CN106799165A - Based on metal-doped nTiO2Visible light catalytic flat-plate ultrafiltration membrane and preparation method - Google Patents

Based on metal-doped nTiO2Visible light catalytic flat-plate ultrafiltration membrane and preparation method Download PDF

Info

Publication number
CN106799165A
CN106799165A CN201611181699.1A CN201611181699A CN106799165A CN 106799165 A CN106799165 A CN 106799165A CN 201611181699 A CN201611181699 A CN 201611181699A CN 106799165 A CN106799165 A CN 106799165A
Authority
CN
China
Prior art keywords
ntio
visible light
doped
metal
ultrafiltration membrane
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201611181699.1A
Other languages
Chinese (zh)
Inventor
王秀菊
王立国
王仲鹏
刘思全
何芳
许伟颖
周凯丽
侯凯
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 CN201611181699.1A priority Critical patent/CN106799165A/en
Publication of CN106799165A publication Critical patent/CN106799165A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/08—Flat membrane modules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • B01D67/0013—Casting processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • B01D67/0016—Coagulation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/0093—Chemical modification
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/06—Flat membranes
    • 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
    • B01D2311/00—Details relating to membrane separation process operations and control
    • B01D2311/26—Further operations combined with membrane separation processes
    • B01D2311/2696—Catalytic reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
    • B01D2321/34—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling by radiation
    • 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
    • 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

Abstract

Metal-doped nTiO is based on the invention discloses one kind2Visible light catalytic flat-plate ultrafiltration membrane and preparation method, belong to technical field of membrane separation.By the polysulfones or polyether sulfone of 8.0%~20.0% (w/w), 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 nTiO2Solvent with 58.0%~86.9% (w/w) is added in three neck round bottom flask in sequence, and to being completely dissolved, standing and defoaming 8~24 hours is made casting solution to stirring and dissolving within 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 >=the 430L/m of prepared milipore filter of the invention2Hr0.1MPa, bovine serum albumin rejection >=90.00%, the degraded clearance to fulvic acid reaches 60% or so（Under simulated visible light, run 1 hour）, with good antifouling property and visible light catalytic performance.Product of the present invention is particularly well-suited to Micro-polluted Water, seawater desalinization pretreatment and biology, chemical industry, the treatment of field of medicaments waste water and reuse etc..

Description

Based on metal-doped nTiO2Visible light catalytic flat-plate ultrafiltration membrane and preparation method
Technical field
It is more particularly to a kind of to be based on metal the present invention relates to a kind of macromolecule mixed-matrix milipore filter and preparation method thereof Doping nTiO2Visible light catalytic flat-plate ultrafiltration membrane and preparation method.
Background technology
The deficient and increasingly serious water pollution of water resource has turned into the bottleneck of restriction social progress and economic development, new water Source is developed and effluent sewage recycling also turns into 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 have turned into 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 to be chemically crosslinked or the microcosmic film being mixed to form organic and inorganic constituents 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, heat resistance and organic film concurrently are excellent Point, becomes one of membrane material modified focus of research.In recent years, domestic and foreign scholars are prepared using blending method or sol-gal process To the nano inorganic material/polymer hybrid milipore filter of ultraviolet light response, it is allowed to while having many work(of photocatalysis and UF membrane Energy property, there is exploitation and application prospect well；As Chinese patent ZL201410312781.8 uses nano inorganic material and film Material blending is prepared for the milipore filter 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.
Nano titanium oxide has the advantage such as photocatalytic activity high, stable chemical nature, nontoxic and inexpensive, is a kind of excellent Good photochemical catalyst, but it only can just show photocatalytic activity under ultraviolet light, it is impossible to carry out light using visible ray Catalytic degradation, and 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, how by nTiO2It is middle to adulterate other elements effectively to extend the electron-hole separation of titanium dioxide, and fill NTiO is waved in distribution2With the synergy of other elements, doping nTiO is further improved2Visible light catalysis activity, and by mixing Miscellaneous nTiO2Blending prepares visible light catalytic milipore filter, and while the resistance tocrocking of milipore filter is improved, again having milipore filter can See photocatalytic activity, expand the range of application of milipore filter, be the focus of milipore filter research in recent years.
Chinese patent CN104383821A uses the magnetic particle@TiO of graphene oxide-loaded core shell structure2Prepare modified Seperation film, it is believed that seperation film shows good Photocatalytic Degradation Property and the dirt of anti-albumen to target contaminant bovine serum albumin 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 preparation technology complicated；Meanwhile, the magnetic particle@TiO of graphene oxide-loaded core shell 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 mercury Lamp（Ultraviolet light）To reactive brilliant red x-3b degradation rate it is then 93.28% under irradiation, provable prepared film is still to ultraviolet The milipore filter of photoresponse, rather than visible light catalytic milipore filter.Chinese patent CN102989329A is by by AgNO3、TiO2Blending It is modified to prepare milipore filter, in fact it is that mainly 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 simultaneously be used for separate and The seperation film of visible light catalytic；Chinese patent CN104383820A is then by Ag3PO4/TiO2Compound（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 matter adsorbed in pellet degradation seperation film application process, to reduce fouling membrane, does not have There is the seperation film separated with visible light catalytic performance simultaneously for preparing；Meanwhile, the two patents are imitated not over collaboration Should be making full use of silver salt and TiO2Catalytic performance, only by blending or deposition 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 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/poly- inclined fluorine After ethene film preparation, then it is that the steps such as silver-colored simple substance, vacuum drying could complete patent product by adsorbing silver ion, reduction silver ion 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.
Because the electron-hole that dopant can effectively extend titanium dioxide is separated, therefore, can be substantially by doping metals Improve the visible light catalytic efficiency of titanium dioxide in ground.The present invention is by nTiO2Middle doped metal salt gives full play to slaine And nTiO2Synergy, further improve nTiO2Visible light catalysis activity, and use metal-doped nTiO2Improve high score The visible light catalytic characteristic of sub- milipore filter, prepares the flat mixed-matrix milipore filter with visible light catalysis activity, can be with bright The aobvious photocatalysis characteristic for improving polymer ultrafiltration membrane, both at home and abroad there is not yet pertinent literature is reported.
The content of the invention
Metal-doped nTiO is based on it is an object of the invention to provide one kind2Visible 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 taken of the present invention is：
One kind is based on metal-doped nTiO2Visible 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), pore-foaming agent 5.0%~15.0% (w/w), surfactant 0.05%~ 2.0% (w/w), metal-doped nTiO2 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 pore-foaming agent 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, aliphatic acid mountain One kind of the smooth grade of pears, content is 0.05%~2.0% (w/w)；
Described metal-doped nTiO2It is visible light catalyst cobalt doped nTiO2, bismuth doping nTiO2, chromium doping nTiO2, iron mixes Miscellaneous nTiO2, Copper-cladding Aluminum Bar nTiO2, aluminium doping nTiO2, molybdenum doping nTiO2, zinc-iron nTiO2, ferrotungsten doping nTiO2, ferro-cobalt doping nTiO2With indium vanadium Copper-cladding Aluminum Bar nTiO2One kind of powder, content is 0.05%~5.0% (w/w)；
Described solvent is DMAC N,N' dimethyl acetamide（DMAc）, N,N-dimethylformamide（DMF）, 1-METHYLPYRROLIDONE （NMP）One or two mixing, content be 58.0%~86.9% (w/w).
One kind is based on metal-doped nTiO2Visible light catalytic flat-plate ultrafiltration membrane preparation method, comprise the following steps：
（1）By a certain amount of solvent, pore-foaming agent, surfactant, metal-doped nTiO2According to certain ratio, order respectively It is added in three neck round bottom flask, stirs；
（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 casting solution that will be obtained static placement at a temperature of stirring and dissolving 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, through ion water washing 24 hours, 50% glycerine immersion treatment 48 hours after taking the film out, you can be obtained and mixed based on metal Miscellaneous nTiO2Visible light catalytic flat-plate ultrafiltration membrane.
Described coagulating bath is deionized water.
Metal-doped nTiO is based on the invention provides one kind2Visible light catalytic flat-plate ultrafiltration membrane and preparation method, By metal-doped nTiO2Visible light catalytic material prepares mixed-matrix milipore filter in being incorporated into polymer, and assigns mixed-matrix The performance of the good resistance tocrocking of milipore filter and visible light photocatalytic degradation of organic pollutants, this is innovation of the invention.For The resistance tocrocking and visible light catalytic performance of the prepared visible light catalytic mixed-matrix milipore filter of inspection, the present invention is to made The resistance enhancement coefficient and contact angle of standby milipore filter are tested, and as a result show that resistance enhancement coefficient and contact angle all substantially drop Low, the resistance tocrocking of milipore filter is greatly improved.Meanwhile, with fulvic acid as target contaminant, will be prepared visible Photocatalysis mixed-matrix milipore filter carries out visible light photocatalytic degradation clearance and the test of milipore filter variations of flux, as a result shows, institute The milipore filter of preparation shows good Photocatalytic Degradation Property and antifouling property when being run 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 nTiO provided by the present invention2Visible light catalytic flat-plate ultrafiltration membrane and biography prepared by blending and modifying System polysulfones, poly (ether-sulfone) ultrafiltration membrane and based on nTiO2Mixed-matrix milipore filter compare, its resistance tocrocking and visible light catalysis activity Be obviously improved, can while UF membrane is carried out catalytic degradation of the realization to organic pollution.
（2）Metal-doped nTiO provided by the present invention2Blending 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 milipore filter visible light catalytic is assigned 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 dimethylacetylamide of 71.0% (w/w), the PEG400 of 13.0% (w/w), the Tween-80 of 0.5% (w/w) and The Fe2O3 doping nTiO of 2.5% (w/w)2It is added separately in three neck round bottom flask in a certain order, 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 that will be obtained exists It is static at a temperature of stirring and dissolving to place 16 hours, the bubble of remaining in removing casting solution.
Casting solution after deaeration is poured on the glass plate of cleaning, using special Flat Membrane scraper striking film forming, in sky After being stopped 15 seconds in gas, solidification forming in 25 DEG C of constant temperature coagulating baths is immersed in, glass plate is automatically disengaged after film shaping, taken the film out Be can be prepared by within 48 hours based on Fe2O3 doping nTiO by deionized water washing 24 hours, 50% glycerine immersion treatment2Visible 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 437.39L/m2·hr· 0.1MPa, bovine serum albumin rejection is 92.06%, and resistance enhancement coefficient is 1.46, and contact angle is 77.5 °；To the drop of fulvic acid Solution clearance is by 35.43%（No light, runs 1 hour）Bring up to 59.52%（Under simulated visible light, run 1 hour）.
Embodiment 2：
By Fe2O3 doping nTiO2Content is reduced to 0.05% (w/w) by 2.5% (w/w), and the content of dimethylacetylamide 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 Fe2O3 doping nTiO2Visible light catalytic it is flat The pure water flux of milipore filter is 383.44 L/m2Hr0.1MPa, bovine serum albumin rejection is 92.39%, resistance increase system Number is 1.77, and contact angle is 85.6 °；To the degraded clearance of fulvic acid by 26.96%（No light, runs 1 hour）Bring up to 36.87%（Under simulated visible light, run 1 hour）.
Embodiment 3：
By Fe2O3 doping nTiO2Content brings up to 5.0% (w/w) by 2.5% (w/w), and the content of dimethylacetylamide is by 71.0% (w/ W) 68.5% (w/w) is reduced to, remaining is with embodiment 1.It is then prepared based on Fe2O3 doping nTiO2Visible light catalytic it is flat The pure water flux of milipore filter is 461.38 L/m2Hr0.1MPa, bovine serum albumin rejection is 91.51%, resistance increase system Number is 1.35, and contact angle is 73.1 °；To the degraded clearance of fulvic acid by 36.39%（No light, runs 1 hour）Bring up to 62.15%（Under simulated visible light, run 1 hour）.
Embodiment 4：
By metal-doped nTiO2By Fe2O3 doping nTiO2Replace with Copper-cladding Aluminum Bar nTiO2, remaining is with embodiment 1.Then prepared base In Copper-cladding Aluminum Bar nTiO2Visible light catalytic flat-plate ultrafiltration membrane pure water flux be 441.94 L/m2Hr0.1MPa, ox blood Albumin rejection is 91.30%, and resistance enhancement coefficient is 1.46, and contact angle is 77.4 °；To the degraded clearance of fulvic acid by 35.65%（No light, runs 1 hour）Bring up to 60.13%（Under simulated visible light, run 1 hour）.
Embodiment 5：
By metal-doped nTiO2By Fe2O3 doping nTiO2Replace with ferro-cobalt doping nTiO2, remaining is with embodiment 1.It is then prepared Based on ferro-cobalt doping nTiO2Visible light catalytic flat-plate ultrafiltration membrane pure water flux be 459.36 L/m2Hr0.1MPa, Bovine serum albumin rejection is 92.05%, and resistance enhancement coefficient is 1.41, and contact angle is 74.4 °；Degraded removal to fulvic acid Rate is by 36.32%（No light, runs 1 hour）Bring up to 61.95%（Under simulated visible light, run 1 hour）.
Embodiment 6：
By metal-doped nTiO2By Fe2O3 doping nTiO2Replace with indium vanadium Copper-cladding Aluminum Bar nTiO2, remaining is with embodiment 1.It is then prepared Based on indium vanadium Copper-cladding Aluminum Bar nTiO2Visible light catalytic flat-plate ultrafiltration membrane pure water flux be 473.91 L/m2·hr· 0.1MPa, bovine serum albumin rejection is 91.64%, and resistance enhancement coefficient is 1.35, and contact angle is 73.6 °；To the drop of fulvic acid Solution clearance is by 37.21%（No light, runs 1 hour）Bring up to 63.06%（Under simulated visible light, run 1 hour）.
Comparative example 1：
By the dimethylacetylamide 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 three neck round bottom flask in a certain order, and stirring and dissolving 7 hours is extremely at a temperature of 70 DEG C It is completely dissolved；Then, the casting solution that will be obtained is static at a temperature of stirring and dissolving to be placed 16 hours, remaining in removing casting solution Bubble.
Casting solution after deaeration is poured on the glass plate of cleaning, using special Flat Membrane scraper striking film forming, in sky After being stopped 15 seconds in gas, solidification forming in 25 DEG C of constant temperature coagulating baths is immersed in, glass plate is automatically disengaged after film shaping, taken the film out Flat polysulphone super-filter membrane is can be prepared by by deionized water washing 24 hours, 50% glycerine immersion treatment within 48 hours.
The pure water flux of the flat polysulphone super-filter 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 removal to fulvic acid 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 dimethylacetylamide of 71.0% (w/w), the PEG400 of 13.0% (w/w), the Tween-80 of 0.5% (w/w) and The nTiO of 2.5% (w/w)2It is added separately in three neck round bottom flask in a certain order, 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, the casting solution that will be obtained is in stirring and dissolving At a temperature of 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 being stopped 15 seconds in gas, solidification forming in 25 DEG C of constant temperature coagulating baths is immersed in, glass plate is automatically disengaged after film shaping, taken the film out Be can be prepared by within 48 hours based on nTiO by deionized water washing 24 hours, 50% glycerine immersion treatment2Flat-plate ultrafiltration membrane.
The pure water flux of the flat-plate ultrafiltration membrane prepared by this comparative example is 433.26L/m2Hr0.1MPa, cow's serum Retention rate of proteins is 92.35%, and resistance enhancement coefficient is 1.55, and contact angle is 82.3 °；To the degraded clearance of fulvic acid by 32.56%（No light, runs 1 hour）Bring up to 33.97%（Under simulated visible light, run 1 hour）.

Claims (6)

1. it is a kind of to be based on metal-doped nTiO2Visible light catalytic flat-plate ultrafiltration membrane, it is characterised in that contain in its casting solution Metal-doped nTiO2, and influence the structure and performance of milipore filter；Casting solution by following mass percent material composition：Polymerization Thing membrane material 8.0%~20.0% (w/w), pore-foaming agent 5.0%~15.0% (w/w), surfactant 0.05%~2.0% (w/w), gold Category doping nTiO2 0.05%~5.0% (w/w), remaining is solvent.
2. according to claim 1 based on metal-doped nTiO2Visible light catalytic flat-plate ultrafiltration membrane, its feature exists In：Described milipore filter is to do-wet method preparation using traditional phase inversion.
3. according to claim 1 based on metal-doped nTiO2Visible light catalytic flat-plate ultrafiltration membrane, its feature exists In：Described metal-doped nTiO2It is visible light catalyst cobalt doped nTiO2, bismuth doping nTiO2, chromium doping nTiO2, Fe2O3 doping nTiO2, Copper-cladding Aluminum Bar nTiO2, aluminium doping nTiO2, molybdenum doping nTiO2, zinc-iron nTiO2, ferrotungsten doping nTiO2, ferro-cobalt doping nTiO2 With indium vanadium Copper-cladding Aluminum Bar nTiO2One kind of powder, content accounts for 0.05%~5.0% (w/w) of casting solution gross weight.
4. according to claim 1 based on metal-doped nTiO2Visible light catalytic flat-plate ultrafiltration membrane, it is characterised in that： Described polymeric film material is polysulfones, one kind of polyether sulfone；Described pore-foaming agent is polyethylene glycol, polyvinylpyrrolidone It is a kind of；Described surfactant is nonionic surfactant, such as polysorbate（Tween）, fatty glyceride, aliphatic acid One kind of the smooth grade of sorb；Described solvent is DMAC N,N' dimethyl acetamide（DMAc）, N,N-dimethylformamide（DMF）, N- first Base pyrrolidones（NMP）One or two mixing.
5. it is a kind of to be based on metal-doped nTiO2Visible light catalytic flat-plate ultrafiltration membrane preparation method, it is characterised in that it wrap Include：
Step（1）By a certain amount of solvent, pore-foaming agent, surfactant and metal-doped nTiO2According to certain ratio, order It is added separately in three neck round bottom flask, stirs；
Step（2）Polysulfones or polyether sulfone are added in three neck round bottom flask, stirring and dissolving 5~16 is small 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 being stopped 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 shaping Depart from glass plate, be can be prepared by based on metal-doped nTiO through deionized water washing, 50% glycerine immersion treatment after taking the film out2 Visible light catalytic flat-plate ultrafiltration membrane.
6. the one kind according to claim 5 is based on metal-doped nTiO2Visible light catalytic flat-plate ultrafiltration membrane preparation Method, it is characterised in that：Described coagulating bath is deionized water.
CN201611181699.1A 2016-12-20 2016-12-20 Based on metal-doped nTiO2Visible light catalytic flat-plate ultrafiltration membrane and preparation method Pending CN106799165A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201611181699.1A CN106799165A (en) 2016-12-20 2016-12-20 Based on metal-doped nTiO2Visible light catalytic flat-plate ultrafiltration membrane and preparation method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201611181699.1A CN106799165A (en) 2016-12-20 2016-12-20 Based on metal-doped nTiO2Visible light catalytic flat-plate ultrafiltration membrane and preparation method

Publications (1)

Publication Number Publication Date
CN106799165A true CN106799165A (en) 2017-06-06

Family

ID=58984846

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201611181699.1A Pending CN106799165A (en) 2016-12-20 2016-12-20 Based on metal-doped nTiO2Visible light catalytic flat-plate ultrafiltration membrane and preparation method

Country Status (1)

Country Link
CN (1) CN106799165A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108212221A (en) * 2017-12-29 2018-06-29 成都优纳新材料有限公司 A kind of visible light catalytic type PTFE/TiO2Biaxial tension tablet membrane preparation method

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102309927A (en) * 2011-07-18 2012-01-11 济南大学 Antibacterial polyethersulfone hollow fiber ultrafiltration membrane and preparation method thereof
CN102895888A (en) * 2012-10-12 2013-01-30 福州大学 Polyvinylidene fluoride film capable of responding to visible light and preparation method of polyvinylidene fluoride film
CN102989329A (en) * 2012-12-13 2013-03-27 华南农业大学 Ag/TiO2 modified PVDF (Polyvinylidene Fluoride) ultrafiltration membrane as well as preparation method and application thereof
CN103121732A (en) * 2013-02-06 2013-05-29 上海交通大学 Method for removing smelly substances in water
CN104084053A (en) * 2014-07-02 2014-10-08 上海交通大学 Nanometer photocatalyst material supported embedded composite film and preparation method and application thereof
CN104190416A (en) * 2014-08-15 2014-12-10 李建明 Method for preparing metal doped TiO2 nanocrystal particles

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102309927A (en) * 2011-07-18 2012-01-11 济南大学 Antibacterial polyethersulfone hollow fiber ultrafiltration membrane and preparation method thereof
CN102895888A (en) * 2012-10-12 2013-01-30 福州大学 Polyvinylidene fluoride film capable of responding to visible light and preparation method of polyvinylidene fluoride film
CN102989329A (en) * 2012-12-13 2013-03-27 华南农业大学 Ag/TiO2 modified PVDF (Polyvinylidene Fluoride) ultrafiltration membrane as well as preparation method and application thereof
CN103121732A (en) * 2013-02-06 2013-05-29 上海交通大学 Method for removing smelly substances in water
CN104084053A (en) * 2014-07-02 2014-10-08 上海交通大学 Nanometer photocatalyst material supported embedded composite film and preparation method and application thereof
CN104190416A (en) * 2014-08-15 2014-12-10 李建明 Method for preparing metal doped TiO2 nanocrystal particles

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
华耀祖: "《超滤技术与应用》", 31 March 2004, 化学工业出版社 *
李经等: "TiO2光致超亲水性能的研究进展", 《钢铁钒钛》 *
林华香等: "TiO2表面羟基及其性质", 《化学进展》 *
胡桢等: "《新型高分子合成与制备工艺》", 31 May 2014, 哈尔滨工业大学出版社 *
高铁等: "TiO2表面超亲水性", 《材料导报》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108212221A (en) * 2017-12-29 2018-06-29 成都优纳新材料有限公司 A kind of visible light catalytic type PTFE/TiO2Biaxial tension tablet membrane preparation method

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
US10625214B2 (en) Titanium dioxide / sulfonated graphene oxide / Ag nanoparticle composite membrane and preparation and application thereof
CN106943897A (en) Based on dopen Nano Cu2O visible light catalytic flat-plate ultrafiltration membrane and preparation method
CN111871234B (en) Loose nanofiltration membrane and preparation method and application thereof
CN107174984A (en) A kind of preparation method of low-pressure high-throughput antipollution hollow fiber nanofiltration membrane
CN105056768A (en) Hydrotalcite-similar composite forward osmosis membrane supporting layer and preparation method thereof
CN107638807A (en) ZIF 8/PVDF milipore filters with catalytic action and preparation method thereof under a kind of normal temperature
CN107376673B (en) Loaded with TiO2PES ultrafiltration membrane of nanotube and preparation method and application thereof
CN106693730B (en) Based on nonmetallic more doping nTiO2Visible light catalytic hollow fiber ultrafiltration membrane and preparation method
CN106731879B (en) Based on metal-doped nTiO2Visible light catalytic hollow fiber ultrafiltration membrane and preparation method
CN107469646A (en) A kind of Ag3PO4/TiO2PVDF is modified composite membrane and preparation method thereof
CN109304088A (en) A kind of sea water desalination membrane of strong alkali-acid resistance and the preparation method and application thereof
CN106693731A (en) Method for preparing high-throughput ultrafiltration membrane from nano calcium carbonate doped polysulfone
CN106310965A (en) Preparation method of poly-dopamine modified PVDF membrane
CN106731876A (en) Visible light catalytic flat-plate ultrafiltration membrane and preparation method based on dopen Nano ZnO
CN104258857A (en) Silver chromate-graphene oxide composite photocatalytic material and preparation method thereof
CN104841296A (en) Nanosized silica sphere/polypiperazine-amide nano composite nanofiltration membrane and preparation method thereof
CN108246129A (en) A kind of sewage disposal antipollution complex reverse osmosis membrane and preparation method thereof
CN106975359A (en) Based on dopen Nano Cu2O visible light catalytic hollow fiber ultrafiltration membrane and preparation method
CN112090296A (en) Based on F-TiO2/Fe-g-C3N4Self-cleaning flat plate type PVDF ultrafiltration membrane and preparation method thereof
CN106799165A (en) Based on metal-doped nTiO2Visible light catalytic flat-plate ultrafiltration membrane and preparation method
CN104801203A (en) Separating membrane capable of decomposing surface organic pollutants, and preparation method thereof
CN106731877A (en) Visible light catalytic flat-plate ultrafiltration membrane and preparation method based on Ag/AgX
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
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20170606