CN116617869A - Composite separation membrane and application thereof - Google Patents
Composite separation membrane and application thereof Download PDFInfo
- Publication number
- CN116617869A CN116617869A CN202310880359.1A CN202310880359A CN116617869A CN 116617869 A CN116617869 A CN 116617869A CN 202310880359 A CN202310880359 A CN 202310880359A CN 116617869 A CN116617869 A CN 116617869A
- Authority
- CN
- China
- Prior art keywords
- composite separation
- separation membrane
- mixed solution
- membrane
- bioreactor
- 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.)
- Pending
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 77
- 238000000926 separation method Methods 0.000 title claims abstract description 59
- 239000002131 composite material Substances 0.000 title claims abstract description 43
- 229920006393 polyether sulfone Polymers 0.000 claims abstract description 41
- 239000004695 Polyether sulfone Substances 0.000 claims abstract description 40
- 239000011347 resin Substances 0.000 claims abstract description 30
- 229920005989 resin Polymers 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000011259 mixed solution Substances 0.000 claims abstract description 17
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 16
- 239000011148 porous material Substances 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 14
- 239000013177 MIL-101 Substances 0.000 claims abstract description 12
- 239000011248 coating agent Substances 0.000 claims abstract description 7
- 238000000576 coating method Methods 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000005345 coagulation Methods 0.000 claims description 9
- 230000015271 coagulation Effects 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 7
- 230000001105 regulatory effect Effects 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 230000002572 peristaltic effect Effects 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 238000007872 degassing Methods 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 239000013178 MIL-101(Cr) Substances 0.000 abstract description 21
- 102000004169 proteins and genes Human genes 0.000 abstract description 11
- 108090000623 proteins and genes Proteins 0.000 abstract description 11
- 230000004907 flux Effects 0.000 abstract description 5
- 238000005191 phase separation Methods 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 239000012456 homogeneous solution Substances 0.000 description 13
- 239000011521 glass Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000012466 permeate Substances 0.000 description 3
- 238000009832 plasma treatment Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000013148 Cu-BTC MOF Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000013207 UiO-66 Substances 0.000 description 1
- -1 ZIF-67 Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- GVHCUJZTWMCYJM-UHFFFAOYSA-N chromium(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GVHCUJZTWMCYJM-UHFFFAOYSA-N 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000010874 maintenance of protein location Effects 0.000 description 1
- 238000009285 membrane fouling Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000013105 nano metal-organic framework Substances 0.000 description 1
- 239000013289 nano-metal-organic framework Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000000614 phase inversion technique Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000003075 superhydrophobic effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 1
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- 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
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
- C02F3/10—Packings; Fillings; Grids
- C02F3/102—Permeable membranes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
- C02F3/10—Packings; Fillings; Grids
- C02F3/105—Characterized by the chemical composition
- C02F3/108—Immobilising gels, polymers or the like
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
- C02F3/12—Activated sludge processes
- C02F3/1236—Particular type of activated sludge installations
- C02F3/1268—Membrane bioreactor systems
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Abstract
The invention discloses a composite separation membrane and application thereof, belonging to the technical field of separation membranes, comprising: obtaining a metal organic framework material MIL-101; obtaining a mixed solution of the metal organic framework material MIL-101 and polyether sulfone resin; and coating the mixed solution into a film to obtain the composite separation film. The method adopts a solvent induced phase separation method, has simple membrane preparation process and easy operation, can control the pore structure and the pore diameter by adding MIL-101 (Cr) with different contents, improves the membrane flux and improves the protein rejection rate.
Description
Technical Field
The invention relates to the technical field of separation membranes, in particular to a composite separation membrane and application thereof.
Background
The Membrane Bioreactor (MBR) is used as a novel water treatment technology, has the characteristics of biological treatment and membrane separation treatment, and has the advantages of low sludge yield, no need of secondary precipitation, small occupied area, high biological treatment organic load and the like. When particles, organic and inorganic compounds are deposited within the separation membrane pores and on the membrane surface, the pores are fouled, thereby increasing the transmembrane pressure and decreasing the permeate flux. At the same time, microorganisms attach around the membrane, grow in the pores or on the surface of the membrane, forming biological contamination, and can produce more serious membrane failure. Therefore, in order to avoid the formation of scale and biofouling, it is very necessary to reduce the operating costs, increase the membrane life, and ensure the quality of the effluent. Membrane fouling and biofouling phenomena of hydrophobic separation membranes are more pronounced than those of hydrophilic separation membranes. Polymer films are not highly hydrophilic and are typically modified using surface coating, chemical grafting, polymer blending, plasma treatment, nanoparticle modification, and other techniques. The nano particles have the advantages of simple and convenient processing, can increase permeation flux, reduce the formation of scale and biological pollution, and are widely applied to silver, silicon dioxide, ferric oxide, magnesium oxide, carbon nano tubes, metal organic frameworks and the like. Wherein the tiny ions/molecules in the Metal Organic Framework (MOF) hybridized by inorganic-organic have high active sites and highly ordered porous structures, so that the separation efficiency is more outstanding. Common MOF materials are ZIF-8, UIO-66, ZIF-67, HKUST-1, MIL-101, etc. The MIL-101 (Cr) has larger specific surface area and pore volume, strong temperature resistance and high stability in air or water, and is more suitable for application in separation membranes. Polyethersulfone is a common water purification and separation membrane with high strength, large water flux, less dissolved substances and low protein adsorption capacity. Many polyethersulfone separation membranes have been prepared by researchers, and more of the polyethersulfones are functionalized to achieve a unique heavy metal adsorption function, for example, a preparation method of polyethersulfone with dendritic polyamide-amine functional groups is provided in Chinese patent publication No. CN107875869A, and the method needs a large amount of experimental treatment on the polyethersulfone to obtain the functionalized membrane, so that the method has the advantages of multiple used experimental reagents, complicated steps and adverse industrial production. There is also a method of performing plasma treatment on a functionalized polyethersulfone membrane to obtain a super hydrophilic polymer membrane, such as chinese patent publication No. CN115337790a, which can prepare a polymer membrane having both super hydrophobic and low protein retention rate, but it is unavoidable that the plasma treatment method is difficult, can penetrate only a thickness of several nanometers per second, and needs to be used as soon as possible after the treatment.
Disclosure of Invention
In order to solve the problems of the prior art, the invention provides a preparation method of a composite separation membrane, which comprises the following steps:
obtaining a metal organic framework material MIL-101;
obtaining a mixed solution of the metal organic framework material MIL-101 and polyether sulfone resin;
and coating the mixed solution into a film to obtain the composite separation film.
Further, the method for obtaining the mixed solution comprises the following steps:
dispersing the metal organic framework material MIL-101 in an organic solvent to obtain a dispersion liquid;
and adding polyether sulfone resin into the dispersion liquid, and mixing to obtain a mixed liquid.
Further, the relation of the dosage of each substance in the mixed solution is as follows:
according to the mass percentage, the polyether sulfone resin is 15-17%, the metal organic framework material MIL-101 is used in an amount of 0.2-1%, and the balance is organic solvent.
Further, the organic solvent is selected from any one or more than two of N-methyl pyrrolidone, N-dimethylformamide, N-dimethylacetamide and dimethyl sulfoxide;
the molecular weight of the polyethersulfone resin is 75kg/mol or 92kg/mol;
the dispersing conditions are as follows: ultrasonic dispersing for 30-120min;
the mixing conditions are as follows: mixing temperature is 25-35 ℃, and mixing time is 12-24h.
Further, before adding the polyethersulfone resin to the organic solution, the method further comprises: and drying the polyether sulfone resin.
Further, the mixed solution is coated into a film, which comprises the following steps:
degassing the mixed solution;
and coating the degassed mixed solution on a substrate, performing coagulation bath film forming, and drying to obtain the composite separation film.
Further, the coagulation bath is any one of pure water, ethanol and 5-75% ethanol aqueous solution.
In another aspect, the present invention provides a composite separation membrane, which is made by the method for preparing a composite separation membrane.
Furthermore, the invention provides the application of the composite separation membrane on a membrane-bioreactor, wherein the composite separation membrane is arranged on a membrane component and is arranged in the bioreactor provided with a blower;
the front end of the bioreactor is provided with a treatment tank with a peristaltic pump, and the rear end of the bioreactor is provided with a regulating tank with a vacuum pump.
The invention has the beneficial effects that:
1. the method adopts a phase inversion method to prepare the composite separation membrane of the metal organic framework modified polyether sulfone, and MIL-101 (Cr) nano particles are embedded in polyether sulfone resin, so that hydrophilicity and water permeability can be increased.
2. The method adopts a solvent induced phase separation method, has simple membrane preparation process and easy operation, can control the pore structure and the pore diameter by adding MIL-101 (Cr) with different contents, improves the membrane flux and improves the protein rejection rate.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for the description of the embodiments will be briefly described below, and it is apparent that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an infrared spectrum of MIL-101 (Cr) in example 2;
FIG. 2 is an SEM image of MIL-101 (Cr) modified polyethersulfone composite separation membrane of example 6;
FIG. 3 shows the protein rejection of the composite separation membranes of examples 2 to 6;
FIG. 4 is the COD removal rate and MLSS concentration of example 6 at different days;
FIG. 5 is a schematic illustration of the application of the composite separation membrane of example 2 to a membrane-bioreactor.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the embodiments of the present invention will be described in further detail with reference to the accompanying drawings.
It should be noted that the main invention point of the present invention is that in order to further reduce the preparation cost of the polyethersulfone separation membrane and maintain the processing performance and heat resistance thereof, a preparation method of a composite separation membrane of metal organic framework modified polyethersulfone is provided, and the application of the prepared composite separation membrane in a membrane-bioreactor.
Example 1:
synthesis of MIL-101 (Cr):
2g of chromium (III) nitrate nonahydrate and 0.83g of terephthalic acid were weighed out and mixed in 20ml of deionized water and stirred for 30 minutes. The resulting dark blue mixture was transferred to a stainless steel autoclave and placed in an oven at 220 ℃ for 20 hours. Taking out, putting into a centrifuge, centrifuging at 5000rpm for 10min, and then washing the precipitate with deionized water and methanol respectively for 3 times to remove unreacted terephthalic acid. The precipitate was dispersed in 10ml of N, N-dimethylacetamide solution and placed in a 70℃oil bath for one night. Finally, the powder was dried at 25 ℃ and activated in a vacuum oven at 150 ℃ for use.
Example 2:
drying polyethersulfone resin with the molecular weight of 75kg/mol at 80 ℃ for 4 hours, then weighing MIL-101 (Cr) with the formula weight (17 percent, 0 percent and 83 percent of the mass percent of the polyethersulfone resin, MIL-101 (Cr) and N, N-dimethylacetamide respectively) to be dispersed in an N, N-dimethylacetamide solution, carrying out ultrasonic treatment for 30 minutes, adding the dried polyethersulfone resin, and stirring for 12 hours at room temperature to obtain a homogeneous solution. The obtained homogeneous solution was degassed for 1 hour, the homogeneous solution was cast on a glass plate using an applicator with a gap of 100 μm, left to stand for 10 minutes, transferred to a coagulation bath (water) for treatment, membrane separation was placed in pure water to achieve complete phase inversion, and finally dried, and a composite separation membrane was obtained, which had a porosity of 70.15% and an average pore diameter of 11.65nm. The scale factor was 74.32% and the protein rejection 70.10% when applied to a membrane bioreactor.
FIG. 1 is an infrared spectrum of MIL-101 (Cr) in example 2; it can be observed at 1607 and 1392cm -1 The absorption bands at which are attributable to O-C-O asymmetric and symmetric stretching vibrations, 1015 and 748cm, respectively -1 The band at the site is attributed to C-H of the benzene ring, indicating efficient synthesis of MIL-101 (Cr).
Example 3:
the polyethersulfone resin with a molecular weight of 75kg/mol was dried at 90℃for 4h. Then weighing the formula amount (17%, 0.2% and 82.8% of MIL-101 (Cr) of polyether sulfone resin, MIL-101 (Cr) and N, N-dimethylacetamide by mass percent) and dispersing the mixture in the N, N-dimethylacetamide solution, carrying out ultrasonic treatment for 60min, adding the dried polyether sulfone resin, and stirring for 12h at room temperature to obtain a homogeneous solution. The obtained homogeneous solution was degassed for 1 hour, the homogeneous solution was cast on a glass plate using an applicator with a gap of 100 μm, left to stand for 15min, transferred to a coagulation bath (water) for treatment, membrane separation was placed in pure water to achieve complete phase inversion, and finally dried, and a composite separation membrane was obtained with a porosity of 73.23% and an average pore diameter of 17.15nm. The scale factor is 52.14% and the protein rejection is 90.01% when the scale factor is applied to a membrane-bioreactor.
Example 4:
the polyethersulfone resin with a molecular weight of 75kg/mol was dried at 100℃for 5 hours. Weighing the formula amount (17%, 0.4% and 82.6% of mass percent of polyether sulfone resin, MIL-101 (Cr) and N, N-dimethylacetamide) respectively, dispersing MIL-101 (Cr) in the N, N-dimethylacetamide solution, carrying out ultrasonic treatment for 60min, adding the dried polyether sulfone resin, and stirring for 16h at room temperature to obtain a homogeneous solution. The obtained homogeneous solution was degassed for 1 hour, the homogeneous solution was cast on a glass plate using an applicator having a gap of 150 μm, left to stand for 20 minutes, transferred to a coagulation bath (pure water) for treatment, membrane separation was placed in pure water to achieve complete phase conversion, and finally dried to obtain a composite separation membrane having a porosity of 77.63% and an average pore diameter of 19.12nm. The scale factor is 48.63% and the protein rejection rate is 98.87% when the scale factor is applied to a membrane-bioreactor.
FIG. 4 is the COD removal rate and MLSS concentration of example 4 on different days; with the increase of treatment days, the concentration of MLSS (short for the concentration of suspended solids in the mixed liquor, which is also called the concentration of sludge in the mixed liquor) correspondingly increases, the COD removal rate is in an ascending trend, and the phenomenon of weakening of the treatment effect does not occur, so that the effective separability of the material can be proved.
Example 5:
the polyethersulfone resin with a molecular weight of 75kg/mol was dried at 110℃for 5h. Weighing the formula amount (17%, 0.8% and 82.2% of the mass percentages of polyether sulfone resin, MIL-101 (Cr) and N, N-dimethylacetamide) respectively, dispersing MIL-101 (Cr) in the N, N-dimethylacetamide solution, carrying out ultrasonic treatment for 60min, adding the dried polyether sulfone resin, and stirring for 16h at room temperature to obtain a homogeneous solution. The obtained homogeneous solution was degassed for 1.5 hours, cast on a glass plate using an applicator with a gap of 250 μm, left stand for 25 minutes, transferred to a coagulation bath (water) for treatment, membrane separation was placed in pure water to achieve complete phase inversion, and finally dried, and a composite separation membrane was obtained with a porosity of 75.08% and an average pore diameter of 16.62nm. The scale factor was 58.62% and the protein rejection 92.18% when applied to a membrane bioreactor.
Example 6:
the polyethersulfone resin with a molecular weight of 92kg/mol was dried at 120℃for 6h. Weighing the formula amount (17% by mass of polyethersulfone resin, 1.0% by mass of MIL-101 (Cr) and 82.0% by mass of N, N-dimethylacetamide) respectively, dispersing MIL-101 (Cr) in the N, N-dimethylacetamide solution, carrying out ultrasonic treatment for 120min, adding the dried polyethersulfone resin, and stirring at room temperature for 24h to obtain a homogeneous solution. The obtained homogeneous solution was degassed for 2 hours, cast on a glass plate using a coater with a gap of 300 μm, left for 30 minutes, transferred to a coagulation bath (ethanol solution) for treatment, membrane separation was placed in pure water to achieve complete phase inversion, and finally dried, and a composite separation membrane was obtained with a porosity of 72.66% and an average pore diameter of 15.65nm. The total fouling rate of the membrane-bioreactor used in the membrane bioreactor is 60.92%, and the protein rejection rate is 73.81%.
FIG. 2 is an SEM image of MIL-101 (Cr) modified polyethersulfone composite separation membrane of example 6; the porosity and average pore size were 72.66% and 15.65nm, respectively, as calculated by scale.
FIG. 3 shows the protein rejection of the composite separation membranes of examples 2 to 6; as can be seen from the graph, the protein rejection rate of the material of example 4 was the highest and was 98.87%, i.e., the amount of MIL-101 (Cr) added was 0.4%.
Example 7:
referring to fig. 5, the application of a composite separation membrane in a membrane-bioreactor specifically operates as follows: installing a composite separation membrane on a membrane assembly and placing the composite separation membrane in a bioreactor equipped with a blower; the front end of the bioreactor is a treatment tank provided with a peristaltic pump, and the rear end is an adjusting tank provided with a vacuum pump.
Wherein the membrane-bioreactor comprises: a treatment tank 1, a peristaltic pump 2, a bioreactor 3, a membrane module 4, a blower 5, a pressure gauge 6, a permeate 7, a regulating tank 8 and a vacuum pump 9;
the peristaltic pump 2 is respectively connected with the treatment tank 1 and the bioreactor 3 through pipelines, and the membrane component 4 is arranged in the bioreactor 3;
the blower 5 is communicated with the bottom of the bioreactor 3 through a pipeline;
the membrane component 4 is connected with the regulating tank 8 through a pipeline, and the pressure gauge 6 is arranged on the pipeline between the membrane component 4 and the regulating tank 8;
the permeate 7 is contained in the regulating tank 8, and the regulating tank 8 is connected with the vacuum pump 9 through a pipeline.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (10)
1. A method for preparing a composite separation membrane, the method comprising the steps of:
obtaining a metal organic framework material MIL-101;
obtaining a mixed solution of the metal organic framework material MIL-101 and polyether sulfone resin;
and coating the mixed solution into a film to obtain the composite separation film.
2. The method for preparing a composite separation membrane according to claim 1, wherein the method for obtaining the mixed solution comprises:
dispersing the metal organic framework material MIL-101 in an organic solvent to obtain a dispersion liquid;
and adding polyether sulfone resin into the dispersion liquid, and mixing to obtain a mixed liquid.
3. The method for preparing a composite separation membrane according to claim 2, wherein the amount of each substance in the mixed solution is as follows:
according to the mass percentage, the polyether sulfone resin is 15-17%, the dosage of the metal organic framework material MIL-101 is more than 0 and less than 1%, and the balance is organic solvent.
4. The method for preparing a composite separation membrane according to claim 2, wherein the amount of each substance in the mixed solution is as follows:
according to the mass percentage, the polyether sulfone resin is 17 percent, the dosage of the metal organic framework material MIL-101 is 0.2-1 percent, and the balance is organic solvent.
5. The method for producing a composite separation membrane according to claim 2, wherein the organic solvent is selected from any one or a mixture of two or more of N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, and dimethylsulfoxide;
the molecular weight of the polyethersulfone resin is 75kg/mol or 92kg/mol;
the dispersing conditions are as follows: ultrasonic dispersing for 30-120min;
the mixing conditions are as follows: mixing temperature is 25-35 ℃, and mixing time is 12-24h.
6. The method for producing a composite separation membrane according to claim 1, wherein before adding the polyethersulfone resin to the organic solution, further comprising: and drying the polyether sulfone resin.
7. The method for producing a composite separation membrane according to claim 1, wherein the step of coating the mixed solution into a membrane comprises:
degassing the mixed solution;
and coating the degassed mixed solution on a substrate, performing coagulation bath film forming, and drying to obtain the composite separation film.
8. The method for producing a composite separation membrane according to claim 7, wherein the coagulation bath is any one of pure water, ethanol, and 5 to 75% aqueous ethanol.
9. A composite separation membrane, characterized in that the composite separation membrane is prepared by the preparation method of any one of claims 1 to 7;
the composite separation membrane prepared by the method has the porosity of 70-78% and the average pore diameter of 11.80-19.85 nm.
10. Use of a composite separation membrane according to claim 9 in a membrane-bioreactor, wherein the composite separation membrane is mounted on a membrane module, placed in a bioreactor equipped with a blower;
the front end of the bioreactor is provided with a treatment tank with a peristaltic pump, and the rear end of the bioreactor is provided with a regulating tank with a vacuum pump.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310880359.1A CN116617869A (en) | 2023-07-18 | 2023-07-18 | Composite separation membrane and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310880359.1A CN116617869A (en) | 2023-07-18 | 2023-07-18 | Composite separation membrane and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116617869A true CN116617869A (en) | 2023-08-22 |
Family
ID=87613725
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310880359.1A Pending CN116617869A (en) | 2023-07-18 | 2023-07-18 | Composite separation membrane and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116617869A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105789668A (en) * | 2016-03-03 | 2016-07-20 | 中国科学院化学研究所 | Preparation method of metal-organic framework material/polymer composite proton exchange membrane |
| CN106076127A (en) * | 2016-06-24 | 2016-11-09 | 盐城海普润膜科技有限公司 | A kind of inner support hollow-fibre membrane and its preparation method and application |
| CN110559884A (en) * | 2019-08-29 | 2019-12-13 | 浙江工业大学 | MIL-101@ PIM-1 composite pervaporation membrane and preparation method and application thereof |
| CN111249928A (en) * | 2020-02-27 | 2020-06-09 | 山东科技大学 | Mixed matrix cation exchange membrane based on metal organic framework compound and preparation method thereof |
| CN114471195A (en) * | 2020-10-23 | 2022-05-13 | 宁波方太厨具有限公司 | Casting solution, hollow fiber membrane prepared by using same and preparation method of hollow fiber membrane |
-
2023
- 2023-07-18 CN CN202310880359.1A patent/CN116617869A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105789668A (en) * | 2016-03-03 | 2016-07-20 | 中国科学院化学研究所 | Preparation method of metal-organic framework material/polymer composite proton exchange membrane |
| CN106076127A (en) * | 2016-06-24 | 2016-11-09 | 盐城海普润膜科技有限公司 | A kind of inner support hollow-fibre membrane and its preparation method and application |
| CN110559884A (en) * | 2019-08-29 | 2019-12-13 | 浙江工业大学 | MIL-101@ PIM-1 composite pervaporation membrane and preparation method and application thereof |
| CN111249928A (en) * | 2020-02-27 | 2020-06-09 | 山东科技大学 | Mixed matrix cation exchange membrane based on metal organic framework compound and preparation method thereof |
| CN114471195A (en) * | 2020-10-23 | 2022-05-13 | 宁波方太厨具有限公司 | Casting solution, hollow fiber membrane prepared by using same and preparation method of hollow fiber membrane |
Non-Patent Citations (1)
| Title |
|---|
| NEGIN ASADI ARBABI 等: "Evaluation of antifouling/biofouling ability of a novel MIL101(Cr)/PES composite membrane for acetate wastewater treatment in MBR application", POLYMER BULLETIN * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Kheirieh et al. | Application and modification of polysulfone membranes | |
| Ahsani et al. | Preparation of antibiofouling nanocomposite PVDF/Ag-SiO2 membrane and long-term performance evaluation in the MBR system fed by real pharmaceutical wastewater | |
| Ladewig et al. | Fundamentals of membrane processes | |
| Zeng et al. | Preparation of a novel poly (vinylidene fluoride) ultrafiltration membrane by incorporation of 3-aminopropyltriethoxysilane-grafted halloysite nanotubes for oil/water separation | |
| Homayoonfal et al. | A comparison between blending and surface deposition methods for the preparation of iron oxide/polysulfone nanocomposite membranes | |
| JP6018790B2 (en) | Separation membrane, manufacturing method thereof, and water treatment apparatus including separation membrane | |
| Ounifi et al. | Synthesis and characterization of a thin-film composite nanofiltration membrane based on polyamide-cellulose acetate: application for water purification | |
| CN104607063B (en) | PVDF permanently hydrophilic ultrafiltration membrane and modification method thereof | |
| Li et al. | Preparation of hydrophilic PVDF/PPTA blend membranes by in situ polycondensation and its application in the treatment of landfill leachate | |
| Xie et al. | Hydrophilic modification and anti-fouling properties of PVDF membrane via in situ nano-particle blending | |
| CN109126480A (en) | Modified forward osmosis membrane of a kind of metal organic frame nanometer sheet and its preparation method and application | |
| Huang et al. | Novel N-doped graphene enhanced ultrafiltration nano-porous polyvinylidene fluoride membrane with high permeability and stability for water treatment | |
| Saberi et al. | Improving the transport and antifouling properties of poly (vinyl chloride) hollow-fiber ultrafiltration membranes by incorporating silica nanoparticles | |
| CN107115796B (en) | Preparation method of hydrophilic polyacrylonitrile separation membrane | |
| Li et al. | Surface synthesis of a polyethylene glutaraldehyde coating for improving the oil removal from wastewater of microfiltration carbon membranes | |
| Koriem et al. | Cellulose acetate/polyvinylidene fluoride based mixed matrix membranes impregnated with UiO-66 nano-MOF for reverse osmosis desalination | |
| Yogarathinam et al. | Harvesting of microalgae Coelastrella sp. FI69 using pore former induced TiO2 incorporated PES mixed matrix membranes | |
| Ji et al. | Organic solvent-free constructing of stable zeolitic imidazolate framework functional layer enhanced by halloysite nanotubes and polyvinyl alcohol on polyvinylidene fluoride hollow fiber membranes for treating dyeing wastewater | |
| CN109081430A (en) | It can accelerate the preparation method of the reproducibility graphene oxide Modified Membrane of water treatment procedure | |
| CN117181004A (en) | Hydrophilic anti-pollution MXene/PVDF composite membrane and preparation method and application thereof | |
| CN116617869A (en) | Composite separation membrane and application thereof | |
| Chen et al. | Preparation and characterization of the charged PDMC/Al2O3 composite nanofiltration membrane | |
| Wan et al. | Biodegradable chitosan-based membranes for highly effective separation of emulsified oil/water | |
| Gao et al. | Constituting a special redox surface-initiating system and realizing graft-polymerization of GMA on polysulfone microfiltration membrane | |
| Barzin et al. | Hemodialysis membranes prepared from poly (vinyl alcohol): Effects of the preparation conditions on the morphology and performance |
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 |