CN110479109A - The preparation method for the Kynoar mixed substrate membrane containing nano-grade molecular sieve that flux is high, resistance tocrocking is strong - Google Patents
The preparation method for the Kynoar mixed substrate membrane containing nano-grade molecular sieve that flux is high, resistance tocrocking is strong Download PDFInfo
- Publication number
- CN110479109A CN110479109A CN201910764635.1A CN201910764635A CN110479109A CN 110479109 A CN110479109 A CN 110479109A CN 201910764635 A CN201910764635 A CN 201910764635A CN 110479109 A CN110479109 A CN 110479109A
- Authority
- CN
- China
- Prior art keywords
- kynoar
- molecular sieve
- containing nano
- membrane containing
- mixed substrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
-
- 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
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
-
- 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
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0013—Casting processes
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/04—Hydrophobization
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/30—Chemical resistance
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/38—Hydrophobic membranes
Abstract
The present invention relates to a kind of preparation methods of the strong Kynoar mixed substrate membrane containing nano-grade molecular sieve of flux height, resistance tocrocking, -8 material of zeolite imidazole ester skeleton that solvent-thermal method is prepared is added in Kynoar casting solution, and the Kynoar mixed substrate membrane containing nano-grade molecular sieve is made in the Kynoar casting solution using phase separation method.Compared with prior art, the present invention has many advantages, such as that the ultrafiltration membrane antifouling property being prepared is excellent, water flux is high and preparation method is simple.
Description
Technical field
The present invention relates to technical field of membrane separation, the Kynoar high more particularly, to a kind of flux, resistance tocrocking is strong
The preparation method of mixed substrate membrane containing nano-grade molecular sieve.
Background technique
Membrane separation technique is a kind of green separation technique of prevalence in recent years.Kynoar (PVDF) since its is heat-resisting,
Corrosion-resistant, radiation hardness has the advantages that dielectric properties and chemical stability outstanding, be as production ultrafiltration membrane preferred material it
One.Zeolite imidazole ester skeleton (ZIF-8) as one kind in metal-organic framework material (MOFs), be with large specific surface area,
The adjustable porous material in molecule aperture, nano zeolite imidazate skeleton are separated in selection, catalysis, and the fields such as absorption possess huge
Potentiality.
Chinese patent (authorization publication number: CN103623714A) discloses a kind of system of nonpolar polyvinylidene fluoride ultrafiltration membrane
Preparation Method.Using Kynoar made from blending method and phase inversion in nonpolarity, high mechanical strength, good hydrophilic property, anti-pollution
Dye ability is strong.Chinese patent (authorization publication number: CN105642127A) discloses a kind of anthraquinone functional poly vinylidene ultrafiltration
The preparation method of film.Using the film-forming method of a kind of blending and interfacial polymerization, the present invention on polyvinylidene fluoride film the result is that consolidate
Fixed anthraquinone molecular is secured, will not fall off.It is super that Chinese patent (publication number: CN102716677A) discloses a kind of Kynoar
Filter membrane and preparation method thereof, the present invention are blended film using ternary polymer material, greatly improve polyvinylidene fluoride film
Hydrophilicity and toughness.But these ultrafiltration membranes limit its specific industrial application since its contamination resistance is to be improved.
Chinese patent CN107638807A disclose a kind of ZIF-8/PVDF ultrafiltration membrane under room temperature with catalytic action and
Preparation method, the specific steps are as follows: (1) by Kynoar, 2-methylimidazole and additive and solvent homogeneous blend, obtain
Casting solution；(2) after casting solution being stirred 6~12h, 8~12h of defoaming is stood；(3) using isopropanol water solution as coagulation bath, by six
Nitric hydrate zinc is added in coagulation bath；(4) ZIF-8 synthesize on film to get to urging by situ synthesis under room temperature
The ZIF-8/PVDF ultrafiltration membrane of change effect；The ultrafiltration membrane is also to the rejection of oralbumin saline solution (OVA saline solution)
Height, retention flux are good.But the ultrafiltration membrane that this method is prepared is to the organic contamination in L ovalbumin (OVA) salting liquid
The resistance tocrocking of object BSA is insufficient.
Summary of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of flux height, antipollution
The preparation method of the strong Kynoar mixed substrate membrane containing nano-grade molecular sieve of property.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of preparation method for the Kynoar mixed substrate membrane containing nano-grade molecular sieve that flux is high, resistance tocrocking is strong, prepared by solvent-thermal method
Obtained -8 material of zeolite imidazole ester skeleton is added in Kynoar casting solution, will using phase separation method (NIPS)
The Kynoar mixed substrate membrane containing nano-grade molecular sieve is made in the Kynoar casting solution.
The preparation method specifically includes the following steps:
(1) solvent-thermal method is prepared -8 material (ZIF-8) of zeolite imidazole ester skeleton, and by the zeolite imidazole ester bone
- 8 material at high temperature of frame removes guest molecule；
(2) preparation of Kynoar casting solution
- 8 material (ZIF-8) of zeolite imidazole ester skeleton, additive and Kynoar (PVDF) are mixed in N, N bis-
In methylacetamide (DMAC), to dissolving completely, standing and defoaming obtains the Kynoar casting solution for stirring；
(3) preparation of Kynoar mixed substrate membrane containing nano-grade molecular sieve
The Kynoar casting solution that step (2) obtains is scratched uniformly on a glass, then will be coated with polyvinylidene fluoride
The glass plate of alkene casting solution is put into coagulation bath progress split-phase and obtains the Kynoar mixed substrate membrane containing nano-grade molecular sieve.
Wherein, in the step (1), the preparation method of -8 material of zeolite imidazole ester skeleton specifically: will be soluble
Zinc salt, which is dissolved in methanol aqueous solution, obtains zinc solution, and it is molten that organic ligand is dissolved in acquisition organic ligand in methanol solvate
Liquid mixes the zinc solution and organic ligand solution, is reacted under stirring condition, by the solution centrifugal treating after reaction
Solid material is obtained, the solid material is washed, is dried to obtain the particle of -8 material of zeolite imidazole ester skeleton.
The soluble zinc salt is Zn (NO3)2·6H2O, the organic ligand are 2-methylimidazole, the soluble zinc salt
Molar ratio with 2-methylimidazole is 1:10~1:6；During the reaction reaction temperature be room temperature, the reaction time 120~
150min；The solid material is washed using methanol, and is dried under the conditions of 40~80 DEG C.
In the step (1), high temperature remove guest molecule temperature be 100~150 DEG C, processing the time be 120~
180min。
In step (2), the additive is polyvinylpyrrolidone (PVP)；The zeolite imidazole ester skeleton: polyethylene pyrrole
Pyrrolidone: the mass values of Kynoar are 0.1~0.5:1:10~20；Polyethylene pyrrole in the Kynoar casting solution
The total mass fraction of pyrrolidone and Kynoar is 10~20%.
In step (2), the stirring and dissolving temperature of the Kynoar casting solution is controlled at 50~80 DEG C；The stirring
Time is 16~20h.
In step (3), the blade coating of the Kynoar casting solution on the glass plate is with a thickness of 100~250 μm.
In step (3), the coagulation bath is deionized water, and temperature is 15~25 DEG C.
The preparation method further includes the preservation of Kynoar mixed substrate membrane containing nano-grade molecular sieve: described gathering inclined fluorine for what step (3) obtained
Ethylene mixed substrate membrane containing nano-grade molecular sieve, which is placed in deionized water, removes residual solvent, is then placed in deionized water and is saved.Test measures,
353.8Lm is up to using pure water flux of the invention-2·h-1, OVA flux recovery rate is up to 99.6%.
When to the processing of ovoserum albumen (OVA) solution, film shows excellent Kynoar mixed substrate membrane containing nano-grade molecular sieve of the invention
Different resistance tocrocking, and hydrophily significantly increases, i.e., and the pure water flux of film increases；Kynoar mixed-matrix of the invention
For film during preparing film forming, the ZIF-8 particle being prepared using hot solvent method is in film surface due to its hydrophobic property shape
At the hole such as ZIF-8 size, increase pure water flux to a certain extent；In addition, ZIF-8 in the mixed-matrix membrane body due to
Itself contain duct, additional duct can be provided during the test for film, this can also enhance the infiltration of mixed substrate membrane containing nano-grade molecular sieve
Performance；Finally, the hydrophobic characteristic of ZIF-8 itself and the difference of different proteins solution institute band are electrically, cause mixed-matrix
Film enhances the resistance tocrocking of the organic pollutant BSA in L ovalbumin (OVA) salting liquid.
Compared in documents CN107638807A by ZIF-8 in polyvinylidene fluoride (PVDF) ultrafiltration membrane fabricated in situ, this hair
Bright preparation method is that Kynoar casting solution is added in the ZIF-8 for having prepared completion in the form of additive, by drawing
Enter inorganic nano-particle blending method and NIPS method modified PVDF membrane improves composite membrane mechanical strength, while hydrophily
It can greatly improve, there is better contamination resistance, blending is most simple and most common membrane modifying method.Relative to it
Its method, blending and modifying have the advantage that modified progress synchronous with film forming, and simple process does not need cumbersome post-processing step
Suddenly；Modifying agent can cover film surface and fenestra inner wall and the destruction that will not cause membrane structure simultaneously.
During synthesizing Kynoar mixed substrate membrane containing nano-grade molecular sieve, the most key technological parameter is zinc salt and 2-methylimidazole
Molar ratio is 1:10~1:6 and zeolite imidazole ester skeleton: polyvinylpyrrolidone: the mass values of Kynoar are 0.1
~0.5:1:10~20.Synthesis technologic parameter by controlling ZIF-8 controls the size of ZIF-8 particle, and further controls
Casting solution proportion, in order to avoid too small agglomeration and the particle of being easy to produce of particle is caused to cause membrane structure to be destroyed greatly very much.
Compared with prior art, the invention has the following advantages that
(1) ZIF-8 particle is prepared using solvent-thermal method, be blended and NIPS method obtains have resistance tocrocking high it is poly- partially
Vinyl fluoride mixed substrate membrane containing nano-grade molecular sieve, the Kynoar mixed substrate membrane containing nano-grade molecular sieve enhance in hydrophily, while pure water flux increases, and
Excellent resistance tocrocking is shown during OVA processing；
(2) preparation process of the invention is simple, and preparation process mild condition is easy to control, and the high efficiency for being conducive to film is raw
It produces.
Detailed description of the invention
Fig. 1 is the surface sweeping electromicroscopic photograph for the ZIF-8 particle that the present invention is prepared；
Fig. 2 is the section surface sweeping electromicroscopic photograph for the Kynoar mixed substrate membrane containing nano-grade molecular sieve that the present invention is prepared.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection scope.
Embodiment 1
The present embodiment is to prepare -8 material (ZIF-8) of zeolite imidazole ester skeleton, specific steps using solvent-thermal method are as follows:
(1) by the Zn (NO of 0.94g3)2·6H2O magnetic agitation is dissolved in (20mLMeOH in 40mLMeOH/DI mixed solution
And 20mLDI) in obtain zinc nitrate solution；
(2) 2-methylimidazole of 2.0762g (HmIM) magnetic agitation is dissolved in 20mL methanol, obtains 2-methylimidazole
Solution；
(3) zinc nitrate solution of step (1) is poured into the 2-methylimidazole solution in step (2), magnetic force after completely dissolution
Stir 120min；
(4) mixed solution that step (3) obtains is centrifuged, again with methanol is put into 60 DEG C of oven dryings after cleaning 4 times
ZIF-8 crystal is obtained, the ZIF-8 crystal of acquisition is characterized, obtains the electromicroscopic photograph of ZIF-8 crystal, as shown in Figure 1, from
The good granular ZIF-8 material of pattern can be obtained in electromicroscopic photograph with the present embodiment.
(5) step (4) particle obtained is put under 120 DEG C of high temperature after 120min removal guest molecule, it is spare.
Embodiment 2
The present embodiment is further to prepare Kynoar mixed substrate membrane containing nano-grade molecular sieve using the ZIF-8 particle in embodiment 1, specifically
The preparation method is as follows:
(1) ZIF-8, PVP, PVDF after removal guest molecule are dissolved in DMAC, component proportion are as follows: PVDF:ZIF-
8:PVP=10:0.1:3, stirring makes it after completely dissolution at 80 DEG C, and standing and defoaming is for 24 hours；
(2) casting solution of step (1) is scraped on a glass to the film of 150 μ m thicks；
(3) glass plate for having film liquid in step (2) is immersed in 15 DEG C of deionized waters and carries out split-phase；
(4) 3~8 days removing excess of solvent will be impregnated in the film transfer ionized water after split-phase in step (3), place into clean
Deionized water in save, obtain Kynoar mixed substrate membrane containing nano-grade molecular sieve, be denoted as ZIF-8/PVDF ultrafiltration membrane.
Structural characterization is carried out to the ZIF-8/PVDF ultrafiltration membrane of acquisition, the mixed-matrix ultrafiltration membrane room temperature prepared is dried
Afterwards, cold quenching being carried out with liquid nitrogen and obtaining cross section, table is carried out to its upper and lower surface and cross section structure with scanning electron microscope (SEM)
Sign obtains the section surface sweeping electron microscope of ZIF-8/PVDF ultrafiltration membrane, as shown in Fig. 2, the performance of film section is fine and close, but has larger
Fenestra.
Embodiment 3
The present embodiment is further to prepare Kynoar mixed substrate membrane containing nano-grade molecular sieve using the ZIF-8 particle in embodiment 1, specifically
The preparation method is as follows:
(1) ZIF-8, PVP, PVDF after removal guest molecule are dissolved in DMAC, component proportion are as follows: PVDF:ZIF-
8:PVP=20:0.3:3, stirring makes it after completely dissolution at 80 DEG C, and standing and defoaming is for 24 hours；
(2) casting solution of step (1) is scraped on a glass to the film of 180 μ m thicks；
(3) glass plate for having film liquid in step (2) is immersed in 20 DEG C of deionized waters and carries out split-phase；
(4) 3~8 days removing excess of solvent will be impregnated in the film transfer ionized water after split-phase in step (3), place into clean
Deionized water in save, obtain Kynoar mixed substrate membrane containing nano-grade molecular sieve, be denoted as ZIF-8/PVDF ultrafiltration membrane.
Embodiment 4
(1) ZIF-8, PVP, PVDF after removal guest molecule are dissolved in DMAC, component proportion are as follows: PVDF:ZIF-
8:PVP=16:0.5:3, stirring makes it after completely dissolution at 80 DEG C, and standing and defoaming is for 24 hours；
(2) casting solution of step (1) is scraped on a glass to the film of 250 μ m thicks；
(3) glass plate for having film liquid in step (2) is immersed in 25 DEG C of deionized waters and carries out split-phase；
(4) 3~8 days removing excess of solvent will be impregnated in the film transfer ionized water after split-phase in step (3), place into clean
Deionized water in save, obtain Kynoar mixed substrate membrane containing nano-grade molecular sieve, be denoted as ZIF-8/PVDF ultrafiltration membrane.
Embodiment 5
The present embodiment is to prepare -8 material (ZIF-8) of zeolite imidazole ester skeleton, specific steps using solvent-thermal method are as follows:
(1) by the Zn (NO of 0.94g3)2·6H2O magnetic agitation is dissolved in (20mLMeOH in 40mLMeOH/DI mixed solution
And 20mLDI) in obtain zinc nitrate solution；
(2) 2-methylimidazole of 3.1131g (HmIM) magnetic agitation is dissolved in 20mL methanol, obtains 2-methylimidazole
Solution；
(3) zinc nitrate solution of step (1) is poured into the 2-methylimidazole solution in step (2), magnetic force after completely dissolution
Stir 150min；
(4) mixed solution that step (3) obtains is centrifuged, again with methanol is put into 40 DEG C of oven dryings after cleaning 4 times
ZIF-8 crystal is obtained, the ZIF-8 crystal of acquisition is characterized, obtains the electromicroscopic photograph of ZIF-8 crystal, as shown in Figure 1, from
The good granular ZIF-8 material of pattern can be obtained in electromicroscopic photograph with the present embodiment.
(5) step (4) particle obtained is put under 100 DEG C of high temperature after 180min removal guest molecule, it is spare.
Embodiment 6
The present embodiment is further to prepare Kynoar mixed substrate membrane containing nano-grade molecular sieve using the ZIF-8 particle of embodiment 5, specifically
The preparation method is as follows:
(1) ZIF-8, PVP, PVDF after removal guest molecule are dissolved in DMAC, component proportion are as follows: PVDF:ZIF-
8:PVP=20:0.5:1, stirring makes it after completely dissolution at 80 DEG C, and standing and defoaming is for 24 hours；
(2) casting solution of step (1) is scraped on a glass to the film of 180 μ m thicks；
(3) glass plate for having film liquid in step (2) is immersed in 30 DEG C of deionized waters and carries out split-phase；
(4) 3~8 days removing excess of solvent will be impregnated in the film transfer ionized water after split-phase in step (3), place into clean
Deionized water in save, obtain Kynoar mixed substrate membrane containing nano-grade molecular sieve, be denoted as ZIF-8/PVDF ultrafiltration membrane.
Embodiment 7
The present embodiment is to prepare -8 material (ZIF-8) of zeolite imidazole ester skeleton, specific steps using solvent-thermal method are as follows:
(1) by the Zn (NO of 0.94g3)2·6H2O magnetic agitation is dissolved in (20mLMeOH in 40mLMeOH/DI mixed solution
And 20mLDI) in obtain zinc nitrate solution；
(2) 2-methylimidazole of 1.0377g (HmIM) magnetic agitation is dissolved in 20mL methanol, obtains 2-methylimidazole
Solution；
(3) zinc nitrate solution of step (1) is poured into the 2-methylimidazole solution in step (2), magnetic force after completely dissolution
Stir 150min；
(4) mixed solution that step (3) obtains is centrifuged, again with methanol is put into 80 DEG C of oven dryings after cleaning 4 times
ZIF-8 crystal is obtained, the ZIF-8 crystal of acquisition is characterized, obtains the electromicroscopic photograph of ZIF-8 crystal, as shown in Figure 1, from
The good granular ZIF-8 material of pattern can be obtained in electromicroscopic photograph with the present embodiment.
(5) step (4) particle obtained is put under 150 DEG C of high temperature after 120min removal guest molecule, it is spare.
Embodiment 8
The present embodiment is further to prepare Kynoar mixed substrate membrane containing nano-grade molecular sieve using the ZIF-8 particle of embodiment 7, specifically
The preparation method is as follows:
(1) ZIF-8, PVP, PVDF after removal guest molecule are dissolved in DMAC, component proportion are as follows: PVDF:ZIF-
8:PVP=10:0.1:3, stirring makes it after completely dissolution at 50 DEG C, and standing and defoaming is for 24 hours；
(2) casting solution of step (1) is scraped on a glass to the film of 180 μ m thicks；
(3) glass plate for having film liquid in step (2) is immersed in 20 DEG C of deionized waters and carries out split-phase；
(4) 3~8 days removing excess of solvent will be impregnated in the film transfer ionized water after split-phase in step (3), place into clean
Deionized water in save, obtain Kynoar mixed substrate membrane containing nano-grade molecular sieve, be denoted as ZIF-8/PVDF ultrafiltration membrane.
Comparative example
The present embodiment is the polyvinylidene fluoride flat film for directlying adopt the preparation of NIPS method and being free of ZIF-8, the preparation method comprises the following steps:
(1) PVP, PVDF are dissolved in DMAC, component proportion are as follows: PVDF:PVP=16:3, stirring fills it at 80 DEG C
After dividing dissolution, standing and defoaming is for 24 hours；
(2) casting solution of step (1) is scraped on a glass to the film of 250 μ m thicks；
(3) glass plate for having film liquid in step (2) is immersed in 25 DEG C of deionized waters and carries out split-phase；
(4) 3~8 days removing excess of solvent will be impregnated in the film transfer ionized water after split-phase in step (3), place into clean
Deionized water in save, obtain unmodified polyvinylidene fluoride flat film, be denoted as PVDF ultrafiltration membrane.
Permeance property test is carried out to the ultrafiltration membrane in Examples 1 to 3 and comparative example, pure water flux in test process,
0.5g/L ovalbumin (OVA) salting liquid flux and recovery rate data are acquired under 0.1MPa by cross-flow filtration device；Every
Film is by acquiring data to ensure accuracy after DI precompressed 30min.1 data of table are every kind of films in embodiment 2~4 and comparative example
Measure three stability numbers derived above.
The performance test results of ultrafiltration membrane in 1 embodiment 2~4 of table and comparative example
As it can be seen from table 1 the film that is, in comparative example 1 is compared, the process in embodiment 2~4 with unmodified ultrafiltration membrane
Modified ultrafiltration membrane is shown high-purity water flux (98% or more), and embodies the good antipollution of film to the processing of OVA solution
Performance, OVA flux recovery rate are up to 99.6%.Concrete reason are as follows: first, ZIF-8 particle is outstanding in film surface in film forming procedure
Its hydrophobic property forms the hole such as ZIF-8 size, this can increase pure water flux to a certain extent；Second, being embedded in mixed-matrix
ZIF-8 in membrane body can provide additional duct due to itself containing duct for film during the test, this can also enhance
The permeance property of mixed substrate membrane containing nano-grade molecular sieve；Third, the difference electricity of the hydrophobic characteristic of ZIF-8 itself and different proteins solution institute band
Property caused by mixed substrate membrane containing nano-grade molecular sieve the resistance tocrocking of BSA is enhanced, therefore, the method is to improve pure water flux, improves PVDF ultrafiltration
The new method of one kind of film resistance tocrocking.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited to above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring substantive content of the invention.
Claims (10)
1. a kind of preparation method for the Kynoar mixed substrate membrane containing nano-grade molecular sieve that flux is high, resistance tocrocking is strong, which is characterized in that by solvent
- 8 material of zeolite imidazole ester skeleton that thermal method is prepared is added in Kynoar casting solution, utilizes phase separation method
The Kynoar mixed substrate membrane containing nano-grade molecular sieve is made in the Kynoar casting solution.
The preparation side for the Kynoar mixed substrate membrane containing nano-grade molecular sieve that 2. a kind of flux according to claim 1 is high, resistance tocrocking is strong
Method, which is characterized in that the preparation method specifically includes the following steps:
(1) solvent-thermal method is prepared -8 material of zeolite imidazole ester skeleton, and by -8 material at high temperature of zeolite imidazole ester skeleton
Remove guest molecule；
(2) preparation of Kynoar casting solution
- 8 material of zeolite imidazole ester skeleton, additive and Kynoar are mixed in N, in N dimethyl acetamide, stirring
Completely to dissolution, standing and defoaming obtains the Kynoar casting solution；
(3) preparation of Kynoar mixed substrate membrane containing nano-grade molecular sieve
The Kynoar casting solution that step (2) obtains is scratched uniformly on a glass, then will be coated with Kynoar casting
The glass plate of film liquid is put into coagulation bath progress split-phase and obtains the Kynoar mixed substrate membrane containing nano-grade molecular sieve.
The preparation side for the Kynoar mixed substrate membrane containing nano-grade molecular sieve that 3. a kind of flux according to claim 1 is high, resistance tocrocking is strong
Method, which is characterized in that following steps are used in step (1): it is molten that soluble zinc salt is dissolved in acquisition zinc salt in methanol aqueous solution
Organic ligand is dissolved in acquisition organic ligand solution in methanol solvate, the zinc solution and organic ligand solution is mixed by liquid
It closes, is reacted under stirring condition, the solution centrifugal treating after reaction is obtained into solid material, the solid material is washed,
It is dried to obtain the particle of -8 material of zeolite imidazole ester skeleton.
The preparation side for the Kynoar mixed substrate membrane containing nano-grade molecular sieve that 4. a kind of flux according to claim 3 is high, resistance tocrocking is strong
Method, which is characterized in that the soluble zinc salt is Zn (NO3)2·6H2O, the organic ligand is 2-methylimidazole, described solvable
Property zinc salt and 2-methylimidazole molar ratio be 1:12~1:4；Reaction temperature is room temperature, reaction time in the reaction process
120~150min；The solid material is washed using methanol, and is dried under the conditions of 40~80 DEG C.
The preparation side for the Kynoar mixed substrate membrane containing nano-grade molecular sieve that 5. a kind of flux according to claim 1 is high, resistance tocrocking is strong
Method, which is characterized in that in the step (1), the temperature that high temperature removes guest molecule is 100~150 DEG C, and the processing time is 120
~180min.
The preparation side for the Kynoar mixed substrate membrane containing nano-grade molecular sieve that 6. a kind of flux according to claim 1 is high, resistance tocrocking is strong
Method, which is characterized in that in step (2), the additive is polyvinylpyrrolidone；- 8 material of zeolite imidazole ester skeleton:
Polyvinylpyrrolidone: the mass values of Kynoar are 0.1~0.5:3:10~20；In the Kynoar casting solution
The total mass fraction of polyvinylpyrrolidone and Kynoar is 10~20%.
The preparation side for the Kynoar mixed substrate membrane containing nano-grade molecular sieve that 7. a kind of flux according to claim 1 is high, resistance tocrocking is strong
Method, which is characterized in that in step (2), the stirring and dissolving temperature of the Kynoar casting solution is controlled at 50~80 DEG C；It is described
The time of stirring is 16~20h.
The preparation side for the Kynoar mixed substrate membrane containing nano-grade molecular sieve that 8. a kind of flux according to claim 1 is high, resistance tocrocking is strong
Method, which is characterized in that in step (3), the blade coating of the Kynoar casting solution on the glass plate is with a thickness of 100~250 μm.
The preparation side for the Kynoar mixed substrate membrane containing nano-grade molecular sieve that 9. a kind of flux according to claim 1 is high, resistance tocrocking is strong
Method, which is characterized in that in step (3), the coagulation bath is deionized water, and temperature is 15~30 DEG C.
The preparation side for the Kynoar mixed substrate membrane containing nano-grade molecular sieve that 10. a kind of flux according to claim 1 is high, resistance tocrocking is strong
Method, which is characterized in that the preparation method further includes the preservation of Kynoar mixed substrate membrane containing nano-grade molecular sieve: step (3) is obtained described
Kynoar mixed substrate membrane containing nano-grade molecular sieve, which is placed in deionized water, removes residual solvent, is then placed in deionized water and is saved.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910764635.1A CN110479109B (en) | 2019-08-19 | 2019-08-19 | Preparation method of polyvinylidene fluoride mixed matrix membrane with high flux and strong pollution resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910764635.1A CN110479109B (en) | 2019-08-19 | 2019-08-19 | Preparation method of polyvinylidene fluoride mixed matrix membrane with high flux and strong pollution resistance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110479109A true CN110479109A (en) | 2019-11-22 |
| CN110479109B CN110479109B (en) | 2022-07-05 |
Family
ID=68551964
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910764635.1A Active CN110479109B (en) | 2019-08-19 | 2019-08-19 | Preparation method of polyvinylidene fluoride mixed matrix membrane with high flux and strong pollution resistance |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110479109B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111760468A (en) * | 2020-06-27 | 2020-10-13 | 上海应用技术大学 | Polyvinylidene fluoride composite ultrafiltration membrane for catalytic reduction of p-nitrophenol and preparation method thereof |
| CN112090293A (en) * | 2020-09-07 | 2020-12-18 | 北京赛诺膜技术有限公司 | Polymer hybrid ultrafiltration membrane and double-pass spinning preparation method thereof |
| CN112569808A (en) * | 2020-11-22 | 2021-03-30 | 上海应用技术大学 | Polyvinylidene fluoride mixed matrix membrane with white spirit catalytic filtration performance and preparation and application thereof |
| CN113083042A (en) * | 2021-04-12 | 2021-07-09 | 大连理工大学 | Mixed matrix membrane based on MXene/ZIF-composite material and preparation method thereof |
| CN115582102A (en) * | 2022-10-08 | 2023-01-10 | 湖南大学 | Porous sponge adsorbent and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102179189A (en) * | 2011-04-01 | 2011-09-14 | 河北科技大学 | Preparation method of pollution-resisting polyvinylidene fluoride ultrafiltration membrane |
| WO2013177199A1 (en) * | 2012-05-25 | 2013-11-28 | Georgia Tech Research Corporation | Metal-organic framework supported on porous polymer |
| CN105642127A (en) * | 2016-01-13 | 2016-06-08 | 厦门理工学院 | Preparation method of anthraquinone functionalized polyvinylidene fluoride ultrafiltration membrane |
| CN107020020A (en) * | 2017-05-22 | 2017-08-08 | 天津工业大学 | A kind of preparation method of new MOFs PVDF composite membranes |
| CN107638807A (en) * | 2017-11-10 | 2018-01-30 | 上海应用技术大学 | ZIF 8/PVDF milipore filters with catalytic action and preparation method thereof under a kind of normal temperature |
| CN108159897A (en) * | 2018-01-02 | 2018-06-15 | 天津工业大学 | A kind of PVDF/ZIF-7 hydrophobic membranes and preparation method with dual microtexture |
-
2019
- 2019-08-19 CN CN201910764635.1A patent/CN110479109B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102179189A (en) * | 2011-04-01 | 2011-09-14 | 河北科技大学 | Preparation method of pollution-resisting polyvinylidene fluoride ultrafiltration membrane |
| WO2013177199A1 (en) * | 2012-05-25 | 2013-11-28 | Georgia Tech Research Corporation | Metal-organic framework supported on porous polymer |
| CN105642127A (en) * | 2016-01-13 | 2016-06-08 | 厦门理工学院 | Preparation method of anthraquinone functionalized polyvinylidene fluoride ultrafiltration membrane |
| CN107020020A (en) * | 2017-05-22 | 2017-08-08 | 天津工业大学 | A kind of preparation method of new MOFs PVDF composite membranes |
| CN107638807A (en) * | 2017-11-10 | 2018-01-30 | 上海应用技术大学 | ZIF 8/PVDF milipore filters with catalytic action and preparation method thereof under a kind of normal temperature |
| CN108159897A (en) * | 2018-01-02 | 2018-06-15 | 天津工业大学 | A kind of PVDF/ZIF-7 hydrophobic membranes and preparation method with dual microtexture |
Non-Patent Citations (3)
| Title |
|---|
| 严建华 等: "《能源与环境研究进展》", 31 October 2008, 浙江大学出版社 * |
| 董秉直 等: "《饮用水膜法处理新技术》", 30 September 2015, 同济大学出版社 * |
| 谢涵 等: "聚偏氟乙烯混合基质超滤膜的制备与研究", 《应用技术学报》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111760468A (en) * | 2020-06-27 | 2020-10-13 | 上海应用技术大学 | Polyvinylidene fluoride composite ultrafiltration membrane for catalytic reduction of p-nitrophenol and preparation method thereof |
| CN111760468B (en) * | 2020-06-27 | 2022-08-23 | 上海应用技术大学 | Polyvinylidene fluoride composite ultrafiltration membrane for catalytic reduction of p-nitrophenol and preparation method thereof |
| CN112090293A (en) * | 2020-09-07 | 2020-12-18 | 北京赛诺膜技术有限公司 | Polymer hybrid ultrafiltration membrane and double-pass spinning preparation method thereof |
| CN112569808A (en) * | 2020-11-22 | 2021-03-30 | 上海应用技术大学 | Polyvinylidene fluoride mixed matrix membrane with white spirit catalytic filtration performance and preparation and application thereof |
| CN112569808B (en) * | 2020-11-22 | 2023-03-21 | 上海应用技术大学 | Polyvinylidene fluoride mixed matrix membrane with white spirit catalytic filtration performance and preparation and application thereof |
| CN113083042A (en) * | 2021-04-12 | 2021-07-09 | 大连理工大学 | Mixed matrix membrane based on MXene/ZIF-composite material and preparation method thereof |
| CN113083042B (en) * | 2021-04-12 | 2021-12-21 | 大连理工大学 | Mixed matrix membrane based on MXene/ZIF-8 composite material and preparation method thereof |
| CN115582102A (en) * | 2022-10-08 | 2023-01-10 | 湖南大学 | Porous sponge adsorbent and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110479109B (en) | 2022-07-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110479109A (en) | The preparation method for the Kynoar mixed substrate membrane containing nano-grade molecular sieve that flux is high, resistance tocrocking is strong | |
| CN109289550B (en) | Preparation method and application of anti-pollution polyvinylidene fluoride hybrid ultrafiltration membrane | |
| CN105457504A (en) | Novel titanium dioxide nano-particle/polymer hybrid membrane and preparation method thereof | |
| CN102068925B (en) | Preparation method of polyaniline nano composite film | |
| CN107376673B (en) | Loaded with TiO2PES ultrafiltration membrane of nanotube and preparation method and application thereof | |
| CN103721575A (en) | Preparation method of polysulfones flat ultrafiltration composite membrane | |
| CN104383818A (en) | Composite microporous diaphragm, preparation method and application thereof | |
| CN110951089A (en) | Method for promoting synthesis of ZIF-8 in aprotic polar solvent | |
| CN110605028A (en) | Preparation method of polyvinylidene fluoride mixed matrix membrane with high mechanical strength | |
| CN106390777A (en) | Copper hydroxide nanowire/polyvinylidene fluoride hybrid ultrafiltration membrane and preparation method thereof | |
| Gao et al. | Development of hydrophilic PES membranes using F127 and HKUST-1 based on the RTIPS method: Mitigate the permeability-selectivity trade-off | |
| Zhou et al. | Preparation of a novel sulfonated polyphenlene sulfone with flexible side chain for ultrafiltration membrane application | |
| Gao et al. | Bimetallic polyphenol networks structure modified polyethersulfone membrane with hydrophilic and anti-fouling properties based on reverse thermally induced phase separation method | |
| CN110975649A (en) | Modified polyvinylidene fluoride ultrafiltration membrane and preparation method thereof | |
| CN114904404A (en) | Mixed matrix forward osmosis membrane based on MOF-808(Zr) and preparation method thereof | |
| CN113318605B (en) | MOF-based mixed matrix membrane and preparation method thereof | |
| WO2021088665A1 (en) | Antifouling and hydrophilic polyethersulfone ultrafiltration membrane and preparation method therefor | |
| CN104785122B (en) | Polyether sulfone-nanocarbon combined gas separation membrane and preparation method thereof | |
| CN115260504B (en) | Zwitterionic-containing polyarylethersulfone block copolymer, anti-pollution ultrafiltration membrane, preparation method and application | |
| CN113813801B (en) | Mixed matrix ultrafiltration membrane doped with ZIFs@polyionic liquid compound and preparation method thereof | |
| CN108619917B (en) | Metal-organic framework based mixed matrix membrane for hydrogen sulfide sensing and preparation method thereof | |
| Zhang et al. | Preparation of polysulfone-based block copolymer ultrafiltration membranes by selective swelling and sacrificing nanofillers | |
| CN101850217A (en) | Method for preparing skin-free homogeneous structural polyvinylidene fluoride transfer film | |
| CN112007523A (en) | Polyvinylidene fluoride mixed matrix film and preparation method thereof | |
| CN112608504B (en) | Cross-linked sulfonated polyarylethersulfone for generating micro-nano bubbles, preparation method and cross-linked sulfonated polyarylethersulfone membrane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |