CN108159888A - A kind of preparation method of the super hydrophilic ultrafiltration membrane with photocatalysis performance - Google Patents
A kind of preparation method of the super hydrophilic ultrafiltration membrane with photocatalysis performance Download PDFInfo
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- CN108159888A CN108159888A CN201810018907.9A CN201810018907A CN108159888A CN 108159888 A CN108159888 A CN 108159888A CN 201810018907 A CN201810018907 A CN 201810018907A CN 108159888 A CN108159888 A CN 108159888A
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- 239000012528 membrane Substances 0.000 title claims abstract description 73
- 238000000108 ultra-filtration Methods 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 19
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000002156 mixing Methods 0.000 claims abstract description 20
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 83
- 239000011259 mixed solution Substances 0.000 claims description 39
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 28
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 23
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 20
- 238000005266 casting Methods 0.000 claims description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 210000002469 basement membrane Anatomy 0.000 claims description 17
- 210000004379 membrane Anatomy 0.000 claims description 16
- 239000004408 titanium dioxide Substances 0.000 claims description 13
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 11
- 229960000583 acetic acid Drugs 0.000 claims description 10
- 239000012362 glacial acetic acid Substances 0.000 claims description 10
- 239000004745 nonwoven fabric Substances 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 239000004695 Polyether sulfone Substances 0.000 claims description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 229920002125 Sokalan® Polymers 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000004584 polyacrylic acid Substances 0.000 claims description 7
- 229920006393 polyether sulfone Polymers 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- 238000003618 dip coating Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 238000002604 ultrasonography Methods 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 238000007654 immersion Methods 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000007790 scraping Methods 0.000 claims 1
- 230000004907 flux Effects 0.000 abstract description 22
- 239000002346 layers by function Substances 0.000 abstract description 6
- 238000012986 modification Methods 0.000 abstract description 4
- 230000010148 water-pollination Effects 0.000 abstract description 4
- 239000002105 nanoparticle Substances 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 12
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 6
- 229940113088 dimethylacetamide Drugs 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000003344 environmental pollutant Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 231100000719 pollutant Toxicity 0.000 description 5
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000002242 deionisation method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000004021 humic acid Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical class CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
Classifications
-
- 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
- B01D69/10—Supported membranes; Membrane supports
-
- 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
- B01D69/10—Supported membranes; Membrane supports
- B01D69/107—Organic support material
- B01D69/1071—Woven, non-woven or net mesh
-
- 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
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/02—Hydrophilization
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
Abstract
The present invention relates to ultrafiltration membrane modificationss field, especially a kind of preparation method of the super hydrophilic ultrafiltration membrane with photocatalysis performance adds TiO by way of blending in basement membrane2, and it is crosslinked TiO in membrane surface2Functional layer not only increases the hydrophily inside ultrafiltration membrane, whole water flux is improved, and ultrafiltration membrane surface is caused to have good hydrophily, resistance tocrocking, photo-catalysis function, additionally using supersound process so that TiO2Nano-particle can be uniformly dispersed in ultrafiltration membrane, and stable rejection is kept under conditions of high water flux.
Description
Technical field
The present invention relates to ultrafiltration membrane modificationss field, especially a kind of super hydrophilic ultrafiltration membrane with photocatalysis performance
Preparation method.
Background technology
Ultrafiltration is the screening process using pressure difference as motive force, can sieve the macromolecular substances in solution, such as suspended matter, part
Natural organic matter etc. realizes the separation of solute and water, is a kind of very promising so as to reach the purpose of purification, purification, concentration
Membrane separation technique.But in use, the pollutant of separation is easily adsorbed in film surface, is formed filter cake or is blocked fenestra, makes
Into fouling membrane, flux is caused to decline, energy consumption increases.So fouling membrane be the problem of restricting the application of ultrafiltration heavy industrialization it
One and one of the key technical problem of UF membrane field urgent need to resolve.
It is a kind of effective way for solving fouling membrane film to be carried out hydrophilically modified.Most of pollutant due to retention is
Lyophobic dust, such as colloid, protein, lipid, when film surface material is all hydrophobicity, contact of the pollutant with film surface
Angle is small, is easily closely adhered on film surface.And film surface is by modified, hydrophobic pollutant and hydrophilic film surface shape
Into contact angle it is larger, pollutant easily forms sphere in film surface, after simply rinsing, you can restores the flux of film.
As CN103394294A discloses a kind of load TiO2High-performance PVDF composite hyperfiltration membranes preparation method, be utilize
Immersion precipitation prepares basement membrane, is immersed into TiO 2 precursor solution after used additives solution treatment basement membrane, makes drive body
Hydrolysis obtains composite hyperfiltration membrane after being rinsed with water.The technology of preparing deficiency is：Only to ultrafiltration membrane surface with titanium dioxide forerunner
Liquid solution is modified, and does not do any processing in basement membrane, and filtration flux is smaller, ineffective.And Li little Yu et al. is to ultrafiltration
Film carries out titania modified research, it is proposed that a kind of nano-TiO2The preparation method of modified PVDF ultrafiltration membrane, but film surface is not
Hydrophilic functional layer is grafted, the water contact angle for causing film surface is smaller, and hydrophily is bad, and because being limited to nano-TiO2's
Agglomeration leads to TiO in ultrafiltration membrane2Content is less, and water flux is insufficient.(referring to Li little Yu etc., nano-TiO2Modified PVDF surpasses
Preparation [J] the synthetic resin and plastics of filter membrane, 2017,34 (4)：51)
Invention content
In order to solve technical problem in the prior art, the present invention provides a kind of super hydrophilic with photocatalysis performance
The technical solution of the preparation method of ultrafiltration membrane.
A kind of preparation method of the super hydrophilic ultrafiltration membrane with photocatalysis performance, includes the following steps：
(1) TiO is prepared2Sol solution：Butyl titanate, glacial acetic acid are added in n,N-dimethylacetamide, mixed
Close solution a；Deionized water, concentrated hydrochloric acid are added in n,N-dimethylacetamide, obtain mixed solution b；In mixed solution a ultrasounds
Under conditions of vibration, mixed solution b is added in mixed solution a, pH to 4 is adjusted with concentrated hydrochloric acid, obtains TiO2Sol solution, and
Keep TiO2Sol solution is in ultrasonic vibration state, for use；
(2) casting solution is prepared：By polyether sulfone, polyvinylpyrrolidone, polyethylene glycol, TiO2Sol solution adds in organic molten
In agent, heating stirring is ultrasonic, and vacuum defoamation obtains casting solution；
(3) ultrafiltration membrane basement membrane is prepared：Using non-woven fabrics as supporting layer, casting solution is poured on non-woven fabrics, with stainless steel spatula
Casting solution is carried out to scrape film process, then immerse in deionized water, cures, obtains ultrafiltration membrane basement membrane；
(4) finished film is prepared：Dip-coating, vacuum drying carry out membrane surface, then immerse pure water using modified solution, i.e.,
.
In the step (1), butyl titanate, glacial acetic acid in mixed solution a, n,N-dimethylacetamide, by 30:1:
50 volume ratio mixing；Deionized water, concentrated hydrochloric acid, n,N-dimethylacetamide in mixed solution b, by 20:1:167 volume
Than mixing；TiO2Mixed solution a, mixed solution b in sol solution, by 1~2:1 volume ratio mixing, the quality of concentrated hydrochloric acid
A concentration of 36%.
In the step (2), the mass percent of polyether sulfone is 14%~19%, the quality percentage of polyvinylpyrrolidone
Than being 1.5%~2.5%, the mass percent of polyethylene glycol is 1%~3%, TiO2The mass percent of sol solution is 2%
~4%.
In the step (2), organic solvent is n,N-Dimethylformamide, n,N-dimethylacetamide, N- methylpyrroles
Any one of alkanone.
In the step (2), heating temperature be 80 DEG C, mixing time be 1~3h, ultrasonic time be 6~8h, vacuum defoamation
Time is 12~18h.
In the step (3), film thickness is scraped as 180~220 μm, and knifing speed is 1.5~5m/min, deionized water temperature
It is 10~20 DEG C.
In the step (4), the preparation method of modified solution is：By ethylene glycol, polyacrylic acid, titanium dioxide addition go from
In sub- water, 10min is stirred, 2~4h of ultrasound, wherein quality of glycol percentage are 1%~1.5%, polyacrylic acid quality percentage
Number is 12%~16%, and titanium dioxide mass percent is 2%~3%.
In the step (4), time of immersion is 8~15min, and vacuum drying drying temperature is 90 DEG C, and drying time is
2h。
Relative to the prior art, the present invention has the following advantages：
1st, by basement membrane dip-coating modified solution, membrane surface crosslinks reaction, is grafted TiO2 functional layers so that film surface
With good hydrophily, the resistant to pollution effect of ultrafiltration membrane is increased；TiO simultaneously2Basement membrane blending is added in solation, it is also sharp
In the transmission of hydrone in ultrafiltration membrane, the water flux of ultrafiltration membrane is improved.
2nd, using ultrasonic power, to TiO2TiO in sol solution and modified solution2Nano-particle is handled, can
It is dispersed in ultrafiltration membrane, the gap of ultrafiltration membrane will not be caused to increase, rejection because of " reunion " phenomenon occurs between particle
It reduces.
3rd, the TiO of membrane surface grafting2Functional layer, under the irradiation of ultraviolet light, ultrafiltration membrane surface TiO2 urges as light
Photocatalysis, the light induced electron of generation and hole occur for agent, then are combined generation with oxidisability with lewis' acid or gone back
Organic matter macromolecules degradation can be carbon dioxide and water and small point inorganic by the living radical of originality, this living radical
Son efficiently reduces the pollution of organic matter, substantially improves the water flux of ultrafiltration membrane, can reach 30%~40% water flux of promotion
Effect.
Specific embodiment
With reference to specific embodiment and test example further solution is made come the technical solution to the invention
It releases and illustrates, in order to which those skilled in the art fully understand the invention, but the explanation and illustration, it is not to this
The further restriction of innovation and creation technical solution, on the basis of the innovation and creation, the replacement for the simple numerical value made and
The improved technical solution routinely adjusted belongs to the protection domain of the invention.
Embodiment 1
A kind of preparation method of the super hydrophilic ultrafiltration membrane with photocatalysis performance, includes the following steps：
(1) TiO is prepared2Sol solution：Butyl titanate, glacial acetic acid are added in n,N-dimethylacetamide, mixed
Close solution a；Deionized water, the concentrated hydrochloric acid that mass concentration is 36% are added in n,N-dimethylacetamide, obtain mixed solution
b；Under conditions of mixed solution a ultrasonic vibrations, mixed solution b is added in mixed solution a, with mass concentration be 36% it is dense
Salt acid for adjusting pH obtains TiO to 42Sol solution, and keep TiO2Sol solution is in ultrasonic vibration state, for use；Wherein, it mixes
It closes the butyl titanate in solution a, glacial acetic acid, DMAC N,N' dimethyl acetamide and presses 30:1:50 volume ratio mixing, mixed solution b
In deionized water, concentrated hydrochloric acid, DMAC N,N' dimethyl acetamide press 20:1:167 volume ratio mixing, TiO2It is mixed in sol solution
It closes solution a, mixed solution b and presses 1:1 volume ratio mixing；
(2) casting solution is prepared：By the polyether sulfone of mass percent 14%, the polyvinylpyrrolidine of mass percent 1.5%
Ketone, the polyethylene glycol of mass percent 1%, mass percent 2% TiO2Sol solution is added in n,N-Dimethylformamide,
1h, ultrasonic 6h are stirred under 80 DEG C of heating temperature, vacuum defoamation 12h obtains casting solution；
(3) ultrafiltration membrane basement membrane is prepared：Using non-woven fabrics as supporting layer, casting solution is poured on non-woven fabrics, with stainless steel spatula
Casting solution is carried out to scrape film process, scrapes film thickness as 180 μm, knifing speed is 1.5m/min, then immerse temperature for 10 DEG C go from
In sub- water, curing obtains ultrafiltration membrane basement membrane；
(4) finished film is prepared：By the ethylene glycol of mass percent 1%, the polyacrylic acid of mass percent 12%, quality hundred
The titanium dioxide of score 2% is added in deionized water, stirs 10min, and ultrasonic 2h obtains modified solution, then using modified solution
To membrane surface dip-coating 8min, be dried in vacuo 2h, drying temperature is 90 DEG C, then immerse pure water to get.
Embodiment 2
A kind of preparation method of the super hydrophilic ultrafiltration membrane with photocatalysis performance, includes the following steps：
(1) TiO is prepared2Sol solution：Butyl titanate, glacial acetic acid are added in n,N-dimethylacetamide, mixed
Close solution a；Deionized water, the concentrated hydrochloric acid that mass concentration is 36% are added in n,N-dimethylacetamide, obtain mixed solution
b；Under conditions of mixed solution a ultrasonic vibrations, mixed solution b is added in mixed solution a, with mass concentration be 36% it is dense
Salt acid for adjusting pH obtains TiO to 42Sol solution, and keep TiO2Sol solution is in ultrasonic vibration state, for use；Wherein, it mixes
It closes the butyl titanate in solution a, glacial acetic acid, DMAC N,N' dimethyl acetamide and presses 30:1:50 volume ratio mixing, mixed solution b
In deionized water, concentrated hydrochloric acid, DMAC N,N' dimethyl acetamide press 20:1:167 volume ratio mixing, TiO2It is mixed in sol solution
It closes solution a, mixed solution b and presses 1.5:1 volume ratio mixing；
(2) casting solution is prepared：By the polyether sulfone of mass percent 16%, mass percent 2% polyvinylpyrrolidone,
The polyethylene glycol of mass percent 2%, the TiO of mass percent 3%2Sol solution is added in n,N-dimethylacetamide,
2h, ultrasonic 7h are stirred under 80 DEG C of heating temperature, vacuum defoamation 15h obtains casting solution；
(3) ultrafiltration membrane basement membrane is prepared：Using non-woven fabrics as supporting layer, casting solution is poured on non-woven fabrics, with stainless steel spatula
Casting solution is carried out to scrape film process, it is 200 μm to scrape film thickness, and knifing speed is 3m/min, then immerses temperature for 15 DEG C of deionizations
In water, curing obtains ultrafiltration membrane basement membrane；
(4) finished film is prepared：By the ethylene glycol of mass percent 1.3%, the polyacrylic acid of mass percent 14%, quality
The titanium dioxide of percentage 2.5% is added in deionized water, stirs 10min, ultrasonic 3h, obtains modified solution, then using modification
Solution is dried in vacuo 2h to membrane surface dip-coating 12min, and drying temperature is 90 DEG C, then immerse pure water to get.
Embodiment 3
A kind of preparation method of the super hydrophilic ultrafiltration membrane with photocatalysis performance, includes the following steps：
(1) TiO is prepared2Sol solution：Butyl titanate, glacial acetic acid are added in n,N-dimethylacetamide, mixed
Close solution a；Deionized water, the concentrated hydrochloric acid that mass concentration is 36% are added in n,N-dimethylacetamide, obtain mixed solution
b；Under conditions of mixed solution a ultrasonic vibrations, mixed solution b is added in mixed solution a, with mass concentration be 36% it is dense
Salt acid for adjusting pH obtains TiO to 42Sol solution, and keep TiO2Sol solution is in ultrasonic vibration state, for use；Wherein, it mixes
It closes the butyl titanate in solution a, glacial acetic acid, DMAC N,N' dimethyl acetamide and presses 30:1:50 volume ratio mixing, mixed solution b
In deionized water, concentrated hydrochloric acid, DMAC N,N' dimethyl acetamide press 20:1:167 volume ratio mixing, TiO2It is mixed in sol solution
It closes solution a, mixed solution b and presses 2:1 volume ratio mixing；
(2) casting solution is prepared：By the polyether sulfone of mass percent 19%, the polyvinylpyrrolidine of mass percent 2.5%
Ketone, the polyethylene glycol of mass percent 3%, mass percent 4% TiO2Sol solution is added in N-Methyl pyrrolidone,
3h, ultrasonic 8h are stirred under 80 DEG C of heating temperature, vacuum defoamation 18h obtains casting solution；
(3) ultrafiltration membrane basement membrane is prepared：Using non-woven fabrics as supporting layer, casting solution is poured on non-woven fabrics, with stainless steel spatula
Casting solution is carried out to scrape film process, it is 220 μm to scrape film thickness, and knifing speed is 5m/min, then immerses temperature for 20 DEG C of deionizations
In water, curing obtains ultrafiltration membrane basement membrane；
(4) finished film is prepared：By the ethylene glycol of mass percent 1.5%, the polyacrylic acid of mass percent 16%, quality
The titanium dioxide of percentage 3% is added in deionized water, stirs 10min, ultrasonic 4h, obtains modified solution, then molten using modification
Liquid is dried in vacuo 2h to membrane surface dip-coating 15min, and drying temperature is 90 DEG C, then immerse pure water to get.
Embodiment 4
TiO described in embodiment 42Sol solution presses 1 by mixed solution a, mixed solution b:1 volume ratio mixing, it is other
Preparation process it is same as Example 1.
Embodiment 5
TiO described in embodiment 52Sol solution presses 3 by mixed solution a, mixed solution b:1 volume ratio mixing, it is other
Preparation process it is same as Example 3.
Embodiment 6
Step (1) described in embodiment 6 replaces ultrasonic power, other preparation processes and embodiment 2 using agitating mode
It is identical.
Embodiment 7
Step (4) described in embodiment 7, not using modified solution, other preparation processes are same as Example 4.
Embodiment 8
Step (4) described in embodiment 8, the titanium dioxide mass percent in modified solution are 1%, and others prepare step
It is rapid same as Example 3.
Embodiment 9
Step (4) described in embodiment 9, the titanium dioxide mass percent in modified solution are 4%, and others prepare step
It is rapid same as Example 2.
Embodiment 10
Step (4) described in embodiment 10, not using ultrasound treatment patterns, other preparation processes are same as Example 1.
Test example 1
Using KrussDSA30 type contact angle measurements, under the conditions of 25 DEG C, pass through drop method determination sample film surface of lying
Water contact angle, used ultra-pure water often drop in 3 μ l or so, image are preserved after the 5s that drips, each sample film measures 10 times, right
Contact angle result takes arithmetic mean of instantaneous value.
Sample mould is ultrafiltration membrane prepared by embodiment 1-10.
Test result is shown in Table 1：
Table 1
| Sample film | Contact angle (°) |
| 1 | 19.2 |
| 2 | 18.4 |
| 3 | 17.1 |
| 4 | 18.8 |
| 5 | 17.0 |
| 6 | 18.7 |
| 7 | 23.6 |
| 8 | 22.5 |
| 9 | 15.8 |
| 10 | 18.3 |
As can be seen from the above table, sample film 7 is not grafted basement membrane titania functional, water contact using modified solution
Angle is bigger than normal；Sample film 8 is with the content of titanium dioxide of 9 surface functional layer of sample film and the water contact angle size of ultrafiltration membrane surface in anti-
Than；Not using ultrasound treatment patterns, water contact angle slightly reduces sample film 10.
Test example 2
By the use of the aqueous solution of the humic acid of 2000ppm as test fluid, pH value 7.3, under 30psi operating pressures, continuously
After filtering 72h, the initial flux of record sample film, rejection and the flux of 72 hours, rejection.
Sample film is the ultrafiltration membrane of embodiment 1-10.
Test result is shown in Table 2：
Table 2
As can be seen from the above table, the flux of sample film 1-3 and rejection are relatively stable；Four fourth of metatitanic acid in 4 basement membrane of sample film
Ester content is less, affects the flux of ultrafiltration membrane；Butyl titanate content is more in 5 basement membrane of sample film, and the flux of ultrafiltration membrane is not
There is notable growth, but result in rejection decline；Not using ultrasound treatment patterns, the flux of ultrafiltration membrane is increased slightly sample film 6,
But rejection is impacted；Modified solution is not used in sample film 7, and membrane structure is single, and ultrafiltration membrane flux is excellent, but rejection occurs
It is apparent to reduce；In the functional layer of sample film 8, content of titanium dioxide is less, and ultrafiltration membrane flux is relatively low；The function of sample film 9
In layer, content of titanium dioxide is more, and the flux of ultrafiltration membrane does not have notable growth, and rejection but has apparent downslide；Sample film 10
Not using ultrasound treatment patterns, rejection significantly decreases.
After 72h is continuously filtered, the flux of ultrafiltration membrane slightly reduces, and attenuation rate is 5% or so, with good
Resistance tocrocking.
Test example 3
By the use of the aqueous solution of the humic acid of 2000ppm as test fluid, pH value 7.1, in 30psi operating pressures and ultraviolet light
Under line irradiation, after continuous filtering 72h, the initial flux of record sample film, rejection and the flux of 72 hours, rejection.
Sample film is the ultrafiltration membrane of embodiment 1-10.
Test result is shown in Table 3：
Table 3
The test result of upper table and the test result of test example 2 are compared, it can be seen that in the irradiation of ultraviolet light
Under, the flux of ultrafiltration membrane improves 30%~40%, but rejection is held essentially constant.
Claims (8)
1. a kind of preparation method of the super hydrophilic ultrafiltration membrane with photocatalysis performance, which is characterized in that include the following steps：
(1) TiO is prepared2Sol solution：Butyl titanate, glacial acetic acid are added in n,N-dimethylacetamide, obtain mixed solution
a；Deionized water, concentrated hydrochloric acid are added in n,N-dimethylacetamide, obtain mixed solution b；In mixed solution a ultrasonic vibrations
Under the conditions of, mixed solution b is added in mixed solution a, pH to 4 is adjusted with concentrated hydrochloric acid, obtains TiO2Sol solution, and keep
TiO2Sol solution is in ultrasonic vibration state, for use；
(2) casting solution is prepared：By polyether sulfone, polyvinylpyrrolidone, polyethylene glycol, TiO2Sol solution is added in organic solvent,
Heating stirring, ultrasound, vacuum defoamation obtain casting solution；
(3) ultrafiltration membrane basement membrane is prepared：Using non-woven fabrics as supporting layer, casting solution is poured on non-woven fabrics, with stainless steel spatula to casting
Film liquid carries out scraping film process, then immerse in deionized water, and curing obtains ultrafiltration membrane basement membrane；
(4) finished film is prepared：Using modified solution to membrane surface carry out dip-coating, vacuum drying, then immerse pure water to get.
2. the preparation method of the super hydrophilic ultrafiltration membrane with photocatalysis performance as described in claim 1, which is characterized in that described
In step (1), butyl titanate, glacial acetic acid in mixed solution a, n,N-dimethylacetamide, by 30:1:50 volume ratio is mixed
It closes；Deionized water, concentrated hydrochloric acid, n,N-dimethylacetamide in mixed solution b, by 20:1:167 volume ratio mixing；TiO2
Mixed solution a, mixed solution b in sol solution, by 1~2:1 volume ratio mixing, the mass concentration of concentrated hydrochloric acid is 36%.
3. the preparation method of the super hydrophilic ultrafiltration membrane with photocatalysis performance as described in claim 1, which is characterized in that described
In step (2), the mass percent of polyether sulfone is 14%~19%, the mass percent of polyvinylpyrrolidone for 1.5%~
2.5%, the mass percent of polyethylene glycol is 1%~3%, TiO2The mass percent of sol solution is 2%~4%.
4. the preparation method of the super hydrophilic ultrafiltration membrane with photocatalysis performance as described in claim 1, which is characterized in that described
In step (2), organic solvent is n,N-Dimethylformamide, any in n,N-dimethylacetamide, N-Methyl pyrrolidone
Kind.
5. the preparation method of the super hydrophilic ultrafiltration membrane with photocatalysis performance as described in claim 1, which is characterized in that described
In step (2), heating temperature is 80 DEG C, and mixing time is 1~3h, and ultrasonic time is 6~8h, the vacuum defoamation time for 12~
18h。
6. the preparation method of the super hydrophilic ultrafiltration membrane with photocatalysis performance as described in claim 1, which is characterized in that described
In step (3), it is 180~220 μm to scrape film thickness, and knifing speed is 1.5~5m/min, and deionized water temperature is 10~20 DEG C.
7. the preparation method of the super hydrophilic ultrafiltration membrane with photocatalysis performance as described in claim 1, which is characterized in that described
In step (4), the preparation method of modified solution is：Ethylene glycol, polyacrylic acid, titanium dioxide are added in deionized water, stirring
10min, wherein 2~4h of ultrasound, quality of glycol percentage are 1%~1.5%, polyacrylic acid mass percent for 12%~
16%, titanium dioxide mass percent is 2%~3%.
8. the preparation method of the super hydrophilic ultrafiltration membrane with photocatalysis performance as described in claim 1, which is characterized in that described
In step (4), time of immersion is 8~15min, and vacuum drying drying temperature is 90 DEG C, drying time 2h.
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