it is smaller on the variation of volume of water sample influence in electrodialytic process, moreover, the present invention is arranged on polymer protective film
There is flow-guiding structure, water sample can be promoted uniform processed in electrodialytic process；The use of partition is avoided, shortens two ions and hands over
Change the spacing between film placement；Residual liquid after cleaning process is avoided in partition gap to influence sample concentration.
Detailed description of the invention
It in order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, below will be to institute in embodiment
Attached drawing to be used is needed to be briefly described, it should be apparent that, the accompanying drawings in the following description is only some implementations of the invention
Example, for those of ordinary skill in the art, puts after not making the creative labor property, can also be according to these attached drawings
Obtain other attached drawings.
Fig. 1 is the structural schematic diagram for the amberplex that the embodiment of the present invention has polymer protective film；
Fig. 2 is the structural schematic diagram for the amberplex flow-guiding structure that the embodiment of the present invention has polymer protective film；
Fig. 3 is the preparation method flow chart for the amberplex that the embodiment of the present invention has polymer protective film.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that the described embodiment is only a part of the embodiment of the present invention, instead of all the embodiments.Based on this
Embodiment in invention, those of ordinary skill in the art put every other reality obtained after not making creative work
Example is applied, shall fall within the protection scope of the present invention.
The object of the present invention is to provide a kind of amberplex and preparation method thereof with polymer protective film, has pair
The feature that organic matter retention rate is high, deionization effect is good.
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, with reference to the accompanying drawing and specific real
Applying mode, the present invention is described in further detail.
Fig. 1 is the structural schematic diagram for the amberplex that the embodiment of the present invention has polymer protective film, as shown in Figure 1,
Amberplex provided by the invention with polymer protective film includes：Amberplex 1 and polymer protective film 2, it is described
Polymer protective film 2 is formed on 1 surface of amberplex, that the polymer protective film 2 forms for high molecular material,
Film with cavernous structure.Average pore size is less than 100 dalton.
Amberplex 1 can choose styrene heterogeneous ion-exchange membrane.This kind of film surface relative coarseness is some, subsequent
When polymer protective film forms a film, macromolecule member material is easier to be attached on amberplex.
The material of polymer protective film 2 is the derivative of chitosan or chitosan.Chitosan or derivatives thereof is easy to form a film,
And polymeric membrane tolerance acid-base degree made of this material higher (can work in broader pH range), to the resistance to of organic matter
By also stronger.
The polymer protective film 2 can be formed in the ion exchange film surface using phase molecule conversion method；It can also
To be formed in the ion exchange film surface using coating membrane formation process.
2 side of polymer protective film is attached on the amberplex 1, and the other side is provided with flow-guiding structure 3, such as
Shown in Fig. 2.Flow-guiding structure be can be a plurality of diameter be less than 1mm cord.Cord may be selected polytetrafluoroethylene (PTFE), PEEK etc. and not lead
Electricity, resistant material.
The present invention also provides a kind of preparation methods of amberplex with polymer protective film, as shown in figure 3, this
Inventing the preparation method provided includes：
Step 301：Preparation is using styrene as the heterogeneous ion-exchange membrane of skeleton；
Step 302：Prepare the solution of chitosan-containing or derivatives thereof；
Step 303：Solution described in step 202 is immersed after amberplex is fixed using fixture, makes amberplex only
There is solution 20min described in a side contacts；
Step 304：It is dried after taking out amberplex in the place that room temperature is protected from light.
To obtain the polymer protective film in fine and close aperture, this coating procedure is repeated, that is, repeats the ion after drying and hands over
After changing the solution 20min of film immersion chitosan-containing or derivatives thereof, takes out and dry step in the place that room temperature is protected from light.
Verification experimental verification is carried out to the amberplex with polymer protective film provided by the invention below：
Embodiment one
It is sample that this example, which chooses common halogenated organic matters, and organic matter is protected after verifying carries out deionization operation using different films
The effect stayed.Sample is prepared with ultrapure water, contains 100 μ g/L of chloroform, 100 μ g/L of bromoform, 100 μ g/ of trichloroacetaldehyde
L, 100 μ g/L of Tritox, 100 μ g/L of trichloroacetic acid, 100 μ g/L of chloroacetic acid, and contain chloride ion 10mg/L.In experiment,
Anions and canons exchange membrane spacing 1mm, voltage is direct current 20V between two electrode plates, is passed through tap water to sample room；Sample feeding stream
Speed is 0.5mL/min, is passed through sodium bicarbonate solution, flow velocity 1mL/min to two electrode chambers.
Initial water quality indicator and index after pretreatment are as shown in Table 1：
Table one
Composite membrane refers to the amberplex provided by the invention with polymer protective film in table one, can from result
Out, there is good removal to chloride ion using the electrodialysis plant of composite membrane, removal rate is all larger than 99%；Two kinds of films are to trichlorine
Methane, bromoform, trichloroacetaldehyde, the rate of recovery of Tritox these substances are all more satisfactory, 95% or more.But for
The substance of this kind of easily ionizable in water of trichloroacetic acid, chloroacetic acid, conventional ion exchange membrane can not recycle it, and the rate of recovery is
0；And after using composite membrane, the rate of recovery to both substances is 76% and 54%, and the rate of recovery has a big promotion.
Embodiment two
This example chooses tap water as tested water sample, verification processing effect.In experiment, anions and canons exchange membrane spacing
1mm, voltage is direct current 20V between two electrode plates, is passed through tap water to sample room；Tap water sample introduction flow velocity is 0.5mL/min, to two
A electrode chamber is passed through sodium bicarbonate solution, flow velocity 1mL/min.Initial water quality indicator and index after pretreatment such as two institute of table
Show：
Table two
From the results, it was seen that the electrodialysis plant using composite membrane has good removal to chloride ion, removal rate is equal
Greater than 98.9%.Originally after application bipolar membrane electrodialysis equipment processing, the retention rate of total organic carbon (TOC) is water sample
89.3%, and the sample TOC retention rate for applying the electrodialysis plant of conventional ion exchange membrane to handle is 62.9%.For total organic
The promotion of the retention rate of object, for electrodialysis plant is applied to detection field, the accuracy for promoting detection method is significant.
Amberplex and preparation method thereof provided by the invention with polymer protective film is high in electrodialytic process
Molecule protective film can effectively obstruct the organic matter in solution, make it that its connecing with amberplex can not or be greatly decreased
Touching, so that the reservation of organic matter can be improved.Moreover, the dense micro-hole structure of polymer protective film, make in solution hydrone and from
Son can pass through polymer protective film, and but having obstructed most of organic matter therefore can with the direct contact of amberplex
Influence of the organic matter to ion-exchange group is reduced, to protect the ion exchanging function of amberplex.In addition, the present invention mentions
Film is not present since polymer protective film is formed in ion exchange film surface in the amberplex with polymer protective film supplied
Gap between film, not will form water layer, so that it is smaller on the variation of volume of water sample influence in electrodialytic process, moreover,
The present invention is provided with flow-guiding structure on polymer protective film, and water sample can be promoted uniform processed in electrodialytic process；
The use of partition is avoided, the spacing between the placement of two amberplexes is shortened；It avoids remaining in partition gap after cleaning every time
Liquid on sample concentration influence.
Each embodiment in this specification is described in a progressive manner, the highlights of each of the examples are with other
The difference of embodiment, the same or similar parts in each embodiment may refer to each other.
Used herein a specific example illustrates the principle and implementation of the invention, and above embodiments are said
It is bright to be merely used to help understand method and its core concept of the invention；At the same time, for those skilled in the art, foundation
Thought of the invention, there will be changes in the specific implementation manner and application range.In conclusion the content of the present specification is not
It is interpreted as limitation of the present invention.
Claims (10)
1. a kind of amberplex with polymer protective film, which is characterized in that including：Polymer protective film and ion exchange
Film, the polymer protective film are formed in the ion exchange film surface, and the polymer protective film is high molecular material group
At, film with cavernous structure.
2. amberplex according to claim 1, which is characterized in that the average pore size of the polymer protective film is less than
100 dalton.
3. amberplex according to claim 1, which is characterized in that the amberplex is styrene different-phase ion
Exchange membrane.
4. amberplex according to claim 1, which is characterized in that the material of the polymer protective film is chitosan
Or the derivative of chitosan.
5. amberplex according to claim 1, which is characterized in that the polymer protective film is to be turned using phase molecule
The film that change method is formed in the ion exchange film surface.
6. amberplex according to claim 1, which is characterized in that the polymer protective film is using coating film forming
The film that method is formed in the ion exchange film surface.
7. amberplex according to claim 1 to 6, which is characterized in that the polymer protective film side
It is attached on the amberplex, the other side is provided with flow-guiding structure.
8. the amberplex according to any one of claim 7, which is characterized in that the flow-guiding structure is a plurality of diameter
Cord less than 1mm.
9. a kind of preparation method of such as described in any item amberplexes with polymer protective film of claim 1-8,
It is characterized in that, the method includes：
Preparation is using styrene as the heterogeneous ion-exchange membrane of skeleton；
Prepare the solution of chitosan-containing or derivatives thereof；
Amberplex is immersed in after fixed to the solution of described chitosan-containing or derivatives thereof using fixture, makes amberplex
Solution 20min described in an only side contacts；
It is dried after taking out amberplex in the place that room temperature is protected from light.
10. the preparation method of the amberplex according to claim 9 with polymer protective film, which is characterized in that
The method also includes：After the solution 20min for repeating amberplex immersion chitosan-containing after drying or derivatives thereof, take
Step is dried in the place that room temperature is protected from light out.
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| CN201810991995.0A CN108905645B (en) | 2018-08-29 | 2018-08-29 | Ion exchange membrane with high molecular protection film and preparation method thereof |
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