CN110813109B - Photocatalytic ultrafiltration membrane and preparation method thereof - Google Patents
Photocatalytic ultrafiltration membrane and preparation method thereof Download PDFInfo
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- CN110813109B CN110813109B CN201911113180.3A CN201911113180A CN110813109B CN 110813109 B CN110813109 B CN 110813109B CN 201911113180 A CN201911113180 A CN 201911113180A CN 110813109 B CN110813109 B CN 110813109B
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- 239000012528 membrane Substances 0.000 title claims abstract description 143
- 238000000108 ultra-filtration Methods 0.000 title claims abstract description 70
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002105 nanoparticle Substances 0.000 claims abstract description 25
- 238000000967 suction filtration Methods 0.000 claims abstract description 19
- 239000006185 dispersion Substances 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 4
- 229920002492 poly(sulfone) Polymers 0.000 claims description 67
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 55
- 239000000243 solution Substances 0.000 claims description 32
- 238000005266 casting Methods 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 22
- 239000011148 porous material Substances 0.000 claims description 21
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 19
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 16
- 239000011521 glass Substances 0.000 claims description 15
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 230000001112 coagulating effect Effects 0.000 claims description 11
- 238000002791 soaking Methods 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 238000007790 scraping Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- 238000003892 spreading Methods 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 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
- 239000004698 Polyethylene Substances 0.000 claims 1
- 239000002202 Polyethylene glycol Substances 0.000 claims 1
- 238000007605 air drying Methods 0.000 claims 1
- 239000004088 foaming agent Substances 0.000 claims 1
- -1 polyethylene Polymers 0.000 claims 1
- 229920000573 polyethylene Polymers 0.000 claims 1
- 229920001223 polyethylene glycol Polymers 0.000 claims 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims 1
- 239000003361 porogen Substances 0.000 claims 1
- 238000007711 solidification Methods 0.000 abstract description 11
- 230000008023 solidification Effects 0.000 abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 229910021389 graphene Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000011941 photocatalyst Substances 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000010954 inorganic particle Substances 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 3
- 238000005345 coagulation Methods 0.000 description 3
- 230000015271 coagulation Effects 0.000 description 3
- 239000004021 humic acid Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000009295 crossflow filtration Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- 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
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B01J35/39—
-
- B01J35/50—
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- 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
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Catalysts (AREA)
Abstract
The invention provides a photocatalytic ultrafiltration membrane and a preparation method thereof, in particular to a photocatalytic ultrafiltration membrane prepared by adding TiO into a reactor2And (3) performing suction filtration and solidification on the semi-solidified ultrafiltration membrane by using the dispersion liquid of the nano particles and water as a solidification liquid, and fixing TiO on the solidified ultrafiltration membrane in comparison with the prior art2The mode has better binding force, and solves the problem of loss of photocatalytic particles in the traditional photocatalytic ultrafiltration membrane.
Description
Technical Field
The invention belongs to the field of photocatalysis, and particularly relates to a photocatalytic polysulfone ultrafiltration membrane capable of realizing photocatalytic degradation.
Background
With the remarkable improvement of the living standard of people, water pollution becomes a great environmental problem and is paid more and more attention by countries. At present, the traditional treatment methods such as physical adsorption method, chemical oxidation method, microbial treatment method and the like can only relieve water pollution to a certain extent, but have a good effect on organic matters which are very difficult to degrade and treat in polluted wastewater. The photocatalytic technology is one of the technologies which are developed more rapidly in recent years, and a photocatalyst such as titanium dioxide can decompose certain organic and inorganic substances efficiently under the irradiation of a specific light source, so that the harm degree of pollutants is greatly reduced. The coupling of the membrane separation and the photocatalyst technology is a brand-new hotspot of the photocatalytic technology, and solves a plurality of problems of catalyst recovery and the like in the photocatalytic technology.
For the existing photocatalytic ultrafiltration membrane, a photocatalyst is generally coated on the surface of the membrane or the photocatalyst and a membrane casting solution are blended to prepare the membrane, wherein the former has higher catalytic efficiency, but in the cross-flow filtration process of ultrafiltration, the catalyst on the surface of the membrane is easily washed and lost by wastewater to cause poorer membrane stability, and the latter solves the problem of catalyst loss through blending the membrane casting, but the common photocatalyst is inorganic particles, the compatibility of the inorganic particles and an organic ultrafiltration membrane is poorer, most of the blended inorganic particles are fixed in the membrane, and the mixed inorganic particles cannot be contacted with the wastewater in the membrane application process, so that the original purpose of photocatalysis is lost. In addition, researchers put commercial ultrafiltration membranes into the titanium dioxide precursor solution to realize in-situ synthesis of titanium dioxide at membrane pore channels, but because the ultrafiltration membranes are cured, the binding force of the titanium dioxide and the ultrafiltration membranes is poor, and the problem of catalyst loss still exists in the ultrafiltration process.
Disclosure of Invention
Aiming at the problems, the invention provides a novel photocatalytic ultrafiltration membrane and a preparation method thereof, and particularly, the invention provides a novel photocatalytic ultrafiltration membrane prepared by adding TiO2The nano particles and pure water are used as solidification liquid to dip the semi-solidified polysulfone ultrafiltration membrane, and the solidification liquid passes through membrane pores of the ultrafiltration membrane in a suction filtration mode, so that TiO is realized2And (4) fixing the nanoparticles on the surface of the membrane pores.
As the first invention point of the invention, the invention provides a photocatalytic ultrafiltration membrane, which comprises a polysulfone ultrafiltration membrane and TiO implanted on the surfaces of polysulfone ultrafiltration pore channels2Nanoparticles, the photocatalytic ultrafiltration membrane is prepared by placing a semi-solidified polysulfone membrane into a membrane containing TiO2The mixed coagulating bath of the nano particles and water is phase-converted.
Preferably, the semi-solidified ultrafiltration membrane is formed by solidifying the polysulfone membrane to be subjected to phase inversion through a primary coagulation bath.
Preferably, the coagulation bath is water.
Preferably, the surface of the photocatalytic ultrafiltration membrane is also implanted with TiO2And (3) nanoparticles.
Preferably, the pore diameter of the ultrafiltration membrane is 50-200nm, and the particle size of the TiO2 nano particles is 3-10 nm.
As a second aspect of the present invention, the present invention provides a method for preparing the photocatalytic ultrafiltration membrane, comprising the steps of:
(1) mixing a certain amount of polysulfone, a solvent and a pore-forming agent, stirring at 30-60 ℃ until the polysulfone, the solvent and the pore-forming agent are completely dissolved to form a mixed solution, and standing and defoaming for 12-24 hours to obtain a membrane casting solution;
(2) mixing nanometer TiO2Mixing with pure water to form 200-600mg/L dispersion, and performing ultrasonic treatment at 60-80 deg.C for 20-60min to uniformly disperse to form nanometer TiO2Solidifying liquid;
(3) pouring the membrane casting solution on a smooth glass plate, and scraping the membrane casting solution into a polysulfone membrane with a certain thickness by using a scraper;
(4) curing the polysulfone membrane formed in the step (2) in a pure water coagulating bath at 60 ℃ for 5-10min, taking the polysulfone membrane off a glass plate, spreading the polysulfone membrane in a suction filtration device, and pouring the polysulfone membrane into the nano TiO prepared in the step (2)2Filtering the solidified liquid to obtain nano TiO2The solidified liquid passes through an ultrafiltration membrane pore passage and is subjected to suction filtration treatment for 10-20min to form a photocatalytic ultrafiltration membrane;
(5) and (4) soaking the polysulfone ultrafiltration membrane formed in the step (4) in deionized water at normal temperature for 12-48h, and airing at room temperature.
Preferably, the solvent is one or more of N, N-dimethylacetamide, N-dimethylformamide and N-methylpyrrolidone.
Preferably, the pore-forming agent is lithium chloride.
Preferably, the polysulfone content in the membrane casting solution is 8-15wt.%, the pore-forming agent content is 4-12 wt.%, and the balance is solvent.
Preferably, said TiO is2The nanoparticles may be selected from pure TiO2Nanoparticles or functionalized TiO2Nanoparticles when selected from pure TiO2In the case of nanoparticles, nano TiO2Adjusting the pH range of the coagulating liquid to 3-5 by hydrochloric acid.
Preferably, graphene oxide and TiO are added into the casting solution2The nano-particles are amino-functionalized TiO2And the binding force of the nano particles is improved by crosslinking carboxyl and amino at the edge of the graphene oxide. When graphene oxide is added, the polysulfone content in the membrane casting solution is 10-18wt.%, the pore-forming agent content is 2-8 wt.%, and the carboxylated graphene oxide content is 2-5 wt.%. When graphene oxide is added, nano TiO2Adjusting the pH value of the coagulating liquid to 7.5-9 by sodium carbonate.
In addition, the invention also provides application of the photocatalytic ultrafiltration membrane in removing organic matters difficult to degrade in water.
The invention has the following effects:
1. the invention is prepared by mixing TiO2And (3) performing suction filtration and solidification on the semi-solidified ultrafiltration membrane by taking the dispersion liquid with water as a solidification liquid, and fixing TiO on the solidified ultrafiltration membrane in comparison with the prior art2The method has better bonding force.
2. According to the invention, the preparation parameters such as additive type/content, polysulfone content, pH of the solidification solution and the like are optimized, so that the aperture of the ultrafiltration membrane is ensured, and TiO with proper particle size is ensured2The nano particles can enter the inside of the pore canal of the ultrafiltration membrane, so that the nano particles are prevented from being only deposited on the surface of the membrane.
Detailed Description
Example 1
This example was prepared using the following procedure:
(1) mixing 10wt% of polysulfone, 78wt% of dimethyl sulfoxide and 12wt% of anhydrous lithium chloride, stirring at 30-60 ℃ until the materials are completely dissolved to form a mixed solution, and standing and defoaming for 24 hours to obtain a membrane casting solution;
(2) mixing nanometer TiO2(10 nm) mixing with pure water to form 300mg/L dispersion, adjusting the pH value to 4 by hydrochloric acid, and performing ultrasonic treatment at 60 ℃ for 60min until the dispersion is uniform to form nano TiO2 solidification liquid;
(3) pouring the membrane casting solution on a smooth glass plate, and scraping the membrane casting solution into a polysulfone membrane with the diameter of 200 mu m by using a scraper;
(4) curing the polysulfone membrane formed in the step (2) in a pure water coagulating bath at 60 ℃ for 5min, taking the polysulfone membrane off a glass plate, spreading the polysulfone membrane in a suction filtration device, and pouring the polysulfone membrane into the nano TiO prepared in the step (2)2Filtering the solidified liquid to obtain nano TiO2The solidified liquid passes through an ultrafiltration membrane pore passage (the suction filtration pressure is adjusted to be reduced continuously, and the mixed solidified liquid just passes through the pore passage is preferably adjusted), and a photocatalytic ultrafiltration membrane is formed after suction filtration treatment for 15 min;
(5) and (4) soaking the polysulfone ultrafiltration membrane formed in the step (4) in deionized water at normal temperature for 24 hours, and airing at room temperature.
Example 2
This example was prepared using the following procedure:
(1) mixing 15wt% of polysulfone, 73wt% of dimethyl sulfoxide and 12wt% of anhydrous lithium chloride, stirring at 30-60 ℃ until the materials are completely dissolved to form a mixed solution, and standing and defoaming for 24 hours to obtain a membrane casting solution;
(2) mixing nanometer TiO2(10 nm) mixing with pure water to form 300mg/L dispersion, adjusting pH to 4 with hydrochloric acid, and performing ultrasonic treatment at 60 deg.C for 60min to disperse uniformly to form nanometer TiO2Solidifying liquid;
(3) pouring the membrane casting solution on a smooth glass plate, and scraping the membrane casting solution into a polysulfone membrane with the diameter of 200 mu m by using a scraper;
(4) curing the polysulfone membrane formed in the step (2) in a pure water coagulating bath at 60 ℃ for 5min, taking the polysulfone membrane off a glass plate, spreading the polysulfone membrane in a suction filtration device, and pouring the polysulfone membrane into the nano TiO prepared in the step (2)2Filtering the solidified liquid to obtain nano TiO2The solidified liquid passes through an ultrafiltration membrane pore passage (the suction filtration pressure is adjusted to be reduced continuously, and the mixed solidified liquid just passes through the pore passage is preferably adjusted), and a photocatalytic ultrafiltration membrane is formed after suction filtration treatment for 15 min;
(5) and (4) soaking the polysulfone ultrafiltration membrane formed in the step (4) in deionized water at normal temperature for 24 hours, and airing at room temperature.
Example 3
This example was prepared using the following procedure:
(1) mixing 10wt% of polysulfone, 82wt% of dimethyl sulfoxide and 8wt% of anhydrous lithium chloride, stirring at 30-60 ℃ until the materials are completely dissolved to form a mixed solution, and standing and defoaming for 24 hours to obtain a membrane casting solution;
(2) mixing nanometer TiO2(10 nm) mixing with pure water to form 300mg/L dispersion, adjusting the pH value to 4 by hydrochloric acid, and performing ultrasonic treatment at 60 ℃ for 60min until the dispersion is uniform to form nano TiO2 solidification liquid;
(3) pouring the membrane casting solution on a smooth glass plate, and scraping the membrane casting solution into a polysulfone membrane with the diameter of 200 mu m by using a scraper;
(4) curing the polysulfone membrane formed in the step (2) in a pure water coagulating bath at 60 ℃ for 5min, taking the polysulfone membrane off a glass plate, spreading the polysulfone membrane in a suction filtration device, and pouring the polysulfone membrane into the nano TiO prepared in the step (2)2Filtering the solidified liquid to obtain nano TiO2The solidified liquid passes through an ultrafiltration membrane pore passage (the suction filtration pressure is adjusted to be reduced continuously, and the mixed solidified liquid just passes through the pore passage is preferably adjusted), and a photocatalytic ultrafiltration membrane is formed after suction filtration treatment for 15 min;
(5) and (4) soaking the polysulfone ultrafiltration membrane formed in the step (4) in deionized water at normal temperature for 24 hours, and airing at room temperature.
Example 4
This example was prepared using the following procedure:
(1) mixing 10wt% of polysulfone, 78wt% of dimethyl sulfoxide and 12wt% of anhydrous lithium chloride, stirring at 30-60 ℃ until the materials are completely dissolved to form a mixed solution, and standing and defoaming for 24 hours to obtain a membrane casting solution;
(2) mixing nanometer TiO2(10 nm) mixing with pure water to form 300mg/L dispersion, adjusting the pH value to 4 by hydrochloric acid, and performing ultrasonic treatment at 60 ℃ for 60min until the dispersion is uniform to form nano TiO2 solidification liquid;
(3) pouring the membrane casting solution on a smooth glass plate, and scraping the membrane casting solution into a polysulfone membrane with the diameter of 200 mu m by using a scraper;
(4) curing the polysulfone membrane formed in step (2) in a pure water coagulation bath at 60 ℃ for 5min, removing the polysulfone membrane from the glass plate, and continuously soaking the polysulfone membrane in the nano TiO prepared in step (2)2Treating the solidified liquid for 15min to form a photocatalytic ultrafiltration membrane;
(5) and (4) soaking the polysulfone ultrafiltration membrane formed in the step (4) in deionized water at normal temperature for 24 hours, and airing at room temperature.
Example 5
This example was prepared using the following procedure:
(1) mixing 10wt% of polysulfone, 78wt% of dimethyl sulfoxide and 12wt% of anhydrous lithium chloride, stirring at 30-60 ℃ until the materials are completely dissolved to form a mixed solution, and standing and defoaming for 24 hours to obtain a membrane casting solution;
(2) mixing nanometer TiO2(10 nm) mixing with pure water to form 300mg/L dispersion, adjusting the pH value to 4 by hydrochloric acid, and performing ultrasonic treatment at 60 ℃ for 60min until the dispersion is uniform to form nano TiO2 solidification liquid;
(3) pouring the membrane casting solution on a smooth glass plate, and scraping the membrane casting solution into a polysulfone membrane with the diameter of 200 mu m by using a scraper;
(4) impregnating the polysulfone membrane formed in the step (2) with the nano TiO prepared in the step (2)2Treating the solidified liquid for 20min to form a photocatalytic ultrafiltration membrane;
(5) and (4) soaking the polysulfone ultrafiltration membrane formed in the step (4) in deionized water at normal temperature for 24 hours, and airing at room temperature.
Example 6
This example was prepared using the following procedure:
(1) mixing 12wt% of polysulfone, 79wt% of dimethyl sulfoxide, 6wt% of anhydrous lithium chloride and 3wt% of graphene oxide, stirring at 30-60 ℃ until the materials are completely dissolved to form a mixed solution, and standing and defoaming for 24 hours to obtain a membrane casting solution;
(2) nano TiO aminated2(10 nm) mixing with pure water to form 300mg/L dispersion, adjusting pH to 8 with sodium carbonate, and performing ultrasonic treatment at 60 deg.C for 60min to disperse uniformly to form nanometer TiO2Solidifying liquid;
(3) pouring the membrane casting solution on a smooth glass plate, and scraping the membrane casting solution into a polysulfone membrane with the diameter of 200 mu m by using a scraper;
(4) curing the polysulfone membrane formed in the step (2) in a pure water coagulating bath at 60 ℃ for 5min, taking the polysulfone membrane off a glass plate, spreading the polysulfone membrane in a suction filtration device, and pouring the polysulfone membrane into the nano TiO prepared in the step (2)2Filtering the solidified liquid to obtain nano TiO2The solidified liquid passes through an ultrafiltration membrane pore passage (the suction filtration pressure is adjusted to be reduced continuously, and the mixed solidified liquid just passes through the pore passage is preferably adjusted), and a photocatalytic ultrafiltration membrane is formed after suction filtration treatment for 15 min;
(5) and (4) soaking the polysulfone ultrafiltration membrane formed in the step (4) in deionized water at normal temperature for 24 hours, and airing at room temperature.
Characterization test
Samples 2 (5 samples prepared in examples are respectively marked by S-1, S-2, S-3, S-4, S-5 and S-6) were prepared according to the steps of examples 1-6, one group is used for characterizing the pore diameter by a bubble point pressure method and SEM characterization of a sample, the other group is used for characterizing the photocatalytic performance, and the performance characterization is that the degradation rate of humic acid of a membrane sample after 1h of ultrafiltration work and 240h of ultrafiltration work is respectively measured by using 2000ppm of humic acid aqueous solution as a photocatalytic ultrafiltration membrane test feed liquid under the radiation of an ultraviolet lamp (the wavelength is 365nm and the power is 15 w) with the pressure of 30psi, and the results are shown in the following table:
table various examples characterization data for samples prepared ("+" indicates the number of nanoparticles per unit area, which were only involved in the longitudinal comparison and not in the transverse comparison)
| Sample (I) | Pore size/nm | Film surface nanoparticles | Nanoparticles of film section | Degradation rate after 1h | Degradation rate after 240h |
| S-1 | 79 | +++++ | +++ | 97.4% | 93.7% |
| S-2 | 34 | +++++ | ++ | 94.1% | 83.1% |
| S-3 | 42 | +++++ | ++ | 93.2% | 79.3% |
| S-4 | 80 | +++++ | + | 96.3% | 77.1% |
| S-5 | 83 | +++++ | + | 92.5% | 80.1% |
| S-1 | 102 | +++++ | ++++ | 98.1% | 97.4% |
As can be seen from the characterization data in Table 1, titanium oxide nanoparticles are embedded in both the surface and the pore channels of the ultrafiltration membrane prepared by the method, and the degradation rate of humic acid by the membrane is not greatly reduced along with the extension of ultrafiltration time, so that the requirement of long-time work of the photocatalytic ultrafiltration membrane can be met. While the photocatalytic ultrafiltration membranes prepared by the methods of examples 2-5 have degradation rates substantially consistent with those of the present invention in the initial stage of ultrafiltration, the degradation rates are obviously reduced with the extension of the working time of ultrafiltration,
the above description is only a preferred embodiment of the present invention, and any reprocessing based on the technical solution of the present invention is within the protection scope of the present invention.
Claims (5)
1. The preparation method of the photocatalytic ultrafiltration membrane is characterized in that the photocatalytic ultrafiltration membrane comprises a polysulfone ultrafiltration membrane and TiO implanted on the surface of a polysulfone ultrafiltration pore channel2Nanoparticles, the photocatalytic ultrafiltration membrane is prepared by placing a semi-solidified polysulfone membrane into a membrane containing TiO2Phase inversion is carried out in a mixed coagulating bath of the nano particles and water; the method comprises the following steps:
(1) mixing a certain amount of polysulfone, a solvent and a pore-forming agent, stirring at 30-60 ℃ until the polysulfone, the solvent and the pore-forming agent are completely dissolved to form a mixed solution, and standing and defoaming for 12-24 hours to obtain a membrane casting solution;
(2) mixing nanometer TiO2Mixing with pure water to form 200-600mg/L dispersion, and performing ultrasonic treatment at 60-80 deg.C for 20-60min to uniformly disperse to form nanometer TiO2Solidifying liquid;
(3) pouring the membrane casting solution on a smooth glass plate, and scraping the membrane casting solution into a polysulfone membrane with a certain thickness by using a scraper;
(4) curing the polysulfone membrane formed in the step (3) in a pure water coagulating bath at 60 ℃ for 5-10min, taking the polysulfone membrane off a glass plate, spreading the polysulfone membrane in a suction filtration device, and pouring the polysulfone membrane into the nano TiO prepared in the step (2)2Filtering the solidified liquid to obtain nano TiO2The solidified liquid passes through an ultrafiltration membrane pore passage and is subjected to suction filtration treatment for 10-20min to form a photocatalytic ultrafiltration membrane;
(5) soaking the polysulfone ultrafiltration membrane formed in the step (4) at normal temperatureSoaking in deionized water for 12-48h, and air drying at room temperature; the TiO is2The particle size of the nano particles is 3-10 nm; the TiO is2The nanoparticles are selected from pure TiO2Nanoparticles, nano TiO2Adjusting the pH range of the coagulating liquid to 3-5 by hydrochloric acid.
2. The method of claim 1, wherein the photocatalytic ultrafiltration membrane is also surface-implanted with TiO2And (3) nanoparticles.
3. The method of claim 1, wherein the ultrafiltration membrane has a pore size of 50 to 200 nm.
4. The method according to claim 1, wherein the solvent is one or more of N, N-dimethylacetamide, N-dimethylformamide, N-methylpyrrolidone, and dimethylsulfoxide; the pore-foaming agent is polyvinylpyrrolidone, polyethylene glycol, polyethylene and lithium chloride.
5. The method of claim 1, wherein the casting solution comprises 8-15wt.% polysulfone, 4-12 wt.% porogen, and the balance solvent.
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| CN106582331A (en) * | 2016-12-30 | 2017-04-26 | 河海大学 | Preparation method of photocatalytic ultrafilter membrane material with visible light activity |
| CN107469646A (en) * | 2017-08-01 | 2017-12-15 | 中国地质大学（武汉） | A kind of Ag3PO4/TiO2PVDF is modified composite membrane and preparation method thereof |
| CN109954411A (en) * | 2019-03-06 | 2019-07-02 | 河海大学 | A kind of load has TiO2/SiO2PES ultrafiltration membrane and its preparation method and application |
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| CN103240007A (en) * | 2013-05-13 | 2013-08-14 | 嵇天浩 | Method for preparing graphene-oxide-filled microfiltration composite material |
| CN106582331A (en) * | 2016-12-30 | 2017-04-26 | 河海大学 | Preparation method of photocatalytic ultrafilter membrane material with visible light activity |
| CN107469646A (en) * | 2017-08-01 | 2017-12-15 | 中国地质大学（武汉） | A kind of Ag3PO4/TiO2PVDF is modified composite membrane and preparation method thereof |
| CN109954411A (en) * | 2019-03-06 | 2019-07-02 | 河海大学 | A kind of load has TiO2/SiO2PES ultrafiltration membrane and its preparation method and application |
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