CN112742222A - Preparation method of PVC aliphatic zwitterionic ion exchange membrane - Google Patents
Preparation method of PVC aliphatic zwitterionic ion exchange membrane Download PDFInfo
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- CN112742222A CN112742222A CN202011584504.4A CN202011584504A CN112742222A CN 112742222 A CN112742222 A CN 112742222A CN 202011584504 A CN202011584504 A CN 202011584504A CN 112742222 A CN112742222 A CN 112742222A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J43/00—Amphoteric ion-exchange, i.e. using ion-exchangers having cationic and anionic groups; Use of material as amphoteric ion-exchangers; Treatment of material for improving their amphoteric ion-exchange properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
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- 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
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- 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
- B01D71/30—Polyalkenyl halides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2325/00—Details relating to properties of membranes
- B01D2325/42—Ion-exchange membranes
Abstract
The invention discloses a preparation method and application of a zwitter-ion exchange membrane. The separation membrane is prepared according to the following method: dissolving polyvinyl chloride (PVC) in N, N-dimethylacetamide and uniformly mixing in a round-bottom flask to obtain a solution for preparing a base membrane; carrying out suction filtration on the obtained solution by using a circulating water vacuum pump to remove insoluble impurities doped in the solution; vacuumizing the solution after suction filtration, coating the solution on a glass plate, and drying the glass plate on a flat heater to obtain a polyvinyl chloride base film; soaking the base membrane in triethylenetetramine for 8-24 hours, taking out, and washing with deionized water to obtain a quaternized membrane; and soaking the quaternized membrane in a 3-chloro-2-sodium hydroxypropanesulfonate solution for 12 hours, taking out and drying to obtain the amphoteric ion exchange separation membrane. The method has the advantages of easily available raw materials, low price and simple preparation process, only needs simple soaking, and solves the problems of electrodeposition, complicated layer-by-layer self-assembly process and falling-off of a modified layer on the surface of a modified membrane by electrostatic adsorption in the prior art.
Description
Technical Field
The invention belongs to the technical field of separation membranes, and relates to a preparation method of a PVC aliphatic amphoteric anion membrane.
Background
Electrodialysis (ED) technology has been widely used for recovery of desalinated seawater for decades. Ion exchange membranes (AEMs) are used as core components of electrodialysis devices and play an important role in determining the seawater desalination performance. In recent years, polymers such as polysulfone, polyethersulfone, and polystyrene have been widely studied as a base material for membrane synthesis. However, the performance of the ionic membrane still has some problems to be solved, such as high price, unstable performance and the like, which result in poor operation performance of the membrane. Therefore, developing low-cost, highly stable ionic membranes is a significant challenge in the development of ED. A feasible preparation method of the low-cost ionic membrane is to graft a functional monomer onto a main chain of a low-cost polymer to prepare the ionic membrane. In addition, aromatic AEMs are prone to organic contaminants adhering to the membrane surface or inside its matrix during ED due to their inherent aromatic and hydrophobic properties in their main chains, resulting in increased membrane filtration resistance and decreased membrane lifetime. The amphoteric ion exchange membrane disclosed by the invention is an ion exchange membrane containing both basic groups and acidic groups, the charge property of the surface of the ion exchange membrane can be changed according to the change of the property of a solution to be treated, and the amphoteric ion exchange membrane has adjustability because the amphoteric ion exchange membrane can be used as a cation exchange membrane and an anion exchange membrane.
Journal of Membrane Science (2016, 490, 301-. Because dopamine can be converted into polydopamine in the air environment, the polydopamine has good adsorption and adhesion effects and amphoteric properties, and is prepared from SO4 2-/Cl-The electrodialysis experiment of the system can realize better selective separation of multivalent ions. However, the method has the problems of falling off of the modified layer and expensive raw materials, and is not suitable for large-scale industrial popularization of future membrane preparation.
The preparation method of the polyvinyl chloride amphoteric ion exchange membrane comprises the following steps that (1) an electrochemical Acta (2015, 174, 1113-; wang et al takes Sodium Dodecyl Benzene Sulfonate (SDBS), sodium humate and bovine serum albumin (BAS) as typical representatives of pollutants, and examines the pollution condition of the pollutants to different ion exchange membranes in the ED operation process, and the result shows that the adhesion degree of organic matters on the membrane surface is mainly determined by the hydrophilicity and hydrophobicity of the membrane surface, the electrostatic repulsion between the membrane surface and the pollutants and the pi-pi conjugation strength, the stronger the hydrophilicity of the membrane surface, the better the anti-pollution capability, and the better the anti-pollution capability of the aliphatic ion membrane than that of the aromatic ion membrane.
The method can fully meet the requirement of membrane ion separation by using low-cost and easily-obtained raw materials and simple means, and has great guiding significance for industrialization in the future.
Disclosure of Invention
The invention aims to provide a preparation method of a PVC aliphatic zwitterionic ion exchange membrane, which solves the problems of easy pollution performance of an aromatic ionic membrane and process cost reduction in the prior art.
The technical scheme adopted by the invention is as follows:
the invention provides a PVC aliphatic zwitterionic exchange membrane, which is prepared by the following method:
(1) uniformly mixing polyvinyl chloride and N, N-dimethylacetamide to obtain a solution for preparing the base membrane.
(2) And (3) carrying out suction filtration on the solution obtained in the step (1) by using a circulating water vacuum pump to remove insoluble impurities in the solution.
(3) And (3) putting the solution obtained in the step (2) into a vacuum box for vacuumizing and defoaming.
(4) And (4) coating the solution obtained in the step (3) on a glass plate, and drying the glass plate on a flat heater (preferably, the drying temperature is 60 ℃ and the drying time is 8 hours) to obtain the polyvinyl chloride base film on the glass plate.
(5) And (3) taking off the film obtained on the glass plate in the step (4) at room temperature, soaking the film in 50-100% (preferably 70%) of triethylenetetramine solution for 8-24h, taking out the film, and washing the film with deionized water to obtain the quaternized film.
(6) And (3) soaking the quaternized membrane obtained in the step (5) into a 3-chloro-2-hydroxypropanesulfonic acid sodium salt solution, soaking for 8-48h (preferably 12h) at 50-90 ℃ (preferably 60 ℃), taking out and drying to obtain the PVC aliphatic amphoteric ion exchange membrane.
Further, the coating thickness in step (4) is 60 to 120. mu.m, preferably 80 μm.
Further, the drying temperature in the step (4) is 60 ℃, and the time is 8 hours.
Further, the concentration by mass of triethylenetetramine in step (5) is preferably 70%.
Compared with the prior art, the invention has the beneficial effects that: the preparation process is simple, only simple soaking is needed, and the problems of electrodeposition, complicated layer-by-layer self-assembly process and falling-off of a modified layer on the surface of a modified film by electrostatic adsorption in the prior art are solved. Meanwhile, the indexes of the basic performance of the membrane, such as ion exchange capacity, mechanical strength and the like, are almost the same as those before the membrane is not modified.
Drawings
FIG. 1 is a diagram of a membrane resistance test apparatus according to the present invention;
FIG. 2 is a Fourier infrared test chart of an ion exchange membrane of the present invention;
FIG. 3 is an electron microscope (SEM) scan of an ion exchange membrane of the present invention;
FIG. 4 is a graph showing changes in membrane resistance (Rn) and ion flux (IEC) of the ion exchange membrane of the present invention;
FIG. 5 is a graph of an electrodialysis test of the present invention as an anion exchange membrane;
FIG. 6 is a graph of an electrodialysis test of the present invention as a cation exchange membrane;
FIG. 7 is a graph showing the voltage trend at both sides of the anti-contamination experimental membrane of the ion exchange membrane of the present invention;
FIG. 8 is a graph showing the trend of the membrane current efficiency of the ion exchange membrane of the present invention;
Detailed Description
The complete steps of the method of the invention are illustrated:
example 1
Adding PVC powder into N, N-dimethylacetamide, heating to 60 ℃, dissolving to obtain a solution, carrying out vacuum defoaming on the PVC solution, pouring the solution onto a glass plate, scraping the solution into a wet film by using a scraper with the thickness of 80 microns, and drying and evaporating the solvent on a flat plate heater at 60 ℃ to obtain the PVC film. Cutting the PVC membrane into a proper size, soaking the PVC membrane in 100mL of 70% triethylene tetramine aqueous solution at the temperature of 60 ℃, reacting for 2 hours respectively, taking out two membranes, soaking one membrane in 0.5mol of NaCl, and soaking the other membrane in 3-chloro-2-hydroxypropanesulfonic acid sodium solution for 12 hours to obtain the ion exchange membrane Q-1.
Example 2
The soaking time of the triethylenetetramine in the example 1 is changed to 3h, and other steps are not changed, so that the ion exchange membrane Q-2 is obtained.
Example 3
The soaking time of the triethylenetetramine in the example 1 is changed to 4h, and other steps are not changed, so that the ion exchange membrane Q-3 is obtained.
The invention is described in detail below with reference to the following figures and detailed description:
from the SEM image of FIG. 2, it can be seen that the QPVC film layer has dense and uniform surface and cross section and no pore cracks. The QPVC ion film prepared in the examples was examined for the film resistance (Rn) infrared and water absorption, and as shown in fig. 4, IEC gradually increased and Rn gradually decreased with the extension of the soaking time of the PVC film in the triethylenetetramine solution. This is because the longer the soaking time, the more the quaternary ammonium salt functional groups grafted to the PVC backbone, the increased ion exchange flux, and the more ion transport channels the more hydrophilic quaternary ammonium salt can provide, resulting in a decrease in membrane surface resistance. In order to examine the anti-contamination effect of the QPVC membrane synthesized in the examples, a contamination experiment was performed, in which the electrodes were silver electrodes and the area of the contamination experiment membrane was 7.065cm, as shown in FIG. 22The cation membrane is German FKB cation membrane, and is compared with commercial membrane JAM-II-05 provided by Kagaku Kogyo high and new technology Co., Ltd, Anhui Hefei, as reference of ion membrane, 0.8g/L sodium dodecyl benzene sulfonate is used as typical pollutant in experiment, initial concentration of NaCl electrolyte is 0.05mol/L, SDBS pollutant is added into a fresh room, concentration is 0.8g/L, and current density is set to be 15mA/cm2. And measuring the change condition of the voltage on two sides of the membrane along with time by adopting an Ag-AgCl electrode.
As shown in fig. 7, the voltage across the Q-2 and Q-3 ion membranes varied less with time, no significant transition time occurred within 720min,exhibits good anti-contamination capability. The anion membrane synthesized in example 1 was subjected to an electrodialysis test using a silver electrode, and the area of the membrane in the electrodialysis test was 7.05cm2The positive membranes are German FKB positive membranes, and are compared with commercial membrane JAM-II-05 provided by JIAOXINGYO technologies GmbH of Anhui fertile Ke, the initial concentration of the stock solution is 0.5mol/LNaCl, 0.8mol/LSDBS is added, and 0.3g/LNa is added2SO4The electrodialytic experiment is carried out for polar liquid with the current maintained at 0.3A, and as can be seen in figures 5-6, under the condition that pollutants exist in a dilute chamber, the conductivity of a commercial membrane JAM-II-05 in the dilute chamber is reduced by 24.69 percent after the electrodialysis is carried out for 200min, which indicates that an ionic membrane is seriously polluted in the electrodialysis process; and the QPVC membrane is reduced by only 9.4 percent, which shows that the ionic membrane has excellent anti-pollution performance.
When the performance of the anion exchange membrane of the amphoteric ion exchange membrane is tested, the change trend of the membrane conductivity-time after the membrane is soaked in triethylenetetramine and reacts with 3-chloro-2-sodium hydroxypropanesulfonate for 12 hours can be seen from fig. 5, the solution conductivity changes of the three membranes at the two sides of the feeding side and the discharging side are large, and the separation effect is good. The effect is enhanced along with the lengthening of the time for soaking the triethylenetetramine to a certain extent, and mainly the reaction degree is continuously improved along with the increasing of the reaction time of the PVC and the triethylenetetramine, so that the amino groups connected to the PVC membrane are continuously increased, and the separation effect is enhanced along with the lengthening of the time for soaking the triethylenetetramine.
FIG. 8 shows the current efficiency of three membrane samples soaked in triethylenetetramine prepared in this experiment. The current efficiency of the membrane with the soaking time of 2 hours is 11.99 percent, the current efficiency of the membrane with the soaking time of 3 hours is 30.05 percent, and the current efficiency of the membrane with the soaking time of 4 hours is 34.05 percent, as can be seen from figure 8, the current efficiency of the three membranes is increased along with the lengthening of the soaking time, and the membrane resistance of the ion membrane is reduced along with the lengthening of the soaking time, so the current efficiency is increased along with the shortening of the soaking time, therefore, the invention has important significance for the energy conservation of the application of the ion exchange membrane.
Claims (7)
1. A PVC aliphatic zwitterionic exchange membrane is prepared by the following method:
(1) uniformly mixing polyvinyl chloride and N, N-dimethylacetamide to obtain a solution for preparing the base membrane.
(2) And (3) carrying out suction filtration on the solution obtained in the step (1) by using a circulating water vacuum pump to remove insoluble impurities in the solution.
(3) And (3) putting the solution obtained in the step (2) into a vacuum box for vacuumizing and defoaming.
(4) And (4) coating the solution obtained in the step (3) on a glass plate, and drying the glass plate on a flat heater to obtain the polyvinyl chloride base film on the glass plate.
(5) And (3) taking down the film obtained on the glass plate in the step (4) at room temperature, soaking the film in 50-100% of triethylene tetramine solution for 8-24h, taking out the film, and washing the film with deionized water to obtain the quaternized film.
(6) And (3) soaking the quaternized membrane obtained in the step (5) into a 3-chloro-2-hydroxypropanesulfonic acid sodium salt solution, soaking for 8-48h at 50-90 ℃, taking out and drying to obtain the PVC aliphatic zwitterionic exchange membrane.
2. The PVC aliphatic zwitterionic ion-exchange membrane of claim 1 wherein said heating to dissolve in step (1) provides a solution having a concentration of 5 to 50 weight percent.
3. The PVC aliphatic zwitterionic ion-exchange membrane of claim 1 wherein said solution applied in step (4) is in the range of 60 to 120 μm thick.
4. The PVC aliphatic zwitterionic ion-exchange membrane of claim 1, wherein the drying temperature in step (4) is 60 ℃ and the heating time is 6-12 h.
5. The PVC aliphatic amphoteric ion exchange membrane as claimed in claim 1, wherein in step (5), the membrane is soaked in 50-100% by mass triethylenetetramine solution for 8-48h, taken out, and washed clean with deionized water to obtain the quaternized membrane.
6. The PVC aliphatic zwitterionic ion-exchange membrane of claim 1, wherein the membrane obtained after quaternization in step (6) is soaked in a 3-chloro-2-hydroxypropanesulfonic acid sodium solution, soaked at 50-90 ℃ for 8-48h, taken out and dried to obtain the PVC aliphatic zwitterionic ion-exchange membrane.
7. Use of the PVC aliphatic zwitterionic ion-exchange membrane of claim 1 in water treatment.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113998762A (en) * | 2021-11-04 | 2022-02-01 | 广东工业大学 | Electrodialysis sewage treatment device with magnet and electrodialysis sewage treatment method |
| CN114405286A (en) * | 2021-12-08 | 2022-04-29 | 华东理工大学 | Ion-crosslinked amphoteric ion exchange membrane, preparation method and application thereof in selective electrodialysis |
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2020
- 2020-12-29 CN CN202011584504.4A patent/CN112742222A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113998762A (en) * | 2021-11-04 | 2022-02-01 | 广东工业大学 | Electrodialysis sewage treatment device with magnet and electrodialysis sewage treatment method |
| CN113998762B (en) * | 2021-11-04 | 2023-02-28 | 广东工业大学 | Electrodialysis sewage treatment device with magnet and electrodialysis sewage treatment method |
| CN114405286A (en) * | 2021-12-08 | 2022-04-29 | 华东理工大学 | Ion-crosslinked amphoteric ion exchange membrane, preparation method and application thereof in selective electrodialysis |
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