CN106669468B - Based on metal-doped g-C3N4Visible light catalytic flat-plate ultrafiltration membrane and preparation method - Google Patents

Based on metal-doped g-C3N4Visible light catalytic flat-plate ultrafiltration membrane and preparation method Download PDF

Info

Publication number
CN106669468B
CN106669468B CN201611181729.9A CN201611181729A CN106669468B CN 106669468 B CN106669468 B CN 106669468B CN 201611181729 A CN201611181729 A CN 201611181729A CN 106669468 B CN106669468 B CN 106669468B
Authority
CN
China
Prior art keywords
ultrafiltration membrane
visible light
doped
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.)
Active
Application number
CN201611181729.9A
Other languages
Chinese (zh)
Other versions
CN106669468A (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 one kind to be based on metal-doped g-C3N4Visible light catalytic flat-plate ultrafiltration membrane and preparation method, belong to technical field of membrane separation.By the polysulfones of 8.0%~20.0% (w/w) or polyether sulfone, the pore-foaming agent of 5.0%~15.0% (w/w), the surfactant of 0.05%~2.0% (w/w), 0.05%~5.0% (w/w) metal-doped g-C3N4It is added in three neck round bottom flask in a certain order with the solvent of 58.0%~86.9% (w/w), standing and defoaming 8~24 hours, casting solution is made to being completely dissolved within stirring and dissolving 5~16 hours at a temperature of 30~80 DEG C；Using phase inversion on clean glass plate knifing, prepare visible light catalytic flat-plate ultrafiltration membrane.Pure water flux >=450L/m of ultrafiltration membrane prepared by the present invention2Hr0.1MPa, bovine serum albumin rejection >=90.00% have good antifouling property and visible light catalytic performance to the degradation removal rate of fulvic acid up to 65% or so (under simulated visible light, running 1 hour).Product of the present invention is especially suitable for Micro-polluted Water, seawater desalinization pretreatment and biology, chemical industry, the processing of field of medicaments waste water and reuse etc..

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 ultrafiltration membranes and preparation method thereof, are based on metal more particularly to one kind Adulterate g-C3N4Visible light catalytic flat-plate ultrafiltration membrane and preparation method.
Background technique
The scarcity of water resource and the water pollution got worse have become the bottleneck for restricting social progress and economic development, new water Source exploitation and effluent sewage resource utilization also become global question of common concern.Since seawater resources are extremely abundant on the earth, And a large amount of effluent sewage is generated, sewage recycling and sea water desalination have become the strategic choice for solving water resources crisis.Many Sewage recycling technology in, membrane separation technique is best one of selection.
Mixed substrate membrane containing nano-grade molecular sieve, also known as hybridized film are by the chemical crosslinking of organic and inorganic constituents or the microcosmic film being mixed to form, again Claim " hybrid organic-inorganic film ", because the high separability and the toughness that have both the corrosion-resistant of inoranic membrane, heat resistance and organic film etc. is excellent Point becomes and studies membrane material modified one of hot spot.In recent years, domestic and foreign scholars are prepared using blending method or sol-gal process To nano inorganic material/polymer hybrid ultrafiltration membrane of ultraviolet light response, it is allowed to more function simultaneously with photocatalysis and UF membrane Energy property has exploitation and application prospect well；As Chinese patent ZL201410312781.8 uses nano inorganic material and film The ultrafiltration membrane being prepared for ultraviolet light response is blended in material, is allowed to the drop for having to organic pollutant in the case where ultraviolet catalytic acts on Solve performance；The solar energy less than 5% is only accounted in view of the luminous energy of ultraviolet light, the reality for seriously limiting titania modified film is answered With.Therefore, visible light catalytic ultrafiltration membrane is prepared by adulterating or coating visible light catalyst, in the resistance tocrocking for improving ultrafiltration membrane While, and make ultrafiltration membrane that there is visible light catalysis activity, the application range of ultrafiltration membrane is expanded, is that ultrafiltration membrane is studied in recent years Hot spot.
Chinese patent CN104383821A uses the magnetic particle@TiO of graphene oxide-loaded core-shell structure2Preparation is 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 prepared separating property of film and the superiority and inferiority of visible light photocatalytic degradation performance are not illustrated in patent application, and institute It is complicated to state seperation film preparation process；Meanwhile the magnetic particle@TiO of graphene oxide-loaded core-shell structure2Preparation method complexity, It is at high cost.Chinese patent CN104117291A is prepared for polyvinylidene fluoride film using the modification of TiO2/C hybrid aerogel, prepared Film in the lower modification PVDF film of xenon lamp (visible light) irradiation be only 13.96% to the degradation rate of reactive brilliant red x-3b, and in mercury It is then 93.28% to reactive brilliant red x-3b degradation rate under lamp (ultraviolet light) irradiation, provable prepared film is still to ultraviolet The ultrafiltration membrane of photoresponse, rather than visible light catalytic ultrafiltration membrane.Chinese patent CN102989329A is by by AgNO3、TiO2It is blended Modification prepares ultrafiltration membrane, is in fact that AgNO is mainly utilized3Visible light catalysis activity, and degradation rate is relatively slow (in patent Carry out Characterization of Its Photocatalytic Activity using the degradation rate of illumination 10 hours to methylene blue), can not prepare simultaneously for separate with The seperation film of visible light catalytic；Chinese patent CN104383820A is then by Ag3PO4/TiO2Compound (Ag3PO4Nanoparticle deposition To TiO2Surface) and polyvinylidene fluoride material blending and modifying, so that Modified Membrane is had visible light catalytic antibacterial anti-pollution, main benefit With being deposited on TiO2The Ag on surface3PO4The organic matter adsorbed in pellet degradation seperation film application process does not have to reduce fouling membrane It is used to prepare while having the seperation film of separation and visible light catalytic performance；Meanwhile the two patents are imitated not over collaboration It should be to make full use of silver salt and TiO2Catalytic performance, only by be blended or deposition and silver salt or silver salt and TiO is utilized2Respectively From catalytic activity, it is seen that photocatalysis efficiency is lower.Chinese patent CN102895888A then first prepares titanium dioxide/polyvinylidene fluoride Then alkene film prepares visible light-responded property polyvinylidene fluoride film, the methylene of prepared film in its adsorption, reduction silver ion Base indigo plant degradation rate is 33%~51%(radiation of visible light 100mins)；Meanwhile the present invention needs complete titanium dioxide/gather inclined fluorine After ethylene film preparation, then by absorption silver ion, reduction silver ion be silver-colored simple substance, vacuum drying and etc. could complete patent and produce The preparation of product, and the conditions such as darkroom, ultraviolet irradiation, vacuum drying are needed in preparation process, complex process, preparation cost are high, produce Industry difficulty is larger.
Graphite phase carbon nitride (g-C3N4) is a kind of polymer semiconductor with layer structure, can substantially be absorbed visible Light has good visible light catalytic performance, and chemical stability is high, is competent at acid or alkali environment, is the novel of most application prospect One of catalyst.However single g-C3N4 itself can only absorb least a portion of visible light, it is very poor to the absorption of ultraviolet light, thus The photocatalytic activity of individual g-C3N4 is not high, and which has limited its practices.Since doping metals can restrained effectively Photogenerated charge it is compound, therefore, metallic element and the synergistic effect of g-C3N4 are given full play to by doping metals, can be significantly The visible light catalysis activity of g-C3N4 after improving doping vario-property；Progress is blended with high molecular material in metal-doped g-C3N4 can The development of light-exposed catalytic mixing matrix ultrafiltration membrane to the application field for improving UF membrane efficiency, widening seperation film, mitigates fouling membrane With certain meaning.
The present invention passes through in g-C3N4Middle doped metal salt gives full play to metal salt and g-C3N4Synergistic effect, into one Step improves g-C3N4Visible light catalysis activity, and use metal-doped g-C3N4Improve the visible light catalytic of polymer ultrafiltration membrane Characteristic prepares the flat mixed-matrix ultrafiltration membrane with visible light catalysis activity, both at home and abroad there is not yet pertinent literature is reported.
Summary of the invention
The object of the present invention is to provide one kind to be based on metal-doped g-C3N4Visible light catalytic flat-plate ultrafiltration membrane, this hair Another bright purpose is to provide the preparation method of the visible light catalytic flat-plate ultrafiltration membrane.
To achieve the above object, the technical scheme adopted by the invention is as follows:
One kind being based on metal-doped g-C3N4Visible light catalytic flat-plate ultrafiltration membrane, be by the object of following mass percent Matter composition: polymeric film material 8.0%~20.0% (w/w), pore-foaming agent 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)；
The polymeric film material is one kind of polysulfones, polyether sulfone, and content is 8.0%~20.0% (w/w)；
The pore-foaming agent is one kind of polyethylene glycol, polyvinylpyrrolidone, and content is 5.0%~15.0% (w/w)；
The surfactant is nonionic surfactant, such as polysorbate (tween), fatty glyceride, fat The smooth equal one kind of sour sorb, content are 0.05%~2.0% (w/w)；
The metal-doped g-C3N4G-C is adulterated for chromium3N4, Fe2O3 doping g-C3N4, Copper-cladding Aluminum Bar g-C3N4, vanadium doping g- C3N4, Ag doping g-C3N4, cadmium adulterate g-C3N4, zinc doping g-C3N4, witch culture g-C3N4, titanium doped g-C3N4With tin dope g- C3N4One kind of equal visible light catalysts, content are 0.05%~5.0% (w/w)；
The solvent is DMAC N,N' dimethyl acetamide (DMAc), N,N-dimethylformamide (DMF), N- crassitude One or two kinds of mixing of ketone (NMP), content are 58.0%~86.9% (w/w).
One kind being based on metal-doped g-C3N4Visible light catalytic flat-plate ultrafiltration membrane preparation method, comprising the following steps:
(1) by a certain amount of solvent, pore-foaming agent, surfactant, metal-doped g-C3N4According to a certain percentage, sequence It is added separately in three neck round bottom flask, stirs evenly；
(2) a certain amount of polymeric film material is added in three neck round bottom flask, is stirred at a temperature of 30~80 DEG C molten Initial casting solution is configured to being completely dissolved within solution 5~16 hours；Then, obtained casting solution is quiet at a temperature of stirring and dissolving Only placing 8~24 hours makes its complete deaeration；
(3) casting solution after deaeration is poured on clean glass plate, is formed a film using special plate membrane scraper striking, 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, it is automatic after film forming It is detached from glass plate, through ion water washing 24 hours, 50% glycerol immersion treatment 48 hours after taking the film out, can be prepared by based on gold Belong to doping g-C3N4Visible light catalytic flat-plate ultrafiltration membrane.
The coagulating bath is deionized water.
The present invention provides one kind to be based on metal-doped g-C3N4Visible light catalytic flat-plate ultrafiltration membrane and preparation method, By metal-doped g-C3N4Visible light catalytic material, which is introduced into polymer, prepares mixed-matrix ultrafiltration membrane, and assigns mixed-matrix The performance of ultrafiltration membrane good resistance tocrocking and visible light photocatalytic degradation of organic pollutants, this is innovation of the invention.For The resistance tocrocking and visible light catalytic performance of prepared visible light catalytic mixed-matrix ultrafiltration membrane are examined, the present invention is to made The resistance enhancement coefficient and contact angle of standby ultrafiltration membrane are tested, the results showed that resistance enhancement coefficient and contact angle all obviously drop Low, the resistance tocrocking of ultrafiltration membrane is greatly improved.It, will be prepared visible meanwhile using fulvic acid as target contaminant Photocatalysis mixed-matrix ultrafiltration membrane carries out visible light photocatalytic degradation removal rate and the test of ultrafiltration membrane variations of flux, the results showed that, institute The ultrafiltration membrane of preparation shows good Photocatalytic Degradation Property and antifouling property when running under simulated visible light, film leads to Amount decaying is substantially reduced.
The present invention is compared with prior art, has following beneficial effect:
(1) metal-doped g-C provided by the present invention3N4Visible light catalytic flat-plate ultrafiltration membrane prepared by blending and modifying With traditional polysulfones, poly (ether-sulfone) ultrafiltration membrane and based on g-C3N4Flat-plate ultrafiltration membrane compare, resistance tocrocking and visible light catalytic are living Property has all obtained apparent improvement, can while carrying out UF membrane catalytic degradation of the realization to organic pollutant.
(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 simple process, and it is living that prepared ultrafiltration membrane visible light catalytic is assigned while film forming Property and resistance tocrocking, Yi Shixian industrialization.
Specific embodiment:
Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
Embodiment 1:
By the dimethyl acetamide of 71.0% (w/w), the polyethylene glycol 400 of 13.0% (w/w), 0.5% (w/w) Tween-80 With the Copper-cladding Aluminum Bar g-C of 2.5% (w/w)3N4It is added separately in three neck round bottom flask, stirs evenly in a certain order；Then The polysulfones of 13.0% (w/w) is added, stirring and dissolving 7 hours is to being completely dissolved at a temperature of 70 DEG C；Then, the casting solution that will be obtained It is static at a temperature of stirring and dissolving to place 16 hours, remove bubble remaining in casting solution.
Casting solution after deaeration is poured on clean glass plate, is formed a film using special plate membrane scraper striking, in sky After being stopped 15 seconds in gas, it is immersed in solidification forming in 25 DEG C of constant temperature coagulating baths, glass plate is automatically disengaged after film forming, takes the film out It can be prepared by within 48 hours by deionized water washing 24 hours, 50% glycerol immersion treatment based on Copper-cladding Aluminum Bar g-C3N4Visible light urge Change flat-plate ultrafiltration membrane.
The pure water flux of visible light catalytic flat-plate ultrafiltration membrane prepared by the present embodiment is 469.43L/m2·hr· 0.1MPa, bovine serum albumin rejection are 91.97%, and resistance enhancement coefficient is 1.35, and contact angle is 73.1 °；To the drop of fulvic acid Removal rate is solved by 37.85%(no light, is run 1 hour) it is increased under 64.69%(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 acetamide is by 71.0% (w/w) it is increased to 73.45% (w/w), remaining is the same as embodiment 1.It is then prepared based on Copper-cladding Aluminum Bar g-C3N4Visible light catalytic The pure water flux of flat-plate ultrafiltration membrane is 397.66 L/m2Hr0.1MPa, bovine serum albumin rejection are 92.51%, resistance Enhancement coefficient is 1.71, and contact angle is 85.2 °；To the degradation removal rate of fulvic acid by 27.58%(no light, run 1 hour) it mentions It under height to 38.35%(simulated visible light, runs 1 hour).
Embodiment 3:
By Copper-cladding Aluminum Bar g-C3N4Content is increased to 5.0% (w/w) by 2.5% (w/w), and the content of dimethyl acetamide is by 71.0% (w/w) it is reduced to 68.5% (w/w), remaining is the same as embodiment 1.It is then prepared based on Copper-cladding Aluminum Bar g-C3N4Visible light catalytic plate The pure water flux of formula ultrafiltration membrane is 498.15 L/m2Hr0.1MPa, bovine serum albumin rejection are 91.36%, and resistance increases Coefficient is 1.32, and contact angle is 72.7 °；To the degradation removal rate of fulvic acid by 38.36%(no light, run 1 hour) it is increased to It under 67.29%(simulated visible light, runs 1 hour).
Embodiment 4:
By metal-doped g-C3N4By Copper-cladding Aluminum Bar g-C3N4Replace with Fe2O3 doping g-C3N4, remaining is the same as embodiment 1.It is then made It is standby based on Fe2O3 doping g-C3N4Visible light catalytic flat-plate ultrafiltration membrane pure water flux be 453.78 L/m2·hr· 0.1MPa, bovine serum albumin rejection are 91.62%, and resistance enhancement coefficient is 1.42, and contact angle is 74.6 °；To the drop of fulvic acid Removal rate is solved by 37.16%(no light, is run 1 hour) it is increased under 64.13%(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 the same as embodiment 1.It is then made It is standby based on titanium doped g-C3N4Visible light catalytic flat-plate ultrafiltration membrane pure water flux be 475.29 L/m2·hr· 0.1MPa, bovine serum albumin rejection are 91.99%, and resistance enhancement coefficient is 1.33, and contact angle is 73.0 °；To the drop of fulvic acid Removal rate is solved by 38.21%(no light, is run 1 hour) it is increased under 66.25%(simulated visible light, run 1 hour).
Comparative example 1:
By the dimethyl acetamide of 73.5% (w/w), the polyethylene glycol of 13.0% (w/w), 0.5% (w/w) Tween-80 and The polysulfones of 13.0% (w/w) is added separately in three neck round bottom flask in a certain order, the stirring and dissolving 7 at a temperature of 70 DEG C Hour to being completely dissolved；Then, obtained casting solution is static at a temperature of stirring and dissolving to place 16 hours, remove casting solution The bubble of middle remaining.
Casting solution after deaeration is poured on clean glass plate, is formed a film using special plate membrane scraper striking, in sky After being stopped 15 seconds in gas, it is immersed in solidification forming in 25 DEG C of constant temperature coagulating baths, glass plate is automatically disengaged after film forming, takes the film out It can be prepared by flat polysulfone ultrafiltration membrane within 48 hours by deionized water washing 24 hours, 50% glycerol immersion treatment.
The pure water flux of flat polysulfone ultrafiltration 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 °；Degradation removal to fulvic acid Rate is run 1 hour by 23.87%(no light) it is increased under 24.09%(simulated visible light, run 1 hour).
Comparative example 2:
By the dimethyl acetamide of 71.0% (w/w), the polyethylene glycol 400 of 13.0% (w/w), 0.5% (w/w) Tween-80 With the g-C of 2.5% (w/w)3N4It is added separately in three neck round bottom flask, stirs evenly in a certain order；Then it is added 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, obtained casting solution is being stirred Static placement 16 hours under solution temperature are mixed, bubble remaining in casting solution is removed.
Casting solution after deaeration is poured on clean glass plate, is formed a film using special plate membrane scraper striking, in sky After being stopped 15 seconds in gas, it is immersed in solidification forming in 25 DEG C of constant temperature coagulating baths, glass plate is automatically disengaged after film forming, takes the film out It can be prepared by within 48 hours by deionized water washing 24 hours, 50% glycerol immersion treatment based on g-C3N4Flat-plate ultrafiltration membrane.
The pure water flux of flat-plate ultrafiltration membrane prepared by this comparative example is 419.39L/m2Hr0.1MPa, cow's serum Retention rate of proteins is 92.61%, and resistance enhancement coefficient is 1.57, and contact angle is 82.6 °；To the degradation removal rate of fulvic acid by 31.79%(no light is run 1 hour) it is increased under 34.36%(simulated visible light, run 1 hour).

Claims (4)

1. one kind is based on metal-doped g-C3N4Visible light catalytic flat-plate ultrafiltration membrane, which is characterized in that by casting solution film and At, casting solution by the material composition of following mass percent: polymeric film material 8.0% ~ 20.0%, pore-foaming agent 5.0% ~ 15.0%, Surfactant 0.05% ~ 2.0%, metal-doped g-C3N4 2.5% ~ 5.0%, remaining is solvent；
The metal-doped g-C3N4G-C is adulterated for chromium3N4, Fe2O3 doping g-C3N4, Copper-cladding Aluminum Bar g-C3N4, vanadium doping g-C3N4, silver Adulterate g-C3N4, cadmium adulterate g-C3N4, zinc doping g-C3N4, witch culture g-C3N4, titanium doped g-C3N4With tin dope g-C3N4In It is a kind of；
The polymeric film material is one kind of polysulfones, polyether sulfone；The pore-foaming agent is polyethylene glycol, polyvinylpyrrolidine One kind of ketone；The solvent be DMAC N,N' dimethyl acetamide, N,N-dimethylformamide, N-Methyl pyrrolidone one kind or Two kinds of mixing；The surfactant is nonionic surfactant, specially polysorbate, fatty glyceride, fat Sour sorb is one of smooth.
2. according to claim 1 be based on metal-doped g-C3N4Visible light catalytic flat-plate ultrafiltration membrane, feature exists In the ultrafiltration membrane is prepared using traditional phase inversion i.e. dry-wet process.
3. a kind of preparation method of visible light catalytic flat-plate ultrafiltration membrane of any of claims 1 or 2, it is characterised in that it is wrapped It includes:
Step (1) is by a certain amount of solvent, pore-foaming agent, surfactant and metal-doped g-C3N4According to a certain percentage, sequence point It is not added in three neck round bottom flask, stirs evenly；
Polysulfones or polyether sulfone are added in three neck round bottom flask by step (2), the stirring and dissolving 5 ~ 16 hours at a temperature of 30 ~ 80 DEG C To being completely dissolved, static placement deaeration 8 ~ 24 hours to get visible light catalytic flat-plate ultrafiltration membrane liquid；
Casting solution after deaeration is poured on clean glass plate by step (3), film is made using special plate membrane scraper, in sky After being stopped 5 ~ 60 seconds in gas, glass plate is gently put into solidification forming in 15 ~ 50 DEG C of constant temperature coagulating baths, is automatically disengaged after film forming Glass plate can be prepared by through deionized water washing, 50% glycerol immersion treatment based on metal-doped g-C after taking the film out3N4Can Light-exposed catalysis flat-plate ultrafiltration membrane.
4. according to claim 3 be based on metal-doped g-C3N4Visible light catalytic flat-plate ultrafiltration membrane preparation method, It is characterized in that, the 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 CN106669468A (en) 2017-05-17
CN106669468B true 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)

Families Citing this family (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
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
CN109594100B (en) * 2018-12-07 2021-04-02 东华大学 C3N4Cu/Sn loaded alloy material and preparation and application thereof
CN109569311B (en) * 2019-01-09 2020-06-16 清华大学 Surface self-cleaning carbon nitride Fenton-photocatalytic nanofiltration membrane and preparation method thereof
CN110538578B (en) * 2019-09-06 2021-01-29 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 (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB201213266D0 (en) * 2012-07-26 2012-09-05 Univ Gent Membranes, azeotropic & catalytic components

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
《g－C3N4/PVDF复合膜的制备及热解性能研究》;王慧雅等;《现代化工》;20130430;第77页第2栏-78页第1栏第1段 *

Also Published As

Publication number Publication date
CN106669468A (en) 2017-05-17

Similar Documents

Publication Publication Date Title
CN106669468B (en) Based on metal-doped g-C3N4Visible light catalytic flat-plate ultrafiltration membrane and preparation method
CN106807257A (en) Based on metal-doped g C3N4Visible light catalytic hollow fiber ultrafiltration membrane and preparation method
CN106540686B (en) Activated carbon supported manganese dioxide-titanium dioxide ozone catalyst and preparation method for advanced treating
CN106693730B (en) Based on nonmetallic more doping nTiO2Visible light catalytic hollow fiber ultrafiltration membrane and preparation method
CN106237869A (en) A kind of polyphenol coating modified hydrophobic hydrophilic method of type polymeric membrane
CN114042387B (en) Photocatalytic degradation dye wastewater separation multilayer composite membrane and preparation method and application thereof
CN106943897A (en) Based on dopen Nano Cu2O visible light catalytic flat-plate ultrafiltration membrane and preparation method
CN105214524A (en) Tunica fibrosa of adsorbable heavy-metal ion removal and photocatalysis degradation organic contaminant and preparation method thereof
CN106731879B (en) Based on metal-doped nTiO2Visible light catalytic hollow fiber ultrafiltration membrane and preparation method
CN109304088A (en) A kind of sea water desalination membrane of strong alkali-acid resistance and the preparation method and application thereof
CN102974236B (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
Gao et al. Superhydrophilic polyethersulfone (PES) membranes with high scale inhibition properties obtained through bionic mineralization and RTIPS
CN106975359A (en) Based on dopen Nano Cu2O visible light catalytic hollow fiber ultrafiltration membrane and preparation method
CN110975626B (en) Preparation method of photo-Fenton catalytic self-cleaning super-hydrophilic PVDF ultrafiltration membrane
CN108246129A (en) A kind of sewage disposal antipollution complex reverse osmosis membrane and preparation method thereof
CN104801203A (en) Separating membrane capable of decomposing surface organic pollutants, and preparation method thereof
CN106731875B (en) Based on nonmetallic more doping nTiO2Visible light catalytic flat-plate ultrafiltration membrane and preparation method
CN106799165A (en) Based on metal-doped nTiO2Visible light catalytic flat-plate ultrafiltration membrane and preparation method
CN113877426A (en) Super-hydrophobic polypropylene modified ultrafiltration membrane and preparation method and application thereof
CN107486025B (en) Preparation method of modified activated carbon fiber composite polyether sulfone ultrafiltration membrane, ultrafiltration membrane obtained by preparation method and application of ultrafiltration membrane
CN106731880A (en) Visible light catalytic hollow fiber ultrafiltration membrane and preparation method based on dopen Nano ZnO
CN110787654A (en) Method for preparing reverse osmosis membrane by using 1-methylimidazole as water phase additive
CN113274890B (en) Porous high-permeability polyethylene sewage treatment membrane and preparation method thereof

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