CN107115795B - Separation membrane with pH-dependent flux under acidic condition and preparation method thereof - Google Patents
Separation membrane with pH-dependent flux under acidic condition and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title description 4
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- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 32
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 230000005855 radiation Effects 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 15
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- 239000000243 solution Substances 0.000 claims description 18
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- 238000001914 filtration Methods 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
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- 230000007423 decrease Effects 0.000 claims description 3
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
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- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
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- 238000002715 modification method Methods 0.000 description 1
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 1
- 229940066842 petrolatum Drugs 0.000 description 1
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- 229920006393 polyether sulfone Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000131 polyvinylidene Polymers 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
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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
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
-
- 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
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention relates to the technical field of surface modification of polymer separation membranes, in particular to a polymer separation membrane surfaceA method for modification. A process for preparing the separating membrane with pH-dependency of flux under acidic condition features that the hydroxyethyl acrylate is grafted to the surface of polyvinylidene fluoride membrane and/or the surface of pores of said membrane in the radiation field of Co 60. The invention is through Co 60High-energy radiation grafting hydroxyethyl acrylate on the PVDF membrane changes the sensitivity of the membrane to solutions with different pH values. The grafted membrane has pH dependence, so that the flux of the membrane is reduced along with the increase of the pH, and the flux of the membrane is remarkably reduced between pH =4 and pH =5, so that the grafted membrane is very suitable for selective separation, and the pollution behavior in the process of controlling the membrane and the separation characteristic of the membrane are changed by changing the pH value of the environment.
Description
Technical Field
The invention relates to the technical field of surface modification of polymer separation membranes, in particular to a method for surface modification of a polymer separation membrane.
Background
Membrane separation technologies that have gained in the 60's of the 20 th century have many advantages such as high efficiency, high selectivity, small footprint, low cost and low energy consumption. Due to its superior filtration and separation performance, it has played a great role in the field of water treatment.
However, membrane fouling is a bottleneck problem that limits the widespread use of membrane-process wastewater treatment technologies (Rana and Matsuura 2010). The membrane pollution can cause the serious reduction of the membrane filtration performance, the filtration efficiency is influenced, and the membrane pollution can be removed to a certain extent by backwashing and chemical cleaning, but the operation cost and the threat to the secondary pollution of the environment are undoubtedly increased.
In recent years, with the research of intelligent high molecular polymers, people begin to pay attention to functional films which have sensitive response and self-regulation to the change of external environmental conditions. Among them, a membrane having pH responsiveness is a hot spot in research. The film shows special separation behavior due to the special charge characteristic of the film, improves the self pollution resistance of the film due to the existence of charge groups, and has development prospect.
The common method for preparing the pH value responsive separation membrane is to modify the common membrane material and introduce monomers with weak electrolyte characteristics, such as acrylic acid, N-isopropyl acrylamide and the like. The monomers generally have certain improvement effect on the hydrophilicity of the membrane material, and the improvement of the hydrophilicity of the membrane material is one of the currently accepted effective methods for reducing membrane pollution.WangYong et al in supercritical CO2As a solvent, acrylic acid is grafted on the surface of the polypropylene separation membrane. When the pH value is increased, the carboxyl in the grafting chains are ionized, the solubility is increased, and under the action of charge repulsion, each grafting chain is in a stretched state in an aqueous solution, so that membrane pores are blocked, and the flux is reduced; when the pH value is recovered, the membrane flux is recovered. Carboxymethylation is carried out on chitosan by Zhao's of Tianjin university, and polyether sulfone is taken as a base film to obtain the separation membrane with pH value response and ionic strength response. The membrane shows high pollution resistance to bovine serum albumin at a pH value of 6.8; on the other hand, at a pH of 4.7 or less, proteins are easily adsorbed. Chitosan modified by glucose in WangJianwenn et al and Li et al, and N2The separation membrane with pH value responsiveness is prepared by the alkylated chitosan, and the separation membrane has the characteristic that the permeability coefficient and the diffusion coefficient are increased along with the reduction of the pH value; the permeability coefficient of vitamin B2 to the latter depends on the change in the pH of the environment. The chemical grafting method has positive experiment results on hydrophilicity and pollution resistance by modifying the surface of the grafted polymer membrane, but has various defects, such as harsh conditions of grafting reaction, difficult effective control of reaction, unsatisfactory grafting efficiency, large amount of catalyst and initiator, and the like. This undoubtedly raises the cost of the separation membrane application, and such complicated experimental conditions are an insurmountable challenge for large-scale industrial application. In addition, although the contamination resistance of the sewage solution after grafting is improved, the decrease of the membrane flux is slowed down when the sewage solution is filtered. Therefore, the development of a more efficient, controllable and environment-friendly polymer separation membrane modification method is of great significance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and the invention aims to provide a preparation method of a separation membrane with pH dependence of flux under an acidic condition, which is more efficient, controllable and environment-friendly, and the flux of the modified membrane has pH dependence under the acidic condition. It is an object of the present invention to provide a separation membrane prepared by the above method.
In order to achieve the purpose, the invention adopts the following technical scheme:
a process for preparing the separating membrane with pH-dependency of flux under acidic condition features that the hydroxyethyl acrylate is grafted to the surface of polyvinylidene fluoride membrane and/or the surface of pores of said membrane in the radiation field of Co 60.
Preferably, said Co60The radiation dose rate is 1-3 kiloCurie/hour, and the radiation time is 5-15 hours.
Preferably, the hydroxyethyl acrylate is hydroxyethyl acrylate solution, and the mass percent solubility of the hydroxyethyl acrylate solution is between 3% and 10%. If the pH value is less than 3%, the response effect on the pH value is not obvious, and if the pH value is more than 10%, the membrane pores are seriously blocked, and the water flux loss is overlarge.
Preferably, the hydroxyethyl acrylate solution is added with a molar salt with the mass percent solubility of 0.5-1.0%. The function of the molar salt is to prevent homopolymerization of the monomer in solution.
Preferably, the polyvinylidene fluoride-propylene membrane has membrane pores with the pore diameter of 0.01-1 micron.
Preferably, the polyvinylidene fluoride membrane is provided with a non-woven fabric support.
Preferably, the grafting reaction is protected by filling nitrogen gas.
Preferably, the method comprises the steps of:
1) adding 500ml of deionized water into a clean beaker, then adding a certain amount of molal salt into the deionized water, stirring and carrying out ultrasonic treatment for 10 minutes to completely and uniformly dissolve the molal salt, thereby obtaining 500ml of a molal salt solution with the mass fraction of 0.7%;
2) 2.5 g of hydroxyethyl acrylate is dripped into the prepared molar salt solution, and in order to prevent the hydroxyethyl acrylate from reacting in the air, the tail part of a dripping pipe is required to extend below the liquid level of the molar salt solution during dripping;
3) cleaning PVDF with a pore diameter of 0.1 micron and a non-woven fabric support by using deionized water, and then soaking in the deionized water for 24 hours to remove residues brought into the membrane in the production process; then, putting the clean PVDF membrane into a 25 ml radiant tube, and adding 200 ml of hydroxyethyl acrylate solution into the radiant tube to ensure that the whole PVDF membrane is always immersed under the liquid level; then sealing with vaseline and charging nitrogen for 30 minutes to completely remove air in the radiant tube;
4) placing a radiant tube soaked with PVDF in Co60In the radiation field, the radiation dose rate is set to be 2 kiloCurie per hour, the radiation time is set to be 10 hours, and finally the grafted PVDF film is obtained.
The invention is through Co 60High-energy radiation grafting hydroxyethyl acrylate on the PVDF membrane changes the sensitivity of the membrane to solutions with different pH values. The grafted membrane has pH dependence, so that the flux of the membrane is reduced along with the increase of the pH, and the flux of the membrane is remarkably reduced between pH =4 and pH =5, so that the grafted membrane is very suitable for selective separation, and the pollution behavior in the process of controlling the membrane and the separation characteristic of the membrane are changed by changing the pH value of the environment.
Further, the present invention is represented by the formula Co 60Grafting hydroxyethyl acrylate on the PVDF membrane by high-energy radiation to realize hydrophilic modification of the PVDF membrane. The method has strong controllability, can realize accurate control of the grafting reaction only by adjusting the radiation metering, has simple equipment and low cost, and is easy to realize large-scale industrial application.
Further, the present invention is represented by the formula Co 60The hydroxyethyl acrylate is grafted on the PVDF membrane by high-energy radiation, only a small amount of polymerization inhibitor is used in the process, and the secondary pollution to the environment is low.
Drawings
FIG. 1 is Co 60Schematic process diagram of experimental method for grafting hydroxyethyl acrylate on PVDF membrane by high-energy radiation.
FIG. 2 is a graph of the Infrared (IR) spectrum of the surface of the film before and after radiation grafting.
FIG. 3 is a Scanning Electron Microscope (SEM) image of the membrane surface before and after radiation grafting.
FIG. 4 is an Atomic Force Microscope (AFM) image of the membrane surface before and after radiation grafting.
FIG. 5 is a graph comparing membrane submergence experiments before and after radiation grafting.
Fig. 6 (a) is a graph showing the results of sequentially filtering pure water with an ungrafted membrane at pH =1 to pH = 14.
Fig. 6 (b) is a graph showing the results of sequentially filtering pure water pH =1 to pH =14 by the membrane after grafting.
Detailed Description
The present invention will be described in more detail with reference to the following examples, which are not intended to limit the present invention. All variations that come within the meaning and range of equivalency of the disclosure are to be considered within the scope of the invention.
Firstly, deionized water is used for preparing 500ml of a 0.7 mass percent molar salt solution, and the molar salt solution has the function of preventing the monomer from homopolymerization in the solution. Then, 2.5 g of hydroxyethyl acrylate was added dropwise to the prepared molar salt solution, and in order to prevent the reaction of hydroxyethyl acrylate in the air, the end of the dropping tube was extended below the liquid level of the molar salt solution during the addition. In the PVDF membrane preparation stage, a commercial PVDF membrane with a pore size of 0.1 micron and a nonwoven support is cut into a membrane with a size of 10 cm × 10 cm, rinsed with deionized water, and then soaked in deionized water for 24 hours. The clean PVDF membrane was then placed in a 250 ml radiant tube, and 200 ml of hydroxyethyl acrylate solution was added to the radiant tube. The tube was sealed with petrolatum and purged with nitrogen for 30 minutes to completely remove the air from the tube. Finally, the radiant tube with the PVDF is placed in Co 60In the radiation field, the radiation dose rate is set to be 2 kiloCurie per hour, the radiation time is set to be 10 hours, and finally the grafted PVDF film is obtained. The specific experimental method is schematically shown in figure 1.
The change in the functional groups on the membrane surface before and after grafting was characterized by infrared spectroscopy (IR), and in fig. 2, the results showed that the grafted membrane exhibited a new characteristic peak at 1731 wavelength, which was assigned to C = O in hydroxyethyl acrylate (Taniguchi et al 2003), which confirmed the successful grafting of hydroxyethyl acrylate onto the membrane surface, and further observed a broad peak at a wavelength of about 3300, which is a characteristic shock peak for-OH, and the grafted membrane had a stronger response value, indicating that the grafted membrane had more hydrophilic groups.
In order to examine the morphology change of the membrane surface before and after grafting, SEM and AFM tests are carried out on the membrane, and the result shows that the grafted membrane surface has a protrusion structure (figure 3), the modified membrane surface has a more fine structure, and the pore size is reduced (figure 4).
The water contact angle of the grafted membrane is found to be 10 degrees lower than that of a pure PVDF membrane by testing, and the water content data show that the grafted membrane is 100.86 percent, the pure PVDF membrane is 32.85 percent, the affinity between the grafted membrane and water is obviously improved, so that in a membrane immersion experiment, after 12 hours of soaking, all the grafted membranes are immersed in the water bottom, and the pure PVDF membrane is floated on the water surface, as shown in figure 5
To observe the effect of pH on membrane flux, pure water at pH =1 to pH =14 was filtered sequentially from low to high using a dead-end filtration apparatus, and 500mL of pure water was adjusted in pH with a 2mol/L HCl solution and a NaOH solution. The test was provided by nitrogen cylinders with a test pressure set at 0.1 mpa. Fig. 6 (a) shows the membrane flux of the ungrafted PVDF membrane at different pH values, showing that the flux is not significantly related to the pH, and fig. 6 (b) shows the membrane flux of the grafted PVDF membrane at different pH values, showing that the flux becomes gradually smaller with the increase of the pH value under the acidic condition, and the flux is significantly reduced between pH =4 and pH =5, showing the pH dependence of the membrane flux after grafting.
Claims (9)
1. A method for producing a separation membrane having a pH dependency of flux under acidic conditions, characterized in that: the method is adopted in Co 60Grafting hydroxyethyl acrylate on the surface of the polyvinylidene fluoride membrane and/or the surface of a membrane hole in a radiation field;
when the separation membrane filters pure water solution with different pH values from low to high under acidic conditions, the result shows that the filtration flux is reduced along with the increase of the pH value, and the separation membrane has a remarkable reduction between pH =4 and pH =5 and has pH dependence.
2. The method for producing a separation membrane having a flux with pH dependency under acidic conditions according to claim 1, wherein: co 60The radiation dose rate is 1-3 kiloCurie/hour, and the radiation time is 5-15 hours.
3. The method for producing a separation membrane having a flux with pH dependency under acidic conditions according to claim 1, wherein: the hydroxyethyl acrylate adopts a hydroxyethyl acrylate solution, and the mass percent solubility of the hydroxyethyl acrylate solution is between 3 percent and 10 percent.
4. A method for producing a separation membrane having a flux with pH dependency under acidic conditions, according to claim 3, characterized in that: adding a mol salt with the mass percent solubility of 0.5-1.0% into the hydroxyethyl acrylate solution.
5. The method for producing a separation membrane having a flux with pH dependency under acidic conditions according to claim 1, wherein: the polyvinylidene fluoride membrane has membrane pores with the pore diameter of 0.01-1 micron.
6. The method for producing a separation membrane having a flux with pH dependency under acidic conditions according to claim 1, wherein: the polyvinylidene fluoride membrane is provided with a non-woven fabric support.
7. The method for producing a separation membrane having a flux with pH dependency under acidic conditions according to claim 1, wherein: and filling nitrogen for protection in the grafting reaction.
8. A method for producing a separation membrane having a flux with pH dependency under acidic conditions according to claim 1, characterized by comprising the steps of:
1) adding 500ml of deionized water into a clean beaker, then adding a certain amount of molal salt into the deionized water, stirring and carrying out ultrasonic treatment for 10 minutes to completely and uniformly dissolve the molal salt, thereby obtaining 500ml of a molal salt solution with the mass fraction of 0.7%;
2) 2.5 g of hydroxyethyl acrylate is dripped into the prepared molar salt solution, and in order to prevent the hydroxyethyl acrylate from reacting in the air, the tail part of a dripping pipe is required to extend below the liquid level of the molar salt solution during dripping;
3) cleaning PVDF with a pore diameter of 0.1 micron and a non-woven fabric support by using deionized water, and then soaking in the deionized water for 24 hours; then, putting the clean PVDF membrane into a 25 ml radiant tube, and adding 200 ml of hydroxyethyl acrylate solution into the radiant tube to ensure that the whole PVDF membrane is always immersed under the liquid level; then sealing with vaseline and charging nitrogen for 30 minutes to completely remove air in the radiant tube;
4) placing a radiant tube soaked with PVDF in Co60In the radiation field, the radiation dose rate is set to be 2 kiloCurie per hour, the radiation time is set to be 10 hours, and finally the grafted PVDF film is obtained.
9. The separation membrane prepared by the method of any one of claims 1 to 8, wherein the flux of the separation membrane has pH dependence under acidic conditions, and when the separation membrane filters pure water solution with different pH from low to high under acidic conditions, the result shows that the filtration flux decreases along with the increase of pH, and the filtration flux significantly decreases between pH =4 and pH =5, and has pH dependence.
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| CN101293184A (en) * | 2008-06-23 | 2008-10-29 | 天津工业大学 | Process for manufacturing large-flux anti-pollution PVDF hollow fiber external pressure film |
| CN103272493A (en) * | 2013-04-27 | 2013-09-04 | 新疆大学 | Method for hydrophilic modification of polyvinylidene fluoride membrane |
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| CN101293184A (en) * | 2008-06-23 | 2008-10-29 | 天津工业大学 | Process for manufacturing large-flux anti-pollution PVDF hollow fiber external pressure film |
| CN103272493A (en) * | 2013-04-27 | 2013-09-04 | 新疆大学 | Method for hydrophilic modification of polyvinylidene fluoride membrane |
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