CN114082302A - Anti-pollution composite nanofiltration membrane and preparation method thereof - Google Patents
Anti-pollution composite nanofiltration membrane and preparation method thereof Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 113
- 238000001728 nano-filtration Methods 0.000 title claims abstract description 61
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 82
- 239000011787 zinc oxide Substances 0.000 claims abstract description 36
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000005266 casting Methods 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 19
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 238000011033 desalting Methods 0.000 claims abstract description 12
- 238000002791 soaking Methods 0.000 claims abstract description 12
- 239000011248 coating agent Substances 0.000 claims abstract description 9
- 238000000576 coating method Methods 0.000 claims abstract description 9
- 239000012452 mother liquor Substances 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 210000004379 membrane Anatomy 0.000 claims description 55
- 239000000243 solution Substances 0.000 claims description 54
- 238000003756 stirring Methods 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 12
- 210000002469 basement membrane Anatomy 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 239000000908 ammonium hydroxide Substances 0.000 claims description 7
- 239000010413 mother solution Substances 0.000 claims description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 7
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical group CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 6
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 claims description 6
- 238000005191 phase separation Methods 0.000 claims description 6
- 229940068918 polyethylene glycol 400 Drugs 0.000 claims description 6
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000004246 zinc acetate Substances 0.000 claims description 5
- IPCXNCATNBAPKW-UHFFFAOYSA-N zinc;hydrate Chemical compound O.[Zn] IPCXNCATNBAPKW-UHFFFAOYSA-N 0.000 claims description 5
- 239000004088 foaming agent Substances 0.000 claims description 2
- 238000000108 ultra-filtration Methods 0.000 abstract description 17
- 230000002035 prolonged effect Effects 0.000 abstract description 7
- 241000894006 Bacteria Species 0.000 abstract description 6
- 230000001954 sterilising effect Effects 0.000 abstract description 5
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000004332 deodorization Methods 0.000 abstract description 4
- 238000012695 Interfacial polymerization Methods 0.000 abstract description 3
- 238000003980 solgel method Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 11
- 230000004907 flux Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 238000010612 desalination reaction Methods 0.000 description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 241000191967 Staphylococcus aureus Species 0.000 description 3
- 229940098773 bovine serum albumin Drugs 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- 229910001887 tin oxide Inorganic materials 0.000 description 3
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229960000074 biopharmaceutical Drugs 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
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- 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
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
-
- 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
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0083—Thermal after-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
-
- 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
- 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
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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
- B01D71/02—Inorganic material
- B01D71/024—Oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/48—Antimicrobial properties
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- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
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Abstract
The invention relates to an anti-pollution composite nanofiltration membrane and a preparation method thereof. The preparation method comprises the steps of preparing nano zinc oxide by a sol-gel method, dissolving the nano zinc oxide in absolute ethyl alcohol to prepare mother liquor, mixing the mother liquor, a solvent and a pore-forming agent to prepare a membrane casting solution, coating the membrane casting solution on a base membrane to obtain a nano zinc oxide ultrafiltration base membrane, then respectively soaking the ultrafiltration base membrane in solutions of piperazine and trimesoyl chloride, and obtaining the anti-pollution composite nanofiltration membrane with a compact cross-linked desalting layer through interfacial polymerization. In the preparation process, the nano zinc oxide with the sterilization and deodorization bacteria performance is mixed, so that the pollution resistance of the nano-filtration membrane is improved, the service life of the nano-filtration membrane is prolonged, the service time of the nano-filtration membrane is prolonged, and the economic benefit is increased.
Description
Technical Field
The invention belongs to the field of nanofiltration membrane preparation, and particularly relates to an anti-pollution composite nanofiltration membrane and a preparation method thereof.
Background
The nanofiltration technology is a membrane separation technology developed in the 80 s of the 20 th century, and is widely applied to the aspects of seawater desalination, brackish water desalination, industrial wastewater treatment, drinking water treatment, biopharmaceutical pure water preparation and the like after 30 years of development. However, the nanofiltration membrane has the difficult problem of membrane pollution in the using process, which causes the reduction of membrane flux, the increase of energy consumption, the shortening of service life and the increase of nanofiltration cost, and limits the application and popularization of the nanofiltration membrane.
With the development of the technology, the nano material gradually enters the visual field of researchers, and compared with the traditional material, the nano material has the properties of high specific surface area, high reaction activity, small-size effect, surface effect, macroscopic quantum tunnel effect and the like, and has excellent performances of photocatalysis, deodorization, antibiosis, formaldehyde removal, photoluminescence, electric conduction, energy conservation, wavelength absorption and the like, so that the nano material can be used for research and development of antibiosis, photocatalysis, infrared sensors, ultraviolet shielding, environment-friendly materials, information storage, stealthy substances and the like.
The nano zinc oxide as an antibacterial agent can show remarkable antibacterial activity to a plurality of bacteria. The antibacterial agent mainly acts on the surface of bacteria through surface contact or dissolution of zinc ions or enters cells to interact with bacterial nuclei, so that the bacteria are killed, and an antibacterial effect is achieved.
Therefore, how to combine the nano zinc oxide with the nanofiltration membrane becomes a new research direction, and the technical scheme of the invention is provided based on the research direction.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides an anti-pollution composite nanofiltration membrane and a preparation method thereof. The preparation method comprises the steps of mixing nano zinc oxide into a membrane casting solution, performing membrane forming phase conversion to obtain a nano zinc oxide ultrafiltration base membrane, immersing the ultrafiltration base membrane in a piperazine aqueous solution and an organic solution of trimesoyl chloride respectively, performing interfacial polymerization to obtain a compact cross-linked desalting layer, and performing heat treatment to obtain the nano zinc oxide ultrafiltration base membrane. In the preparation of the ultrafiltration base membrane, the nano zinc oxide with the sterilization and deodorization bacteria performance is mixed, so that the pollution resistance of the nanofiltration membrane is improved, the service life of the nanofiltration membrane is prolonged, the service time of the nanofiltration membrane is prolonged, and the economic benefit is increased.
The invention provides a preparation method of an anti-pollution composite nanofiltration membrane, which comprises the following steps:
(1) mixing and dissolving zinc acetate and water, adding ammonium hydroxide, and stirring to obtain a gel mixture;
(2) washing the gel mixture with an ammonium nitrate solution, drying until the solvent is completely volatilized, and continuously calcining to obtain nano zinc oxide powder;
(3) mixing and stirring the nano zinc oxide powder and absolute ethyl alcohol to obtain mother liquor;
(4) mixing and stirring the mother solution, the pore-forming agent and the solvent to obtain a membrane casting solution;
(5) standing and defoaming the casting solution, coating, and preparing a nano zinc oxide basement membrane through sinking phase conversion; and sequentially soaking the composite nanofiltration membrane in a piperazine solution and a trimesoyl chloride organic solution, and finally performing heat treatment to obtain the anti-pollution nano zinc oxide composite nanofiltration membrane with a compact cross-linked desalting layer.
Preferably, in step (1), ammonium hydroxide is added and stirred to a pH of 8.5.
Preferably, in the step (2), the concentration of the ammonium nitrate solution is 0.1 mol/L; the drying temperature is 80-90 ℃; the calcining temperature is 380-400 ℃, and the calcining time is 4-5 h.
Preferably, in the step (3), the stirring time is 1-2 h; the mass concentration of the nano zinc oxide in the mother solution is 0.1-0.5 wt.%.
Preferably, in the step (4), the weight ratio of the mother liquor to the pore-forming agent to the solvent is 15-30: 5-15: 60-80; the pore-foaming agent is polyethylene glycol-400; the solvent is N, N-dimethylacetamide.
Preferably, in the step (4), the stirring temperature is 70-80 ℃, and the stirring time is 10-24 hours.
Preferably, in the step (5), the standing and defoaming are carried out for 10-48 h at room temperature; and after coating, standing for 10-20 min, putting the mixture into a water bath, and performing phase separation at the temperature of 30-35 ℃.
Preferably, in the step (5), the concentration of the piperazine solution is 0.05 to 5 wt.%, and the piperazine solution is soaked for 1 to 5 min; the organic solution is n-hexane solution, the concentration of trimesoyl chloride is 0.01-0.25 wt.%, and the organic solution is soaked in the trimesoyl chloride organic solution for 10-120 s.
Preferably, in the step (5), the heat treatment temperature is 40-45 ℃, and the heat treatment drying time is 15-20 min.
Based on the same technical concept, the invention further provides the anti-pollution composite nanofiltration membrane prepared by the preparation method.
The anti-pollution composite nanofiltration membrane sequentially comprises a crosslinked desalting layer, a nano tin oxide film layer, an ultrafiltration base membrane layer and a support base membrane layer from top to bottom.
The invention has the beneficial effects that:
the preparation method comprises the steps of mixing nano zinc oxide into a membrane casting solution, carrying out membrane forming phase conversion to obtain a nano zinc oxide ultrafiltration base membrane, respectively immersing the ultrafiltration base membrane into a piperazine aqueous solution and an organic solution of trimesoyl chloride, carrying out interfacial polymerization to obtain a compact cross-linked desalting layer, and carrying out heat treatment to obtain the nano zinc oxide ultrafiltration base membrane. In the preparation of the ultrafiltration base membrane, the nano zinc oxide with the sterilization and deodorization bacteria performance is mixed, so that the pollution resistance of the nanofiltration membrane is improved, the service life of the nanofiltration membrane is prolonged, the service time of the nanofiltration membrane is prolonged, and the economic benefit is increased.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a schematic view of the anti-pollution composite nanofiltration membrane of the invention.
FIG. 2 is a schematic view of a splitting structure of the anti-pollution composite nanofiltration membrane.
The reference numbers in the figures are:
1-crosslinking a desalting layer; 2-a nano tin oxide film layer; 3-ultrafiltration basal membrane layer; 4-supporting the base film layer.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
Example 1
The embodiment provides a preparation method of an anti-pollution composite nanofiltration membrane, which comprises the following steps:
(1) mixing and dissolving zinc acetate and water, adding ammonium hydroxide, stirring until the pH value of the system is 8.5, and reacting at room temperature to obtain a gel mixture;
(2) washing the gel mixture with 0.1mol/L ammonium nitrate solution, drying at 80 ℃ until the solvent is completely volatilized, and finally placing in a muffle furnace at 380 ℃ for continuous calcination for 5 hours to obtain nano zinc oxide powder;
(3) mixing and stirring the nano zinc oxide powder and absolute ethyl alcohol for 1h to obtain mother liquor with the mass concentration of nano zinc oxide of 0.1 wt.%;
(4) mixing and stirring the mother solution, polyethylene glycol-400 and N, N-dimethylacetamide according to a weight ratio of 15:5:60, wherein the stirring temperature is 70 ℃, and the stirring time is 10 hours, so as to obtain a casting solution;
(5) standing and defoaming the membrane casting solution for 10 hours at room temperature, coating the membrane casting solution on the surface of a basement membrane, standing for 10 minutes, then placing the basement membrane in a water bath, carrying out phase separation at 30 ℃, and preparing the nano zinc oxide basement membrane by sinking phase conversion;
(6) soaking the nano zinc oxide-based membrane in a piperazine solution with the concentration of 0.05 wt.% for 1min, taking out, drying in the shade, soaking the nano zinc oxide-based membrane in a trimesoyl chloride n-hexane organic solution with the concentration of 0.01 wt.% for 10s, taking out, drying in the shade, performing heat treatment in an oven at the heat treatment temperature of 40 ℃, and drying for 15min to obtain the anti-pollution nano zinc oxide composite nanofiltration membrane with the compact cross-linked desalting layer.
Example 2
The embodiment provides a preparation method of an anti-pollution composite nanofiltration membrane, which comprises the following steps:
(1) mixing and dissolving zinc acetate and water, adding ammonium hydroxide, stirring until the pH value of the system is 8.5, and reacting at room temperature to obtain a gel mixture;
(2) washing the gel mixture with 0.1mol/L ammonium nitrate solution, drying at 90 ℃ until the solvent is completely volatilized, and finally placing in a muffle furnace for continuous calcination at 400 ℃ for 4h to obtain nano zinc oxide powder;
(3) mixing and stirring the nano zinc oxide powder and absolute ethyl alcohol for 2 hours to obtain mother liquor with the mass concentration of nano zinc oxide of 0.5 wt.%;
(4) mixing and stirring the mother solution, polyethylene glycol-400 and N, N-dimethylacetamide according to a weight ratio of 30:15:80, wherein the stirring temperature is 80 ℃, and the stirring time is 24 hours, thus obtaining a casting solution;
(5) standing and defoaming the membrane casting solution for 48h at room temperature, coating the membrane casting solution on the surface of a basement membrane, standing for 20min, then placing the basement membrane in a water bath, carrying out phase separation at 35 ℃, and preparing the nano zinc oxide basement membrane by sinking phase conversion;
(6) soaking the nano zinc oxide-based membrane into a piperazine solution with the concentration of 5 wt.% for 5min, taking out and drying in the shade, soaking the nano zinc oxide-based membrane into a trimesoyl chloride n-hexane organic solution with the concentration of 0.25 wt.% for 120s, taking out and drying in the shade, performing heat treatment in an oven at the heat treatment temperature of 45 ℃, and drying for 20min to obtain the anti-pollution nano zinc oxide composite nanofiltration membrane with the compact cross-linked desalting layer.
Example 3
The embodiment provides a preparation method of an anti-pollution composite nanofiltration membrane, which comprises the following steps:
(1) mixing and dissolving zinc acetate and water, adding ammonium hydroxide, stirring until the pH value of the system is 8.5, and reacting at room temperature to obtain a gel mixture;
(2) washing the gel mixture with 0.1mol/L ammonium nitrate solution, drying at 85 ℃ until the solvent is completely volatilized, and finally placing in a muffle furnace at 390 ℃ for continuous calcination for 4.5h to obtain nano zinc oxide powder;
(3) mixing and stirring the nano zinc oxide powder and absolute ethyl alcohol for 1.5 hours to obtain mother liquor with the mass concentration of nano zinc oxide of 0.3 wt.%;
(4) mixing and stirring the mother solution, polyethylene glycol-400 and N, N-dimethylacetamide according to a weight ratio of 23:10:70, wherein the stirring temperature is 75 ℃, and the stirring time is 17 hours, thus obtaining a casting solution;
(5) standing and defoaming the membrane casting solution for 29h at room temperature, coating the membrane casting solution on the surface of a basement membrane, standing for 15min, then placing the basement membrane in a water bath, carrying out phase separation at 32 ℃, and preparing the nano zinc oxide basement membrane by sinking phase conversion;
(6) soaking the nano zinc oxide-based membrane into a piperazine solution with the concentration of 2.5 wt.% for 3min, taking out and drying in the shade, soaking the nano zinc oxide-based membrane into a trimesoyl chloride n-hexane organic solution with the concentration of 0.13 wt.% for 65s, taking out and drying in the shade, performing heat treatment in an oven at the heat treatment temperature of 42 ℃, and drying for 18min to obtain the anti-pollution nano zinc oxide composite nanofiltration membrane with the compact cross-linked desalting layer.
Example 4
The embodiment provides an anti-pollution composite nanofiltration membrane, which sequentially comprises a crosslinked desalting layer 1, a nano tin oxide film layer 2, an ultrafiltration base film layer 3 and a support base film layer 4 from top to bottom.
Comparative example
The comparative example provides a preparation method of a composite nanofiltration membrane, which comprises the following steps:
(1) mixing solvent N, N-dimethylacetamide and pore-forming agent polyethylene glycol-400 according to a mass ratio of 75: 10, continuously stirring for 10 hours at the temperature of 80 ℃, standing and defoaming for 12 hours at room temperature to obtain a casting solution;
(2) coating the membrane casting solution on the surface of a base membrane, standing for 10min, placing the base membrane in a water bath, carrying out phase separation at 30 ℃, and preparing an ultrafiltration base membrane through sinking phase conversion;
(3) and soaking the ultrafiltration base membrane in a piperazine solution with the mass concentration of 0.2 wt% for 3min, taking out, drying in the shade, soaking the ultrafiltration base membrane in an organic solution with the mass concentration of 0.15 wt% of trimesoyl chloride for 45s, taking out, drying in the shade, performing heat treatment in an oven at the heat treatment temperature of 45 ℃, drying for 15min, and soaking the ultrafiltration base membrane in deionized water to obtain the composite nanofiltration membrane with the compact cross-linked desalting layer.
In order to show the performance of the anti-pollution composite nanofiltration membrane, the following experiments are carried out to verify the performance of the anti-pollution composite nanofiltration membrane.
(I) inorganic salt magnesium chloride removal test
And (3) sampling the nanofiltration membranes prepared in the examples 1-3 and the comparative example, testing on a membrane detection table, and measuring the desalination rate, water flux and tensile strength of the membrane after the membrane runs for 30min under the test conditions of 4000ppm of magnesium chloride raw water solution, the operation pressure of 0.6Mpa, the temperature of 25 ℃ and the pH of 6.5-7.5. The results of the experiments are summarized in table 1.
TABLE 1 Water flux, salt rejection and tensile Strength of membranes
| Group of | Water flux (GFD) | Salt rejection (wt.%) | Tensile Strength (N/50mm) |
| Example 1 | 45.5 | 96.2 | 83 |
| Example 2 | 46.1 | 97.6 | 92 |
| Example 3 | 46.3 | 96.9 | 91 |
| Comparative example | 22.6 | 85.5 | 72 |
(II) anti-contamination test-bovine serum albumin test
The nanofiltration membranes prepared in examples 1-3 and comparative examples were sampled, immersed in bovine serum albumin culture medium, cultured at 37 ℃ for 24 hours, and then taken out, and tested in a membrane test bench, and then the desalination rate, water flux and tensile strength of the membrane after 30min operation were measured under the test conditions of 3000ppm sodium chloride in raw water, operating pressure 0.6Mpa, temperature 25 ℃, pH 6.5-7.5. The results of the experiments are summarized in table 2.
TABLE 2 Water flux, salt rejection and tensile Strength of the membranes
(III) Staphylococcus aureus test
The nanofiltration membranes prepared in examples 1 to 3 and comparative examples were sampled, and membranes were immersed in staphylococcus aureus broth (CFU 105/mL), cultured at 37 ℃ for 24 hours, tested in a membrane test bench, and tested for desalination rate, water flux and tensile strength after 30min at an operating pressure of 0.6Mpa, a temperature of 25 ℃ and a pH of 6.5 to 7.5 with 3000ppm sodium chloride in water. The results of the experiments are summarized in table 3.
TABLE 3 Water flux, salt rejection and tensile Strength of the membranes
Firstly, inorganic salt magnesium sulfate performance tests were performed on the nanofiltration membranes prepared in examples 1 to 3 and comparative examples, and the results are shown in table 1. As can be seen from Table 1, the nanofiltration membranes prepared in examples 1 to 3 have better salt rejection rate, water flux and tensile strength for magnesium sulfate than those of comparative example 1. Secondly, the anti-pollution performance of the nanofiltration membranes prepared in the examples 1 to 3 and the comparative examples is tested, the bovine serum albumin anti-pollution performance is tested in the table 2, the staphylococcus aureus is tested in the table 3, and the data of the examples 1 to 3 and the comparative examples in the tables 2 and 3 are observed, so that the anti-pollution sterilization effects of the examples 1 to 3 are better than those of the comparative examples.
In conclusion, the nano zinc oxide is used for preparing the composite nanofiltration membrane, so that the sterilization and pollution resistance effects of the nanofiltration membrane can be obviously improved, the service life of the nanofiltration membrane is prolonged, and the economic value of the nanofiltration membrane is improved.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (10)
1. The preparation method of the anti-pollution composite nanofiltration membrane is characterized by comprising the following steps:
(1) mixing and dissolving zinc acetate and water, adding ammonium hydroxide, and stirring to obtain a gel mixture;
(2) washing the gel mixture with an ammonium nitrate solution, drying until the solvent is completely volatilized, and continuously calcining to obtain nano zinc oxide powder;
(3) mixing and stirring the nano zinc oxide powder and absolute ethyl alcohol to obtain mother liquor;
(4) mixing and stirring the mother solution, the pore-forming agent and the solvent to obtain a membrane casting solution;
(5) standing and defoaming the casting solution, coating, and preparing a nano zinc oxide basement membrane through sinking phase conversion; and sequentially soaking the composite nanofiltration membrane in a piperazine solution and a trimesoyl chloride organic solution, and finally performing heat treatment to obtain the anti-pollution nano zinc oxide composite nanofiltration membrane with a compact cross-linked desalting layer.
2. The method for preparing an anti-pollution composite nanofiltration membrane according to claim 1, wherein in the step (1), ammonium hydroxide is added and stirred until the pH value is 8.5.
3. The method for preparing the anti-pollution composite nanofiltration membrane according to claim 1, wherein in the step (2), the concentration of the ammonium nitrate solution is 0.1 mol/L; the drying temperature is 80-90 ℃; the calcining temperature is 380-400 ℃, and the calcining time is 4-5 h.
4. The method for preparing the anti-pollution composite nanofiltration membrane according to claim 1, wherein in the step (3), the stirring time is 1-2 h; the mass concentration of the nano zinc oxide in the mother solution is 0.1-0.5 wt.%.
5. The method for preparing the anti-pollution composite nanofiltration membrane according to claim 1, wherein in the step (4), the weight ratio of the mother liquor to the pore-forming agent to the solvent is 15-30: 5-15: 60-80; the pore-foaming agent is polyethylene glycol-400; the solvent is N, N-dimethylacetamide.
6. The method for preparing the anti-pollution composite nanofiltration membrane according to claim 1, wherein in the step (4), the stirring temperature is 70-80 ℃, and the stirring time is 10-24 hours.
7. The method for preparing the anti-pollution composite nanofiltration membrane according to claim 1, wherein in the step (5), the standing defoaming is carried out for 10-48 hours at room temperature; and after coating, standing for 10-20 min, putting the mixture into a water bath, and performing phase separation at the temperature of 30-35 ℃.
8. The method for preparing the anti-pollution composite nanofiltration membrane according to claim 1, wherein in the step (5), the piperazine solution with the concentration of 0.05-5 wt.% is soaked in the piperazine solution for 1-5 min; the organic solution is n-hexane solution, the concentration of trimesoyl chloride is 0.01-0.25 wt.%, and the organic solution is soaked in the trimesoyl chloride organic solution for 10-120 s.
9. The method for preparing the anti-pollution composite nanofiltration membrane according to claim 1, wherein in the step (5), the heat treatment temperature is 40-45 ℃, and the heat treatment drying time is 15-20 min.
10. An anti-pollution composite nanofiltration membrane obtained by the preparation method of any one of claims 1 to 9.
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| CN104667759A (en) * | 2013-11-29 | 2015-06-03 | 贵阳时代沃顿科技有限公司 | Preparation method of high-throughput anti-pollution composite nanofiltration membrane |
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| CN104667759A (en) * | 2013-11-29 | 2015-06-03 | 贵阳时代沃顿科技有限公司 | Preparation method of high-throughput anti-pollution composite nanofiltration membrane |
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