CN106669468A - Metal doped g-C3N4 based visible light catalysis flat plate type ultra-filtration membrane and preparation method - Google Patents

Metal doped g-C3N4 based visible light catalysis flat plate type ultra-filtration membrane and preparation method Download PDF

Info

Publication number
CN106669468A
CN106669468A CN201611181729.9A CN201611181729A CN106669468A CN 106669468 A CN106669468 A CN 106669468A CN 201611181729 A CN201611181729 A CN 201611181729A CN 106669468 A CN106669468 A CN 106669468A
Authority
CN
China
Prior art keywords
visible light
doped
membrane
metal
light catalytic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201611181729.9A
Other languages
Chinese (zh)
Other versions
CN106669468B (en
Inventor
王秀菊
王立国
王仲鹏
刘思全
何芳
许伟颖
侯凯
周凯丽
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of Jinan
Original Assignee
University of Jinan
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by University of Jinan filed Critical University of Jinan
Priority to CN201611181729.9A priority Critical patent/CN106669468B/en
Publication of CN106669468A publication Critical patent/CN106669468A/en
Application granted granted Critical
Publication of CN106669468B publication Critical patent/CN106669468B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/06—Flat membranes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/30—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
    • B01D2325/10—Catalysts being present on the surface of the membrane or in the pores
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/30—Chemical resistance
    • 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
    • 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
    • C02F2101/34—Organic compounds containing oxygen
    • 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
    • C02F2101/38—Organic compounds containing nitrogen
    • 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
    • C02F2101/40—Organic compounds containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/10—Photocatalysts
    • 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
    • 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
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

Abstract

The invention discloses a metal doped g-C3N4 based visible light catalysis flat plate type ultra-filtration membrane and a preparation method and belongs to the technical field of membrane separation. The method comprises the following steps: adding 8.0%-20.0% (w/w) of polysulfone or polyether sulfone, 5.0%-15.0% (w/w) of pore-foaming agent, 0.05%-2.0% (w/w) of surface active agent, 0.05%-5.0% (w/w) of metal doped g.C3N4 and 58.0%-86.9% (w/w) of solvent into a three-necked round-bottom flask in a certain sequence; stirring and dissolving for 5-16 hours at 30-80 DEG C till fully dissolving; standing by and de-foaming for 8-24 hours, thereby preparing a casting membrane solution; and adopting a phase inversion method for wiping the membrane on a clean glass plate, thereby preparing the visible light catalysis flat plate type ultra-filtration membrane. The visible light catalysis flat plate type ultra-filtration membrane prepared according to the method disclosed by the invention has the advantages that the pure water flux is more than or equal to 450L/m<2>.hr.0.1MPa; the reject rate of bovine serum albumin is more than or equal to 90.00%; the degrading removal rate of fulvic acid can reach about 65% (running for 1 hour under the simulated visible light); and the antifouling property and the visible light catalysis property are excellent. The metal doped g-C3N4 based visible light catalysis flat plate type ultra-filtration membrane is especially suitable for water treatment of micro-polluted water source, pretreatment of sea water desalination and treatment and recycling of wastewater in the fields of biology, chemical industry and medicines.

Description

Based on metal-doped g-C3N4Visible light catalytic flat-plate ultrafiltration membrane and preparation method
Technical field
The present invention relates to a kind of macromolecule mixed-matrix ultrafilter membrane and preparation method thereof, more particularly to a kind of to be based on metal Doping g-C3N4Visible light catalytic flat-plate ultrafiltration membrane and preparation method.
Background technology
The deficient and increasingly serious water pollution of water resource becomes the bottleneck of restriction social progress and economic development, new water Source is developed and effluent sewage recycling also becomes global question of common concern.Because seawater resources extremely enrich on the earth, And substantial amounts of effluent sewage is produced, sewage recycling and desalinization become the strategic choice for solving water resources crisis.Many Sewage recycling technology in, membrane separation technique is one of best selection.
Mixed substrate membrane containing nano-grade molecular sieve, is the film for being mixed to form the chemical crosslinking of organic and inorganic constituentss or microcosmic also known as hybridized film, and Claim " hybrid organic-inorganic film ", because the high separability and toughness etc. that have the corrosion-resistant of inoranic membrane, thermostability and organic membrane concurrently it is excellent Point, becomes one of membrane material modified focus of research.In recent years, Chinese scholars are prepared using blending method or sol-gal process Nano inorganic material/polymer hybrid ultrafilter membrane to ultraviolet light response, is allowed to many work(with photocatalysis and membrance separation Energy property, there is exploitation and application prospect well；If Chinese patent ZL201410312781.8 is using nano inorganic material and film Material blending is prepared for the ultrafilter membrane to ultraviolet light response, is allowed to the drop for having to organic pollution in the case where ultraviolet catalytic is acted on Solution performance；In view of the luminous energy of ultraviolet light only accounts for the solar energy less than 5%, the reality for seriously limiting titania modified film should With.Therefore, visible light catalytic ultrafilter membrane is prepared by adulterating or coating visible light catalyst, in the resistance tocrocking for improving ultrafilter membrane While, make ultrafilter membrane that there is visible light catalysis activity again, the range of application of ultrafilter membrane is expanded, it is ultrafilter membrane research in recent years Focus.
Chinese patent CN104383821A adopts the magnetic particle@TiO of graphene oxide-loaded nucleocapsid structure2Prepare modified Seperation film, it is believed that seperation film shows good Photocatalytic Degradation Property to target contaminant bovine serum albumin and anti-albumen is dirty Metachromia energy, but the separating property of prepared film and the quality of visible light photocatalytic degradation performance, and institute are not illustrated in patent application State seperation film complicated process of preparation；Meanwhile, the magnetic particle@TiO of graphene oxide-loaded nucleocapsid structure2Preparation method complexity, High cost.Chinese patent CN104117291A is prepared for polyvinylidene fluoride film using TiO2/C hybrid aerogels are modified, prepared Film in xenon lamp（Visible ray）The lower modified PVDF films of irradiation are only 13.96% to the degradation rate of reactive brilliant red x-3b, and in hydrargyrum Lamp（Ultraviolet light）To reactive brilliant red x-3b degradation rate it is then 93.28% under irradiation, provable prepared film is remained to ultraviolet The ultrafilter membrane of photoresponse, rather than visible light catalytic ultrafilter membrane.Chinese patent CN102989329A is by by AgNO3、TiO2Blending It is modified to prepare ultrafilter membrane, in fact it is mainly to make use of AgNO3Visible light catalysis activity, and degradation rate is slower（In patent Employing 10 hours degradation rates to methylene blue of illumination carries out Characterization of Its Photocatalytic Activity）, it is impossible to prepare be used for simultaneously separate and The seperation film of visible light catalytic；Chinese patent CN104383820A is then by Ag3PO4/TiO2Complex（Ag3PO4Nanoparticle deposition To TiO2Surface）With polyvinylidene fluoride material blending and modifying, Modified Membrane is set to possess visible light catalytic antibacterial antifouling property, main profit With being deposited on TiO2The Ag on surface3PO4The Organic substance adsorbed in pellet degradation seperation film application process, to reduce fouling membrane, does not have Have simultaneously the seperation film separated with visible light catalytic performance for preparing；Meanwhile, the two patents are not over collaboration effect Should be making full use of silver salt and TiO2Catalytic performance, only by blending or deposit and make use of silver salt or silver salt and TiO2Respectively From catalysis activity, it is seen that photocatalysis efficiency is relatively low.Chinese patent CN102895888A then first prepares titanium dioxide/polyvinylidene fluoride Alkene film, then in its surface adsorption, reduction silver ion preparing visible light-responded property polyvinylidene fluoride film, the methylene of prepared film Base indigo plant degradation rate is 33%~51%（Radiation of visible light 100mins）；Meanwhile, the present invention needs complete titanium dioxide/poly- inclined fluorine After ethylene film preparation, then patent product can be just completed for steps such as silver-colored simple substance, vacuum drying by adsorbing silver ion, reduction silver ion The preparation of product, and the conditions such as darkroom, ultra-vioket radiation, vacuum drying are needed in preparation process, complex process, preparation cost are high, produce Industry difficulty is larger.
Graphite phase carbon nitride（g-C3N4）It is a kind of polymer semiconductor with layer structure, can significantly absorbs visible Light, with good visible light catalytic performance, chemical stability is high, is competent at acid or alkali environment, is the new of most application prospect One of catalyst.But single g-C3N4 itself can only absorb least a portion of visible ray, the absorption to ultraviolet light is very poor, thus Individually the photocatalytic activity of g-C3N4 is not high, which has limited its practice.Because doping metals can restrained effectively Photogenerated charge it is compound, therefore, the synergism of metallic element and g-C3N4 is given full play to by doping metals, can be significantly Improve the visible light catalysis activity of the g-C3N4 after doping vario-property；Metal-doped g-C3N4 and macromolecular material blending are carried out can The development of photocatalysis mixed-matrix ultrafilter membrane is seen, to improving membrance separation efficiency, widening the application of seperation film, mitigate fouling membrane With certain meaning.
The present invention is by g-C3N4Middle doped metal salt is giving full play to slaine and g-C3N4Synergism, enter one Step improves g-C3N4Visible light catalysis activity, and using metal-doped g-C3N4Improve the visible light catalytic of polymer ultrafiltration membrane Characteristic, prepares the flat mixed-matrix ultrafilter membrane with visible light catalysis activity, both at home and abroad there is not yet pertinent literature report.
The content of the invention
It is an object of the invention to provide a kind of be based on metal-doped g-C3N4Visible light catalytic flat-plate ultrafiltration membrane, this Another bright purpose is to provide the preparation method of the visible light catalytic flat-plate ultrafiltration membrane.
For achieving the above object, the technical scheme taken of the present invention is：
One kind is based on metal-doped g-C3N4Visible light catalytic flat-plate ultrafiltration membrane, be by the material group of following mass percent Into：Polymeric film material 8.0%~20.0% (w/w), porogen 5.0%~15.0% (w/w), surfactant 0.05%~ 2.0% (w/w), metal-doped g-C3N4 0.05%~5.0% (w/w), solvent 58.0%~86.9% (w/w)；
Described polymeric film material is polysulfones, one kind of polyether sulfone, and content is 8.0%~20.0% (w/w)；
Described porogen is Polyethylene Glycol, one kind of polyvinylpyrrolidone, and content is 5.0%~15.0% (w/w)；
Described surfactant is nonionic surfactant, such as Polysorbate（Tween）, fatty glyceride, fatty acid mountain One kind of the smooth grade of pears, content is 0.05%~2.0% (w/w)；
Described metal-doped g-C3N4For chromium doping g-C3N4, Fe2O3 doping g-C3N4, Copper-cladding Aluminum Bar g-C3N4, vanadium doping g-C3N4, silver Doping g-C3N4, cadmium doping g-C3N4, zinc doping g-C3N4, witch culture g-C3N4, titanium doped g-C3N4With tin dope g-C3N4Etc. can See one kind of photocatalyst, content is 0.05%~5.0% (w/w)；
Described solvent is DMAC N,N' dimethyl acetamide（DMAc）, N,N-dimethylformamide（DMF）, N-Methyl pyrrolidone （NMP）One or two mixing, content be 58.0%~86.9% (w/w).
One kind is based on metal-doped g-C3N4Visible light catalytic flat-plate ultrafiltration membrane preparation method, comprise the following steps：
（1）By a certain amount of solvent, porogen, surfactant, metal-doped g-C3N4According to certain ratio, order respectively In being added to three neck round bottom flask, stir；
（2）A certain amount of polymeric film material is added in three neck round bottom flask, at a temperature of 30~80 DEG C stirring and dissolving 5~ To being completely dissolved, initial casting solution is configured within 16 hours；Then, the static placement at a temperature of stirring and dissolving by the casting solution for obtaining Make within 8~24 hours its complete deaeration；
（3）Casting solution after deaeration is poured on the glass plate of cleaning, using special Flat Membrane scraper striking film forming, in air After middle stop 5~60 seconds, glass plate is gently put into solidification forming in 15~50 DEG C of constant temperature coagulating baths, is automatically disengaged after film shaping Glass plate, Jing ions water washing 24 hours, 50% glycerol immersion treatment 48 hours after taking the film out, you can be obtained and mixed based on metal Miscellaneous g-C3N4Visible light catalytic flat-plate ultrafiltration membrane.
Described coagulating bath is deionized water.
The invention provides a kind of be based on metal-doped g-C3N4Visible light catalytic flat-plate ultrafiltration membrane and preparation method, By metal-doped g-C3N4Visible light catalytic material is incorporated in polymer and prepares mixed-matrix ultrafilter membrane, and gives mixed-matrix The performance of the good resistance tocrocking of ultrafilter membrane and visible light photocatalytic degradation of organic pollutants, this is the innovation of the present invention.For The resistance tocrocking and visible light catalytic performance of the prepared visible light catalytic mixed-matrix ultrafilter membrane of inspection, the present invention is to made The resistance enhancement coefficient and contact angle of standby ultrafilter membrane is tested, and as a result shows that resistance enhancement coefficient and contact angle all substantially drop Low, the resistance tocrocking of ultrafilter membrane is greatly improved.Meanwhile, with fulvic acid as target contaminant, will be prepared visible Photocatalysis mixed-matrix ultrafilter membrane carries out visible light photocatalytic degradation clearance and the test of ultrafilter membrane variations of flux, as a result shows, institute The ultrafilter membrane of preparation shows good Photocatalytic Degradation Property and antifouling property when running under simulated visible light, film it is logical Amount decay is substantially reduced.
The present invention is compared with prior art, with following beneficial effect：
（1）Metal-doped g-C provided by the present invention3N4Visible light catalytic flat-plate ultrafiltration membrane prepared by blending and modifying and biography System polysulfones, poly (ether-sulfone) ultrafiltration membrane and based on g-C3N4Flat-plate ultrafiltration membrane compare, its resistance tocrocking and visible light catalysis activity are all Obtained obvious improvement, can while membrance separation is carried out catalytic degradation of the realization to organic pollution.
（2）Metal-doped g-C provided by the present invention3N4Blending and modifying prepares the side of visible light catalytic flat-plate ultrafiltration membrane Method, equipment used is simple, easily-controllable, film preparation process is simple, prepared ultrafilter membrane visible light catalytic is given while film forming and is lived Property and resistance tocrocking, easily realize industrialization.
Specific embodiment：
With reference to embodiment, the present invention is described in further detail, but embodiments of the present invention not limited to this.
Embodiment 1：
By the dimethyl acetylamide of 71.0% (w/w), the PEG400 of 13.0% (w/w), the tween 80 of 0.5% (w/w) and The Copper-cladding Aluminum Bar g-C of 2.5% (w/w)3N4It is added separately in a certain order in three neck round bottom flask, stirs；Then plus Enter the polysulfones of 13.0% (w/w), stirring and dissolving 7 hours is to being completely dissolved at a temperature of 70 DEG C；Then, the casting solution for obtaining is existed The static bubble placed 16 hours, remove remaining in casting solution at a temperature of stirring and dissolving.
Casting solution after deaeration is poured on the glass plate of cleaning, using special Flat Membrane scraper striking film forming, in sky After stopping 15 seconds in gas, solidification forming in 25 DEG C of constant temperature coagulating baths is immersed in, after film shaping glass plate is automatically disengaged, taken the film out Can be prepared by within 48 hours based on Copper-cladding Aluminum Bar g-C by deionized water wash 24 hours, 50% glycerol immersion treatment3N4Visible ray urge Change flat-plate ultrafiltration membrane.
The pure water flux of the visible light catalytic flat-plate ultrafiltration membrane prepared by the present embodiment is 469.43L/m2·hr· 0.1MPa, bovine serum albumin rejection is 91.97%, and resistance enhancement coefficient is 1.35, and contact angle is 73.1 °；Drop to fulvic acid Solution clearance is by 37.85%（No light, runs 1 hour）Bring up to 64.69%（Under simulated visible light, run 1 hour）.
Embodiment 2：
By Copper-cladding Aluminum Bar g-C3N4Content is reduced to 0.05% (w/w) by 2.5% (w/w), and the content of dimethyl acetylamide is by 71.0% (w/ W) 73.45% (w/w) is brought up to, remaining is with embodiment 1.It is then prepared based on Copper-cladding Aluminum Bar g-C3N4Visible light catalytic flat board The pure water flux of formula ultrafilter membrane is 397.66 L/m2Hr0.1MPa, bovine serum albumin rejection is 92.51%, resistance increase Coefficient is 1.71, and contact angle is 85.2 °；To the degraded clearance of fulvic acid by 27.58%（No light, runs 1 hour）Bring up to 38.35%（Under simulated visible light, run 1 hour）.
Embodiment 3：
By Copper-cladding Aluminum Bar g-C3N4Content brings up to 5.0% (w/w) by 2.5% (w/w), and the content of dimethyl acetylamide is by 71.0% (w/ W) 68.5% (w/w) is reduced to, remaining is with embodiment 1.It is then prepared based on Copper-cladding Aluminum Bar g-C3N4Visible light catalytic it is flat The pure water flux of ultrafilter membrane is 498.15 L/m2Hr0.1MPa, bovine serum albumin rejection is 91.36%, resistance increase system Number is 1.32, and contact angle is 72.7 °；To the degraded clearance of fulvic acid by 38.36%（No light, runs 1 hour）Bring up to 67.29%（Under simulated visible light, run 1 hour）.
Embodiment 4：
By metal-doped g-C3N4By Copper-cladding Aluminum Bar g-C3N4Replace with Fe2O3 doping g-C3N4, remaining is with embodiment 1.It is then prepared Based on Fe2O3 doping g-C3N4Visible light catalytic flat-plate ultrafiltration membrane pure water flux be 453.78 L/m2Hr0.1MPa, cattle Serum albumin rejection is 91.62%, and resistance enhancement coefficient is 1.42, and contact angle is 74.6 °；Degraded clearance to fulvic acid By 37.16%（No light, runs 1 hour）Bring up to 64.13%（Under simulated visible light, run 1 hour）.
Embodiment 5：
By metal-doped g-C3N4By Copper-cladding Aluminum Bar g-C3N4Replace with titanium doped g-C3N4, remaining is with embodiment 1.It is then prepared Based on titanium doped g-C3N4Visible light catalytic flat-plate ultrafiltration membrane pure water flux be 475.29 L/m2Hr0.1MPa, cattle Serum albumin rejection is 91.99%, and resistance enhancement coefficient is 1.33, and contact angle is 73.0 °；Degraded clearance to fulvic acid By 38.21%（No light, runs 1 hour）Bring up to 66.25%（Under simulated visible light, run 1 hour）.
Comparative example 1：
By the dimethyl acetylamide of 73.5% (w/w), the Polyethylene Glycol of 13.0% (w/w), 0.5% (w/w) tween 80 and 13.0% (w/w) polysulfones is added separately in a certain order in three neck round bottom flask, and stirring and dissolving 7 hours is extremely at a temperature of 70 DEG C It is completely dissolved；Then, by the casting solution for obtaining at a temperature of stirring and dissolving it is static place 16 hours, removing casting solution in remaining Bubble.
Casting solution after deaeration is poured on the glass plate of cleaning, using special Flat Membrane scraper striking film forming, in sky After stopping 15 seconds in gas, solidification forming in 25 DEG C of constant temperature coagulating baths is immersed in, after film shaping glass plate is automatically disengaged, taken the film out Flat polysulphones hyperfiltration membrane is can be prepared by by deionized water wash 24 hours, 50% glycerol immersion treatment within 48 hours.
The pure water flux of the flat polysulphones hyperfiltration membrane prepared by this comparative example is 356.25 L/m2Hr0.1MPa, Bovine serum albumin rejection is 92.65%, and resistance enhancement coefficient is 1.82, and contact angle is 88.9 °；Degraded to fulvic acid is removed Rate is by 23.87%（No light, runs 1 hour）Bring up to 24.09%（Under simulated visible light, run 1 hour）.
Comparative example 2：
By the dimethyl acetylamide of 71.0% (w/w), the PEG400 of 13.0% (w/w), the tween 80 of 0.5% (w/w) and The g-C of 2.5% (w/w)3N4It is added separately in a certain order in three neck round bottom flask, stirs；It is subsequently adding 13.0% (w/w) polysulfones, stirring and dissolving 7 hours is to being completely dissolved at a temperature of 70 DEG C；Then, by the casting solution for obtaining in stirring and dissolving At a temperature of it is static place 16 hours, remove casting solution in remaining bubble.
Casting solution after deaeration is poured on the glass plate of cleaning, using special Flat Membrane scraper striking film forming, in sky After stopping 15 seconds in gas, solidification forming in 25 DEG C of constant temperature coagulating baths is immersed in, after film shaping glass plate is automatically disengaged, taken the film out Can be prepared by within 48 hours based on g-C by deionized water wash 24 hours, 50% glycerol immersion treatment3N4Flat-plate ultrafiltration membrane.
The pure water flux of the flat-plate ultrafiltration membrane prepared by this comparative example is 419.39L/m2Hr0.1MPa, Ox blood serum Retention rate of proteins is 92.61%, and resistance enhancement coefficient is 1.57, and contact angle is 82.6 °；To the degraded clearance of fulvic acid by 31.79%（No light, runs 1 hour）Bring up to 34.36%（Under simulated visible light, run 1 hour）.

Claims (6)

1. it is a kind of to be based on metal-doped g-C3N4Visible light catalytic flat-plate ultrafiltration membrane, it is characterised in that contain in its casting solution Metal-doped g-C3N4, and affect the structure and performance of ultrafilter membrane；Casting solution by following mass percent material composition：Polymerization Thing membrane material 8.0%~20.0% (w/w), porogen 5.0%~15.0% (w/w), surfactant 0.05%~2.0% (w/w), gold Category doping g-C3N4 0.05%~5.0% (w/w), remaining is solvent.
2. according to claim 1 based on metal-doped g-C3N4Visible light catalytic flat-plate ultrafiltration membrane, its feature exists In：Described ultrafilter membrane be using traditional phase inversion it is i.e. dry-it is prepared by wet method.
3. according to claim 1 based on metal-doped g-C3N4Visible light catalytic flat-plate ultrafiltration membrane, its feature exists In：Described metal-doped g-C3N4For chromium doping g-C3N4, Fe2O3 doping g-C3N4, Copper-cladding Aluminum Bar g-C3N4, vanadium doping g-C3N4, silver Doping g-C3N4, cadmium doping g-C3N4, zinc doping g-C3N4, witch culture g-C3N4, titanium doped g-C3N4With tin dope g-C3N4Etc. can See one kind of photocatalyst, content accounts for 0.05%~5.0% (w/w) of casting solution gross weight.
4. according to claim 1 based on metal-doped g-C3N4Visible light catalytic flat-plate ultrafiltration membrane, its feature exists In：Described polymeric film material is polysulfones, one kind of polyether sulfone；Described porogen is Polyethylene Glycol, polyvinylpyrrolidine One kind of ketone；Described surfactant is nonionic surfactant, such as Polysorbate（Tween）, fatty glyceride, fat One kind of the smooth grade of fat acid Pyrusussuriensiss；Described solvent is DMAC N,N' dimethyl acetamide（DMAc）, N,N-dimethylformamide（DMF）、 N-Methyl pyrrolidone（NMP）One or two mixing.
5. it is a kind of to be based on metal-doped g-C3N4Visible light catalytic flat-plate ultrafiltration membrane preparation method, it is characterised in that it wrap Include：
Step（1）By a certain amount of solvent, porogen, surfactant and metal-doped g-C3N4According to certain ratio, order In being added separately to three neck round bottom flask, stir；
Step（2）Polysulfones or polyether sulfone are added in three neck round bottom flask, stirring and dissolving 5~16 is little at a temperature of 30~80 DEG C Up to being completely dissolved, static placement deaeration 8~24 hours obtains visible light catalytic flat-plate ultrafiltration membrane casting solution；
Step（3）Casting solution after deaeration is poured on the glass plate of cleaning, using special Flat Membrane scraper striking film forming, After stopping 5~60 seconds in air, glass plate is gently put into solidification forming in 15~50 DEG C of constant temperature coagulating baths, after film shaping automatically Depart from glass plate, Jing deionized water wash, 50% glycerol immersion treatment can be prepared by based on metal-doped g-C after taking the film out3N4 Visible light catalytic flat-plate ultrafiltration membrane.
6. according to claim 5 based on metal-doped g-C3N4Visible light catalytic flat-plate ultrafiltration membrane preparation side Method, it is characterised in that：Described coagulating bath is deionized water.
CN201611181729.9A 2016-12-20 2016-12-20 Based on metal-doped g-C3N4Visible light catalytic flat-plate ultrafiltration membrane and preparation method Active CN106669468B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201611181729.9A CN106669468B (en) 2016-12-20 2016-12-20 Based on metal-doped g-C3N4Visible light catalytic flat-plate ultrafiltration membrane and preparation method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201611181729.9A CN106669468B (en) 2016-12-20 2016-12-20 Based on metal-doped g-C3N4Visible light catalytic flat-plate ultrafiltration membrane and preparation method

Publications (2)

Publication Number Publication Date
CN106669468A true CN106669468A (en) 2017-05-17
CN106669468B CN106669468B (en) 2019-10-25

Family

ID=58869733

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201611181729.9A Active CN106669468B (en) 2016-12-20 2016-12-20 Based on metal-doped g-C3N4Visible light catalytic flat-plate ultrafiltration membrane and preparation method

Country Status (1)

Country Link
CN (1) CN106669468B (en)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107715904A (en) * 2017-10-13 2018-02-23 华中农业大学 A kind of titanium dioxide/Zn g C3N4The preparation method of/graphene composite material and application
CN108816059A (en) * 2018-06-08 2018-11-16 太原理工大学 A kind of preparation method and application of the mixed substrate membrane containing nano-grade molecular sieve of doped graphite carbonitride
CN109248701A (en) * 2018-09-03 2019-01-22 福建工程学院 Modification wallpaper of photocatalytic degradation of indoor toluene gas and its preparation method and application
CN109569311A (en) * 2019-01-09 2019-04-05 清华大学 A kind of self-cleaning surface type nitridation carbons Fenton-photocatalysis nanofiltration membrane and preparation method thereof
CN109594100A (en) * 2018-12-07 2019-04-09 东华大学 A kind of C3N4Loaded Cu/Sn alloy material and its preparation and application
CN109775798A (en) * 2017-11-15 2019-05-21 天津淼宇科技发展有限公司 Water purification method integrating photocatalysis and membrane filtration
CN110538578A (en) * 2019-09-06 2019-12-06 苏州清溪环保科技有限公司 Sewage treatment membrane with high decontamination efficiency and preparation method thereof
CN110961132A (en) * 2019-11-14 2020-04-07 济南市环境研究院 C3N4Preparation method and application of modified organic membrane
CN112090296A (en) * 2020-08-31 2020-12-18 济南大学 Based on F-TiO2/Fe-g-C3N4Self-cleaning flat plate type PVDF ultrafiltration membrane and preparation method thereof
CN115193476A (en) * 2022-07-14 2022-10-18 中国科学院生态环境研究中心 Photoelectrocatalysis membrane and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014016405A1 (en) * 2012-07-26 2014-01-30 Technology For Renewable Energy Systems (Tfres) Bvba Membranes, azeotropic & catalytic components
CN104307552A (en) * 2014-11-06 2015-01-28 江苏理工学院 Method for preparing TiO2/g-C3N4 composite visible light catalyst
CN105582822A (en) * 2016-03-10 2016-05-18 台州学院 Preparation method of dopamine-modified polysulfone membrane

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014016405A1 (en) * 2012-07-26 2014-01-30 Technology For Renewable Energy Systems (Tfres) Bvba Membranes, azeotropic & catalytic components
CN104307552A (en) * 2014-11-06 2015-01-28 江苏理工学院 Method for preparing TiO2/g-C3N4 composite visible light catalyst
CN105582822A (en) * 2016-03-10 2016-05-18 台州学院 Preparation method of dopamine-modified polysulfone membrane

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
王慧雅等: "《g－C3N4/PVDF复合膜的制备及热解性能研究》", 《现代化工》 *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107715904A (en) * 2017-10-13 2018-02-23 华中农业大学 A kind of titanium dioxide/Zn g C3N4The preparation method of/graphene composite material and application
CN109775798A (en) * 2017-11-15 2019-05-21 天津淼宇科技发展有限公司 Water purification method integrating photocatalysis and membrane filtration
CN108816059A (en) * 2018-06-08 2018-11-16 太原理工大学 A kind of preparation method and application of the mixed substrate membrane containing nano-grade molecular sieve of doped graphite carbonitride
CN109248701A (en) * 2018-09-03 2019-01-22 福建工程学院 Modification wallpaper of photocatalytic degradation of indoor toluene gas and its preparation method and application
CN109594100A (en) * 2018-12-07 2019-04-09 东华大学 A kind of C3N4Loaded Cu/Sn alloy material and its preparation and application
CN109569311A (en) * 2019-01-09 2019-04-05 清华大学 A kind of self-cleaning surface type nitridation carbons Fenton-photocatalysis nanofiltration membrane and preparation method thereof
CN110538578A (en) * 2019-09-06 2019-12-06 苏州清溪环保科技有限公司 Sewage treatment membrane with high decontamination efficiency and preparation method thereof
CN110961132A (en) * 2019-11-14 2020-04-07 济南市环境研究院 C3N4Preparation method and application of modified organic membrane
WO2021093832A1 (en) * 2019-11-14 2021-05-20 济南市环境研究院 C3n4 modified organic film preparation method and application
CN112090296A (en) * 2020-08-31 2020-12-18 济南大学 Based on F-TiO2/Fe-g-C3N4Self-cleaning flat plate type PVDF ultrafiltration membrane and preparation method thereof
CN115193476A (en) * 2022-07-14 2022-10-18 中国科学院生态环境研究中心 Photoelectrocatalysis membrane and preparation method and application thereof

Also Published As

Publication number Publication date
CN106669468B (en) 2019-10-25

Similar Documents

Publication Publication Date Title
CN106669468A (en) Metal doped g-C3N4 based visible light catalysis flat plate type ultra-filtration membrane and preparation method
CN106807257A (en) Based on metal-doped g C3N4Visible light catalytic hollow fiber ultrafiltration membrane and preparation method
CN111871234B (en) Loose nanofiltration membrane and preparation method and application thereof
CN106237869A (en) A kind of polyphenol coating modified hydrophobic hydrophilic method of type polymeric membrane
CN107174984A (en) A kind of preparation method of low-pressure high-throughput antipollution hollow fiber nanofiltration membrane
CN106943897A (en) Based on dopen Nano Cu2O visible light catalytic flat-plate ultrafiltration membrane and preparation method
CN105327627B (en) A kind of block sulfonated polyether aromatic phosphine blending/polyamide of polysulfones is combined the preparation method of forward osmosis membrane
CN106693730B (en) Based on nonmetallic more doping nTiO2Visible light catalytic hollow fiber ultrafiltration membrane and preparation method
CN103861476A (en) Preparation method of polyvinylidene fluoride (PVDF) composite mesoporous membrane
CN104841296A (en) Nanosized silica sphere/polypiperazine-amide nano composite nanofiltration membrane and preparation method thereof
CN106731879B (en) Based on metal-doped nTiO2Visible light catalytic hollow fiber ultrafiltration membrane and preparation method
CN108246129A (en) A kind of sewage disposal antipollution complex reverse osmosis membrane and preparation method thereof
CN102974236A (en) Composite flat-sheet polysulfone membrane doped with active carbon and nanometer zinc oxide and preparation method thereof
CN106731876A (en) Visible light catalytic flat-plate ultrafiltration membrane and preparation method based on dopen Nano ZnO
CN112090296A (en) Based on F-TiO2/Fe-g-C3N4Self-cleaning flat plate type PVDF ultrafiltration membrane and preparation method thereof
CN110975649A (en) Modified polyvinylidene fluoride ultrafiltration membrane and preparation method thereof
CN106474939A (en) A kind of modified carbon nano-tube/graphene oxide shitosan is combined poly (ether-sulfone) ultrafiltration membrane and its preparation method and application
CN110787654B (en) Method for preparing reverse osmosis membrane by using 1-methylimidazole as water phase additive
CN106975359A (en) Based on dopen Nano Cu2O visible light catalytic hollow fiber ultrafiltration membrane and preparation method
CN106799165A (en) Based on metal-doped nTiO2Visible light catalytic flat-plate ultrafiltration membrane and preparation method
CN116212640A (en) Preparation method of quaternized and sulfonated polyethersulfone ultrafiltration membrane
CN114618313B (en) High-flux anti-pollution reverse osmosis composite membrane and preparation method thereof
CN105664739A (en) Preparation method of highly hydrophilic polysulfone ultrafiltration membrane
CN106731875B (en) Based on nonmetallic more doping nTiO2Visible light catalytic flat-plate ultrafiltration membrane and preparation method
CN106731880A (en) Visible light catalytic hollow fiber ultrafiltration membrane and preparation method based on dopen Nano ZnO

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant