CN106975359A - Based on dopen Nano Cu2O visible light catalytic hollow fiber ultrafiltration membrane and preparation method - Google Patents

Based on dopen Nano Cu2O visible light catalytic hollow fiber ultrafiltration membrane and preparation method Download PDF

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Publication number
CN106975359A
CN106975359A CN201710096026.4A CN201710096026A CN106975359A CN 106975359 A CN106975359 A CN 106975359A CN 201710096026 A CN201710096026 A CN 201710096026A CN 106975359 A CN106975359 A CN 106975359A
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visible light
hollow fiber
ultrafiltration membrane
fiber ultrafiltration
light catalytic
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王秀菊
王立国
许伟颖
何芳
王仲鹏
刘思全
周凯丽
侯凯
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University of Jinan
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University of Jinan
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/14—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
    • B01D63/02—Hollow fibre modules
    • 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
    • B01D69/08—Hollow fibre 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
    • 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
    • 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
    • C02F2305/04—Surfactants, used as part of a formulation or alone
    • 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

Dopen Nano Cu is based on the invention discloses one kind2O visible light catalytic hollow fiber ultrafiltration membrane and preparation method, belongs to technical field of membrane separation.By 10.0%~25.0% (w/w) polysulfones or polyether sulfone, 8.0%~17.0% (w/w) pore-foaming agent, 0.1%~2.0% (w/w) surfactant, 0.1%~5.0% (w/w) dopen Nano Cu2O and 51.0%~81.8% (w/w) solvent are added in dissolving tank in a certain order, and to being completely dissolved, casting solution is made in standing and defoaming 8~36 hours to stirring and dissolving within 5~16 hours at a temperature of 35~95 DEG C；Visible light catalytic hollow fiber ultrafiltration membrane is prepared using traditional dry-wet spinning technique.Pure water flux >=320L/m of prepared milipore filter of the invention2Hr0.1MPa, bovine serum albumin rejection >=90.00%, to degraded clearance >=60% of fulvic acid（Under simulated visible light, run 1 hour）, with good antifouling property and visible light catalytic performance.Product of the present invention is particularly suitable for use in micro-polluted source water advanced treating, seawater desalinization pretreatment and biochemical industry, the advanced treating of field of medicaments waste water and reuse etc..

Description

Based on dopen Nano Cu2O visible light catalytic hollow fiber ultrafiltration membrane and preparation method
Technical field
It is more particularly to a kind of based on doping the present invention relates to a kind of macromolecule mixed-matrix milipore filter and preparation method thereof Nanometer Cu2O visible light catalytic hollow fiber ultrafiltration membrane and preparation method.
Background technology
The deficient and increasingly serious water pollution of water resource turns 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 turn 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, also known as hybridized film, are to be chemically crosslinked organic and inorganic constituents or the microcosmic film being mixed to form, again Claim " hybrid organic-inorganic film ", high separability and toughness because having the corrosion-resistant of inoranic membrane, heat resistance and organic film concurrently etc. are excellent Point, becomes and studies one of membrane material modified focus.In recent years, domestic and foreign scholars are prepared using blending method or sol-gal process To 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 Solve 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 milipore filter is prepared by adulterating or coating visible light catalyst, is improving the resistance tocrocking of milipore filter While, make milipore filter that there is visible light catalysis activity again, expand the application of milipore filter, be milipore filter research in recent years Focus.
Chinese patent CN104383821A uses the magnetic particle@TiO of graphene oxide-loaded core shell structure2Prepare and be 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 and the quality of visible light photocatalytic degradation performance of prepared film, 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, Cost is high.Chinese patent CN104117291A is modified using TiO2/C hybrid aerogels and is prepared for polyvinylidene fluoride film, 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）It is then 93.28% to reactive brilliant red x-3b degradation rate 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 Modification prepares milipore filter, is in fact that mainly make use of AgNO3Visible light catalysis activity, and degradation rate is slower（In patent Employ 10 hours degradation rates to methylene blue of illumination and carry out Characterization of Its Photocatalytic Activity）, it is impossible to prepare simultaneously 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 of separation and visible light catalytic performance simultaneously for preparing；Meanwhile, the two patents are imitated not over collaboration Should be to make 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 catalytic 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 by adsorbing silver ion, reduction silver ion it is that the steps such as silver-colored simple substance, vacuum drying could complete patent production 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, production Industry difficulty is larger.
With nTiO2Photocatalytic activity could be only produced under ultraviolet light for most of photochemical catalysts of representative, because This, development visible-light-responsive photocatalyst tool is of great significance.Cuprous oxide（Cu2O）It is a kind of important inorganic Industrial chemicals, it has semiconductor property, and energy gap only has 1.92eV, can be by 600nm wavelength（Visible ray）Catalysis.Research hair It is existing, Cu2O is a kind of stable semiconductor visible light catalyst of performance, and certain photocatalytic activity can be shown under visible light, But nonmetallic it can improve by doping metals or significantly a nanometer Cu2O visible light catalytic efficiency；By dopen Nano Cu2O and height Molecular material blending carries out the development of visible light catalytic mixed-matrix milipore filter, to improving UF membrane efficiency, widening seperation film Application field, mitigation fouling membrane have certain meaning.
The present invention is using dopen Nano Cu2O improves the photocatalysis characteristic of polymer ultrafiltration membrane, and preparing has visible light catalytic The hollow fiber ultrafiltration membrane of activity, does not see the life of similar visible light catalytic hollow fiber ultrafiltration membrane product so far both at home and abroad Production, both at home and abroad also there is not yet pertinent literature is reported.
The content of the invention
Dopen Nano Cu is based on it is an object of the invention to provide one kind2O visible light catalytic hollow fiber ultrafiltration membrane, this hair Another bright purpose is to provide the preparation method of the visible light catalytic hollow fiber ultrafiltration membrane.
To achieve the above object, the technical scheme taken of the present invention is：
One kind is based on dopen Nano Cu2O visible light catalytic hollow fiber ultrafiltration membrane, is the material group by following mass percent Into：Polymeric film material 10.0%~25.0% (w/w), pore-foaming agent 8.0%~17.0% (w/w), surfactant 0.1%~ 2.0% (w/w), dopen Nano Cu2O0.1%~5.0% (w/w), solvent 51.0%~81.8% (w/w)；
Described polymeric film material is polysulfones, one kind of polyether sulfone, and content is 10.0%~25.0% (w/w)；
Described pore-foaming agent is polyethylene glycol, one kind of polyvinylpyrrolidone, and content is 8.0%~17.0% (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 0.1%~2.0% (w/w)；
Described dopen Nano Cu2O is Ag doped with nano Cu2O, zinc doping nanometer Cu2O, cerium-doped nanometer Cu2O, Fe2O3 doping are received Rice Cu2O, nitrogen-doped nanometer Cu2O, carbon nano tube-doped nanometer Cu2O and graphene dopen Nano Cu2The visible light catalysts such as O One kind, content is 0.1%~5.0% (w/w)；
Described solvent is DMAC N,N' dimethyl acetamide（DMAc）, N,N-dimethylformamide（DMF）, 1-METHYLPYRROLIDONE （NMP）One or two kinds of mixing, content is 51.0%~81.8% (w/w).
One kind is based on dopen Nano Cu2The preparation method of O visible light catalytic hollow fiber ultrafiltration membrane, including following step Suddenly：
（1）By a certain amount of solvent, pore-foaming agent, surfactant, dopen Nano Cu2O adds respectively according to certain ratio, order Enter into dissolving tank, stirred under normal temperature；
（2）A certain amount of polymeric film material is added in dissolving tank, stirring and dissolving 5~16 hours at a temperature of 35~95 DEG C To being completely dissolved, initial casting solution is configured to；Then, the static placement 8~36 at a temperature of stirring and dissolving by obtained casting solution Hour makes its complete deaeration；
（3）Using traditional dry-wet spinning technique, casting film 3.0~20.0mL/min of flow velocity is controlled, casting solution temperature is 35 ~95 DEG C, coagulation bath temperature be 15~35 DEG C, between air highly be 0~15cm, hollow fiber ultrafiltration membrane setting time be 0.5~ 5.0 minutes, prepare visible light catalytic hollow fiber ultrafiltration membrane；
（4）Finally, prepared hollow fiber ultrafiltration membrane is put into deionized water and soaks, rinses 24 hours, to clean addition Agent；Then it is put into the glycerite that concentration is 50% and handles 48 hours, that is, prepares based on dopen Nano Cu2O visible ray is urged Change hollow fiber ultrafiltration membrane.
Described coagulating bath is deionized water.
Dopen Nano Cu is based on the invention provides one kind2O visible light catalytic hollow fiber ultrafiltration membrane and preparation method, By dopen Nano Cu2O visible light catalytic materials, which are incorporated into polymer, prepares mixed-matrix milipore filter, and it is super to assign mixed-matrix The performance of the good resistance tocrocking of filter membrane and visible light photocatalytic degradation of organic pollutants, this is the innovation of the present invention.In order to The resistance tocrocking and visible light catalytic performance of prepared visible light catalytic milipore filter are examined, the present invention is to prepared milipore filter Resistance enhancement coefficient and contact angle are tested, and as a result show that resistance enhancement coefficient and contact angle are all substantially reduced, milipore filter Resistance tocrocking be greatly improved.Meanwhile, using fulvic acid as target contaminant, by prepared visible light catalytic ultrafiltration Film carries out visible light photocatalytic degradation clearance and the test of milipore filter variations of flux, as a result shows, prepared milipore filter is in simulation Good Photocatalytic Degradation Property and antifouling property is shown when being run under visible ray, the flux decline of film is substantially reduced.
The present invention is compared with prior art, with following beneficial effect：
（1）Dopen Nano Cu provided by the present invention2Visible light catalytic hollow fiber ultrafiltration membrane prepared by O blending and modifyings is with passing Unite polysulfones, poly (ether-sulfone) ultrafiltration membrane and based on nanometer Cu2O milipore filter is compared, and its resistance tocrocking and visible light catalysis activity are obtained To being obviously improved, can while UF membrane is carried out catalytic degradation of the realization to organic pollution.
（2）Dopen Nano Cu provided by the present invention2O blending and modifyings prepare the side of visible light catalytic hollow fiber ultrafiltration membrane Method, equipment used is as traditional hollow fiber ultrafiltration membrane spinning equipment, and simple, easily-controllable, film preparation technique is simple, film forming Prepared milipore filter visible light catalysis activity and resistance tocrocking are assigned simultaneously, easily realize industrialization.
Embodiment：
With reference to embodiment, the present invention is described in further detail, but the implementation of the present invention is not limited to this.
Embodiment 1：
By 62.0% (w/w) dimethyl acetamide, 15.0% (w/w) polyethylene glycol 400,1.0% (w/w) Tween-80 and 3.0% (w/w) nitrogen-doped nanometer Cu2O is added separately in dissolving tank in a certain order, is stirred；Then add 19.0% (w/w) polysulfones, stirring and dissolving 8 hours is to being completely dissolved at a temperature of 85 DEG C；Then, obtained casting solution is being stirred Mix bubble remaining in static placement 24 hours under solution temperature, removing casting solution.
Casting film flow velocity 10.0mL/min is controlled, casting solution temperature is 35 DEG C, and coagulation bath temperature is 23 DEG C, height between air For 5cm, hollow fiber ultrafiltration membrane setting time is 1.0 minutes, prepares visible ray using traditional dry-wet spinning technique and urges Change hollow fiber ultrafiltration membrane.Prepared hollow fiber ultrafiltration membrane, which is put into deionized water, soaks, rinses 24 hours, to clean Additive.Then it is put into the glycerite that concentration is 50% and handles 48 hours, that is, prepares based on nitrogen-doped nanometer Cu2O's Visible light catalytic hollow fiber ultrafiltration membrane.
The pure water flux of visible light catalytic hollow fiber ultrafiltration membrane prepared by the present embodiment is 326.91L/m2·hr· 0.1MPa, bovine serum albumin rejection is 91.97%, and resistance enhancement coefficient is 1.41, and dynamic contact angle is 74.1 °；To fulvic acid Degraded clearance by 39.43%（No light, runs 1 hour）Bring up to 63. 62%（Under simulated visible light, run 1 hour）.
Embodiment 2：
By nitrogen-doped nanometer Cu2O content is reduced to 0.1% (w/w) by 3.0% (w/w), and the content of dimethyl acetamide is by 62.0% (w/ W) 64.9% (w/w) is brought up to, remaining be the same as Example 1.It is then prepared based on nitrogen-doped nanometer Cu2In O visible light catalytic The pure water flux of fibre ultrafiltration film is 302.12 L/m2Hr0.1MPa, bovine serum albumin rejection is 92.69%, resistance Enhancement coefficient is 1.77, and contact angle is 85.3 °；To the degraded clearance of fulvic acid by 26.76%（No light, runs 1 hour）Carry It is high to 39.04%（Under simulated visible light, run 1 hour）.
Embodiment 3：
By nitrogen-doped nanometer Cu2O content brings up to 5.0% (w/w) by 3.0% (w/w), and the content of dimethyl acetamide is by 62.0% (w/w) 60.0% (w/w) is reduced to, remaining be the same as Example 1.It is then prepared based on nitrogen-doped nanometer Cu2O visible light catalytic The pure water flux of hollow fiber ultrafiltration membrane is 341.41 L/m2Hr0.1MPa, bovine serum albumin rejection is 91.56%, resistance Power enhancement coefficient is 1.36, and contact angle is 73.1 °；To the degraded clearance of fulvic acid by 41.79%（No light, runs 1 hour） Bring up to 65. 64%（Under simulated visible light, run 1 hour）.
Embodiment 4：
By dopen Nano Cu2O is by nitrogen-doped nanometer Cu2O replaces with zinc doping nanometer Cu2O, remaining be the same as Example 1.It is then made It is standby based on zinc doping nanometer Cu2The pure water flux of O visible light catalytic hollow fiber ultrafiltration membrane is 321.33 L/m2·hr· 0.1MPa, bovine serum albumin rejection is 92.44%, and resistance enhancement coefficient is 1.43, and contact angle is 74.4 °；To the drop of fulvic acid Clearance is solved by 39.11%（No light, runs 1 hour）Bring up to 61.37%（Under simulated visible light, run 1 hour）.
Embodiment 5：
By dopen Nano Cu2O is by nitrogen-doped nanometer Cu2O replaces with graphene dopen Nano Cu2O, remaining be the same as Example 1.Then It is prepared based on graphene dopen Nano Cu2The pure water flux of O visible light catalytic hollow fiber ultrafiltration membrane is 351.72 L/ m2Hr0.1MPa, bovine serum albumin rejection is 92.76%, and resistance enhancement coefficient is 1.39, and contact angle is 73.2 °；To Huang The degraded clearance of rotten acid is by 40.23%（No light, runs 1 hour）Bring up to 64.93%（Under simulated visible light, operation 1 is small When）.
Comparative example 1：
By 65.0% (w/w) dimethyl acetamide, 15.0% (w/w) polyethylene glycol 400,1.0% (w/w) Tween-80 and 19.0% (w/w) polysulfones is added separately in dissolving tank in a certain order, and stirring and dissolving 8 hours is extremely at a temperature of 85 DEG C It is completely dissolved；Then, it is obtained casting solution is remaining in static placement 24 hours, removing casting solution at a temperature of stirring and dissolving Bubble.
Casting film flow velocity 10.0mL/min is controlled, casting solution temperature is 35 DEG C, and coagulation bath temperature is 23 DEG C, height between air For 5cm, hollow-fibre membrane setting time is 1.0 minutes, and it is fine to prepare polysulfone hollow using traditional dry-wet spinning technique Tie up milipore filter.Prepared hollow-fibre membrane, which is put into deionized water, to be soaked, rinses 24 hours, to clean additive.Then put To concentration to be handled 48 hours in 50% glycerite, that is, prepare the polysulfone hollow fibre milipore filter of commercialization.
The pure water flux of polysulfone hollow fibre milipore filter prepared by this comparative example is 287.26 L/m2·hr· 0.1MPa, bovine serum albumin rejection is 93.46%, and resistance enhancement coefficient is 1.83, and contact angle is 89.0 °；To the drop of fulvic acid Clearance is solved by 23.96%（No light, runs 1 hour）Bring up to 24.23%（Under simulated visible light, run 1 hour）.
Comparative example 2：
By 62.0% (w/w) dimethyl acetamide, 15.0% (w/w) polyethylene glycol 400,1.0% (w/w) Tween-80 and 3.0% (w/w) nanometer Cu2O is added separately in dissolving tank in a certain order, is stirred；Then 19.0% (w/ is added W) polysulfones, stirring and dissolving 8 hours is to being completely dissolved at a temperature of 85 DEG C；Then, by obtained casting solution in stirring and dissolving temperature It is static under degree to place 24 hours, remaining bubble in removing casting solution.
Casting film flow velocity 10.0mL/min is controlled, casting solution temperature is 35 DEG C, and coagulation bath temperature is 23 DEG C, height between air For 5cm, hollow fiber ultrafiltration membrane setting time is 1.0 minutes, prepares visible ray using traditional dry-wet spinning technique and urges Change hollow fiber ultrafiltration membrane.Prepared hollow fiber ultrafiltration membrane, which is put into deionized water, soaks, rinses 24 hours, to clean Additive.Then it is put into the glycerite that concentration is 50% and handles 48 hours, that is, prepares based on nanometer Cu2O doughnut Milipore filter.
The pure water flux of hollow fiber ultrafiltration membrane prepared by this comparative example is 302.37L/m2Hr0.1MPa, ox blood Albumin rejection is 92.82%, and resistance enhancement coefficient is 1.58, and dynamic contact angle is 82.3 °；Degraded to fulvic acid is removed Rate is by 33.62%（No light, runs 1 hour）Bring up to 45.16%（Under simulated visible light, run 1 hour）.

Claims (6)

1. one kind is based on dopen Nano Cu2O visible light catalytic hollow fiber ultrafiltration membrane, it is characterised in that contain in its casting solution There is dopen Nano Cu2O, and influence the structure and performance of milipore filter；Casting solution by following mass percent material composition：Polymerization Thing membrane material 10.0%~25.0% (w/w), pore-foaming agent 8.0%~17.0% (w/w), surfactant 0.1%~2.0% (w/w), mix Miscellaneous nanometer Cu2O 0.1%~5.0% (w/w), remaining is solvent.
2. according to claim 1 based on dopen Nano Cu2O visible light catalytic hollow fiber ultrafiltration membrane, its feature exists In：Described milipore filter be done using traditional phase inversion-it is prepared by wet method.
3. according to claim 1 based on dopen Nano Cu2O visible light catalytic hollow fiber ultrafiltration membrane, its feature exists In：Described dopen Nano Cu2O is Ag doped with nano Cu2O, zinc doping nanometer Cu2O, cerium-doped nanometer Cu2O, Fe2O3 doping nanometer Cu2O, nitrogen-doped nanometer Cu2O, carbon nano tube-doped nanometer Cu2O and graphene dopen Nano Cu2The one of the visible light catalysts such as O Kind, content accounts for 0.1%~5.0% (w/w) of casting solution gross weight.
4. according to claim 1 be based on dopen Nano Cu2O visible light catalytic hollow fiber ultrafiltration membrane, its feature exists In：Described polymeric film material is polysulfones, one kind of polyether sulfone；The pore-foaming agent is polyethylene glycol, polyvinylpyrrolidone One kind；Described surfactant is nonionic surfactant, such as polysorbate（Tween）, fatty glyceride, fat One kind of the sour smooth grade of sorb；Described solvent is DMAC N,N' dimethyl acetamide（DMAc）, N,N-dimethylformamide（DMF）、N- Methyl pyrrolidone（NMP）One or two kinds of mixing.
5. one kind is based on dopen Nano Cu2The preparation method of O visible light catalytic hollow fiber ultrafiltration membrane, it is characterised in that it is wrapped Include：
Step（1）By a certain amount of solvent, pore-foaming agent, surfactant and dopen Nano Cu2O is according to certain ratio, order point It is not added in dissolving tank, is stirred under normal temperature；
Step（2）Polysulfones or polyether sulfone are added in dissolving tank, stirring and dissolving 5~16 hours is to complete at a temperature of 35~95 DEG C Fully dissolved, static placement deaeration 8~36 hours obtains visible light catalytic hollow fiber ultrafiltration membrane casting solution；
Step（3）Using traditional dry-wet spinning technique, casting film 3.0~20.0mL/min of flow velocity, casting solution temperature are controlled For 35~95 DEG C, coagulation bath temperature is 15~35 DEG C, is highly 0~15cm between air, and hollow fiber ultrafiltration membrane setting time is 0.5~5.0 minute, prepare visible light catalytic hollow fiber ultrafiltration membrane；
Step（4）Prepared hollow fiber ultrafiltration membrane is put into deionized water and soaks, rinse 24 hours, to clean addition Agent；Then it is put into the glycerite that concentration is 50% and handles 48 hours, that is, prepares based on dopen Nano Cu2O visible ray It is catalyzed hollow fiber ultrafiltration membrane.
6. according to claim 5 based on dopen Nano Cu2The preparation side of O visible light catalytic hollow fiber ultrafiltration membrane Method, it is characterised in that：Described coagulating bath is deionized water.
CN201710096026.4A 2017-02-22 2017-02-22 Based on dopen Nano Cu2O visible light catalytic hollow fiber ultrafiltration membrane and preparation method Pending CN106975359A (en)

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CN116139933A (en) * 2023-04-23 2023-05-23 北京科技大学 Nanofiber membrane with ethylene degradation capability by visible light catalysis and visible light catalysis device

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Application publication date: 20170725