CN109925893A - A kind of visible light catalytic type composite ceramics nanofiltration membrane and its preparation method and application - Google Patents
A kind of visible light catalytic type composite ceramics nanofiltration membrane and its preparation method and application Download PDFInfo
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Abstract
The present invention provides a kind of visible light catalytic type composite ceramics nanofiltration membranes and its preparation method and application, belong to ceramic membrane technology field.Visible light catalytic type composite ceramics nanofiltration membrane provided by the invention includes ceramic super-filtering film and the nanometer N-TiO for being attached to the Ceramic excessive filtration film surface2Coating.The present invention is by nanometer N-TiO2It is attached to the surface of ceramic super-filtering film, due to N-TiO2The coating of nanoparticle can make Ceramic excessive filtration film surface more fine and close, and membrane aperture reduces, and improve the separation accuracy of ceramic super-filtering film, reach nanofiltration effect；Under visible light action, by N-TiO2Light-catalyzed reaction is capable of the pollutant of the efficient oxidation degradation ceramic membrane surface deposition, alleviates fouling membrane.
Description
Technical field
The present invention relates to ceramic membrane technology field more particularly to a kind of visible light catalytic type composite ceramics nanofiltration membranes and its system
Preparation Method and application.
Background technique
Ceramic membrane is a kind of inorganic functional membrane material with excellent chemical stability, thermal stability and mechanical strength,
Can acidproof, alkaline-resisting, organic solvent-resistant, high temperature resistant, thus in environmental project, bioengineering, chemical industry, food industry, stone
The field that oiling work, metallurgical industry etc. are related to harsh system is widely applied, and the market sales revenue is with 30% annual growth
Rapid growth is one of most promising membrane material.
Nanofiltration membrane refers to that filtering accuracy reaches the ceramic membrane of nanofiltration rank.Nanofiltration rank refers between ultrafiltration and reverse osmosis
Between thoroughly, average pore size is 1~2nm, can separate the membrane material that molecular weight is 200~1000Da substance.In recent years, with liquid
Substance separation demand of the body separation field to the separation of different valence state ion and relative molecular weight within the scope of 200~1000Da
Increasingly increase, the especially national pay attention to day by day to process industrial energy-saving and emission-reduction, the higher nanofiltration membrane of separation accuracy is more next
The concern for more causing everybody becomes one of the research hotspot in ceramic membrane field.
On the other hand, membrane pollution problem is always the problem for perplexing membrane separation technique practical application, and especially ceramic membrane is normal
For the separation of substance extraordinary in harsh system, film surface is easily contaminated and leads to the decline of membrane flux, reduced service life.It is slow
The conventional method for solving fouling membrane is mainly cleaned, but there is the problems such as energy consumption is high, at high cost and film device down time is long.
Summary of the invention
The purpose of the present invention is to provide a kind of visible light catalytic type composite ceramics nanofiltration membrane and its preparation method and application,
Nanofiltration membrane prepared by the present invention separation accuracy with higher and antifouling property.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of visible light catalytic type composite ceramics nanofiltration membrane, including ceramic super-filtering film and it is attached to described
The nanometer N-TiO of Ceramic excessive filtration film surface2Coating.
Preferably, the ceramic super-filtering film and nanometer N-TiO2It further include binder between coating.
Preferably, the nanometer N-TiO2Coating with a thickness of 2~50 μm.
Preferably, the nanometer N-TiO2The molar ratio of N and Ti is 0.05~0.2:1 in coating.
The present invention also provides the preparation method of the visible light catalytic type composite ceramics nanofiltration membrane described in above-mentioned technical proposal,
The following steps are included:
(1) by titanium source, dehydrated alcohol and inhibitor mixed, the pH value of mixed liquor is adjusted, solution A is obtained；Adjust anhydrous second
The pH value of alcohol solution, obtains solution B；The pH value of the solution A and solution B is 2~4；
(2) solution B is slowly added dropwise into solution A, obtains TiO2Colloidal sol；
(3) Xiang Suoshu TiO2Nitrogen source is added in colloidal sol, forms N-TiO after ageing2Gel；
(4) by the N-TiO2Gel coating successively passes through naturally dry, drying and calcining to Ceramic excessive filtration film surface,
Obtain visible light catalytic type composite ceramics nanofiltration membrane.
Preferably, the volume ratio of titanium source in the step (2), dehydrated alcohol, inhibitor and water is preferably (5~10): (20
~40): (0.5~2): (5~10).
It preferably, further include in Ceramic excessive filtration film surface coated with adhesive before carrying out step (4).
Preferably, the temperature dried in the step (4) is 60~80 DEG C, and the time of drying is 2~12h.
Preferably, the temperature calcined in the step (4) is 250~400 DEG C, and heating rate is 0.5~3 DEG C/min, is forged
The time of burning is 0.5~2h.
The present invention separately provides visible light catalytic type composite ceramics nanofiltration membrane described in above-mentioned technical proposal or using above-mentioned
The visible light catalytic type composite ceramics nanofiltration membrane that preparation method described in technical solution is prepared is separating under visible light action
Application in field.
The present invention provides a kind of visible light catalytic type composite ceramics nanofiltration membrane, including ceramic super-filtering film and it is attached to described
The nanometer N-TiO of Ceramic excessive filtration film surface2Coating.The present invention is by nanometer N-TiO2Coating is attached to the surface of ceramic super-filtering film, by
In N-TiO2The coating of nanoparticle keeps Ceramic excessive filtration film surface more fine and close, and membrane aperture reduces, and improves point of ceramic super-filtering film
From precision, reach nanofiltration effect；Under visible light action, by N-TiO2Light-catalyzed reaction, being capable of the efficient oxidation degradation ceramics
The pollutant of film surface deposition, alleviates fouling membrane.Embodiment the result shows that, composite ceramics nanofiltration membrane produced by the present invention is averaged
Aperture is about 1.5~1.8nm, illustrates composite ceramics nanofiltration membrane separation accuracy with higher of the invention, can reach nanofiltration
Effect；Composite ceramics nanofiltration membrane of the invention under visible light, reaches 92% to the removal rate of methylene blue solution in 5h, explanation
N-TiO is utilized under sunlight irradiation2Coating can fall the contaminant degradation of film surface, to alleviate the pollution feelings of film surface
Condition.
In addition, the light-catalyzed reaction of film surface can also play organic pollutant in further Decomposition Wastewater, killing bacterium etc.
The effect of microorganism；Due to N-TiO2Raw light-catalyzed reaction can be issued in excited by visible light, whole energy consumption ratio when process operation
Ultraviolet catalytic substantially reduces.
The present invention also provides the preparation method of the visible light catalytic type composite ceramics nanofiltration membrane, systems provided by the invention
Preparation Method reaction condition is mild, reaction is uniform and easy to operate.
Specific embodiment
The present invention provides a kind of visible light catalytic type composite ceramics nanofiltration membrane, including ceramic super-filtering film and it is attached to described
The nanometer N-TiO of Ceramic excessive filtration film surface2Coating.
In the present invention, the nanometer N-TiO2The thickness of coating is preferably 2~50 μm, and further preferably 5~45 μm,
Most preferably 10~40 μm；Chemically on composition, the nanometer N-TiO2Coating includes nanometer N-TiO2, the N-TiO2Refer to
It is the TiO of N doping2.In the present invention, the nanometer N-TiO2The molar ratio of N and Ti is preferably 0.05~0.2:1 in coating.This
Invention passes through control nanometer N-TiO2The molar ratio of middle N and Ti makes finally obtained composite ceramics nanofiltration membrane have excellent light
Catalytic performance and preventing membrane pollution performance.The present invention is to the nanometer N-TiO2Partial size be not particularly limited, by the present invention it is subsequent
Preparation method determines.
In the present invention, the ceramic super-filtering film preferably includes Al2O3Ceramic super-filtering film；The ceramic super-filtering film is averaged
Aperture is preferably 2~20nm.
In the present invention, the ceramic super-filtering film and nanometer N-TiO2It further include binder between coating, preferably with bonding
The form of oxidant layer exists.In the present invention, the binder is preferably -2 pyrrolidone solution of 1- methyl of Kynoar, gathers
The N,N-dimethylformamide solution of vinylidene, -2 pyrrolidone solution of 1- methyl of polyvinyl chloride or the N, N- of polyvinyl chloride
Dimethyl formamide solution；The concentration of the binder is preferably 10~30wt%.In the present invention, the thickness of the adhesive layer
Preferably 2~30 μm, further preferably 6~25 μm of degree.Binder of the present invention can make a nanometer N-TiO2Coating is secured
The surface for being attached to ceramic super-filtering film, increase coating stability.
The present invention is by nanometer N-TiO2It is attached to the surface of ceramic super-filtering film, due to N-TiO2The coating of nanoparticle, can
Keep Ceramic excessive filtration film surface more fine and close, membrane aperture reduces, and improves the separation accuracy of ceramic super-filtering film, reaches nanofiltration effect；?
It can be seen that under light action, by N-TiO2Light-catalyzed reaction is capable of the pollutant of the efficient oxidation degradation ceramic membrane surface deposition, is alleviated
Fouling membrane.
In addition, the light-catalyzed reaction of film surface can also play organic pollutant in further Decomposition Wastewater, killing bacterium etc.
The effect of microorganism；Due to N-TiO2Raw light-catalyzed reaction can be issued in excited by visible light, whole energy consumption ratio when process operation
Ultraviolet catalytic substantially reduces.
The present invention also provides the preparation method of the visible light catalytic type composite ceramics nanofiltration membrane described in above-mentioned technical proposal,
The following steps are included:
(1) by titanium source, dehydrated alcohol and inhibitor mixed, the pH value of mixed liquor is adjusted, solution A is obtained；Adjust anhydrous second
The pH value of alcohol solution, obtains solution B；The pH value of the solution A and solution B is 2~4；
(2) solution B is slowly added dropwise into solution A, obtains TiO2Colloidal sol；
(3) Xiang Suoshu TiO2Nitrogen source is added in colloidal sol, forms N-TiO after ageing2Gel；
(4) by the N-TiO2Gel coating successively passes through naturally dry, drying and calcining to Ceramic excessive filtration film surface,
Obtain visible light catalytic type composite ceramics nanofiltration membrane.
Titanium source, dehydrated alcohol and inhibitor mixed are adjusted the pH value of mixed liquor, obtain solution A by the present invention；In the present invention
Described in pH value be 2~4.
In the present invention, the titanium source is preferably butyl titanate or titanium tetrachloride, and the inhibitor is preferably glacial acetic acid
Or concentrated nitric acid.The present invention does not have particular/special requirement to the mixed mode, using hybrid mode well known to those skilled in the art
?.PH value present invention preferably employs concentrated nitric acid adjustment mixed liquor is 2~4, obtains solution A.The present invention is to the titanium source, nothing
The source of water-ethanol and inhibitor does not have particular/special requirement, using commercial goods well known to those skilled in the art.
The pH value that the present invention adjusts dehydrated alcohol aqueous solution is identical as the pH value of above-mentioned solution A, obtains solution B.The present invention
It is preferred that using the pH value of concentrated nitric acid adjustment dehydrated alcohol aqueous solution.
In the present invention, the solution A and solution B prepare no chronological order, i.e., first prepare solution A or first make
Standby solution B.
After obtaining solution A and solution B, the solution B is slowly added dropwise into solution A the present invention, obtains TiO2Colloidal sol.
The solution B is preferably added dropwise in solution A under conditions of being vigorously stirred by the present invention.In the present invention, described
The rate of stirring is preferably 800r/min~1200r/min.Using the solution B and the solution A reaction system total as one, institute
The volume ratio for stating titanium source in reaction system, dehydrated alcohol, inhibitor and water is preferably (5~10): (20~40): (0.5~2):
(5~10).The dosage of inhibitor of the present invention does not include the dosage of concentrated nitric acid when adjusting pH value.The present invention exists to the ethyl alcohol
Allocation proportion in solution B and solution A does not have particular/special requirement, system can be made to be uniformly dispersed.In the present invention, described molten
The volume ratio of ethyl alcohol and ethyl alcohol in solution A is preferably 2~1:1 in liquid B, most preferably 1:1.In the present invention, the dropwise addition
Speed is preferably 0.05~0.2mL/s.The water that butyl titanate occurs to the process of solution A is slowly added dropwise in solution B by the present invention
Solution, condensation reaction.The present invention prepares the ethanol solution (solution A) and ethanol water (solution B) of butyl titanate respectively, makes two
A reactive component (butyl titanate and water) is first scattered, then the reaction of solution A and solution B occurs, and it is violent to slow down hydrolysis
Degree cooperates rate of addition, makes reaction uniformly, guarantee the titanium dioxide generated in nanoscale, and it is of uniform size.Solution B is dripped
After adding, the present invention preferably continues to 0.5~3h of stirring, further preferably 0.5~2h, to guarantee that solution B and solution A are sufficiently mixed
Conjunction is uniform, reacts, and avoids local concentration excessively high, reacts excessively violent, so that the crystal grain ultimately produced is excessive.
Obtain TiO2After colloidal sol, the present invention is to the TiO2Nitrogen source is added in colloidal sol, forms N-TiO after ageing2Gel.
In the present invention, the nitrogen source is preferably urea, ammonium chloride or ammonium hydroxide；The nitrogen source preferably adds as a solution
Add, the concentration of the nitrogen source solution is preferably 1~2mol/L, the nitrogen source solution and TiO2The volume ratio of colloidal sol is preferably 1:13
~20.The present invention is to TiO2Nitrogen source is added in colloidal sol, the bonding reaction of N-Ti occurs, generates N-TiO2Nucleus.The present invention preferably exists
The nitrogen source is added to TiO under conditions of being vigorously stirred2In colloidal sol.In the present invention, the rate of the stirring is preferably
500r/min~1000r/min generates state depending on gel and gradually decreases stirring rate.In the present invention, the time of the stirring
Preferably 2~6h, further preferably 2h.Nitrogen source is added to TiO by present invention selection2In colloidal sol, rather than by TiO2Colloidal sol is added
It is to make mixed system be easier to be uniformly dispersed into nitrogen source.After stirring, mixed system is aged by the present invention.At this
In invention, the ageing is preferably still aging, and the still aging time is preferably 2~12h.It is of the present invention to be aged
Cheng Zhong slowly polymerize between colloidal sol, forms the N-TiO of three-dimensional net structure2Gel.Obtain N-TiO2After gel, the present invention will
The N-TiO2Gel coating successively passes through naturally dry, drying and calcining, obtains visible light catalytic to Ceramic excessive filtration film surface
Type composite ceramics nanofiltration membrane.
The present invention is preferred first in Ceramic excessive filtration film surface coated with adhesive, obtains the ceramic super-filtering film for being covered with binder, so
Afterwards by the N-TiO2Gel coating is to the Ceramic excessive filtration film surface for being covered with binder.In the present invention, the binder is preferred
For -2 pyrrolidone solution of 1- methyl of Kynoar, N,N-dimethylformamide solution, the polyvinyl chloride of Kynoar
- 2 pyrrolidone solution of 1- methyl or polyvinyl chloride N,N-dimethylformamide solution；The concentration of the binder is preferably
10~30wt%.The present invention does not have particular/special requirement to the coating method of the binder, and use is well known to those skilled in the art
The modes such as coating method, such as scraper smearing, dipping-lifting.In the present invention, the thickness of the adhesive coated is corresponding
The thickness of adhesive layer in visible light catalytic type composite ceramics nanofiltration membrane described in above-mentioned technical proposal, which is not described herein again.
It obtains after being covered with the ceramic super-filtering film of binder, the present invention is by the N-TiO2Gel coating is to being covered with binder
Ceramic excessive filtration film surface obtains the presoma of visible light catalytic type composite ceramics nanofiltration membrane.
The present invention is to the N-TiO2The coating method of gel does not have particular/special requirement, and use is well known to those skilled in the art
Coating method.In the present invention, the N-TiO2The thickness of gel coating corresponds to nanometer N- described in above-mentioned technical proposal
TiO2The thickness of coating.The present invention is preferably coated with 3~5 times and reaches target thickness.
After obtaining the presoma of visible light catalytic type composite ceramics nanofiltration membrane, the present invention is compound by the visible light catalytic type
The presoma of nanofiltration membrane successively passes through naturally dry, drying and calcining, obtains visible light catalytic type composite ceramics nanofiltration membrane.
In the present invention, the naturally dry can remove the Free water and part pore water on presoma surface.The present invention
There is no particular/special requirement to the time of the naturally dry, enables to presoma dry tack free.In the present invention, the baking
Dry temperature is preferably 60~80 DEG C, and the time of the drying is preferably 2~12h.Drying of the present invention can further be gone
Except presoma pore water and materialization combination water.The present invention uses low temperature drying, can alleviate surface in drying process and acutely shrink
Caused duct collapses, reunion and specific surface area reduce.For the present invention using first naturally dry, the mode then dried is dried
Journey is incremental, can prevent in the drying process since moisture evaporation causes nano-powder to be reunited, particle increases, specific surface area
Reduce to reduce catalytic activity.In the present invention, the temperature of the calcining is preferably 250~400 DEG C, the time of the calcining
Preferably 0.5~2h.The present invention preferably rises to calcination temperature from room temperature, and the rate of the heating is preferably 0.5~3 DEG C/min.
The process of calcining of the present invention can remove presoma internal crystallization water.
Preparation method provided by the invention is easy to operate, the N-TiO that will be prepared2Nanogel is coated on ceramic super-filtering film
Surface, successively passes through naturally dry, drying and calcining, and finally obtained composite ceramics nanofiltration membrane has good visible light catalytic
Function.
The present invention also provides the visible light catalytic type composite ceramics nanofiltration membranes described in above-mentioned technical proposal to make in visible light
Application under in separation field.The present invention does not have particular/special requirement to the isolated object, common for nanofiltration membrane
Separation object.The present invention does not have particular/special requirement to the specific embodiment of the application, using those skilled in the art
Well known embodiment.The present invention does not have particular/special requirement to the source of the visible light, and natural light can be used or simulation can
It is light-exposed.When using simulated visible light, the present invention does not have particular/special requirement to the light intensity of the simulated visible light, can be for processing feelings
Condition is adjusted.
Below with reference to embodiment to visible light catalytic type composite ceramics nanofiltration membrane provided by the invention and preparation method thereof and
Using being described in detail, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
Take 10mL dehydrated alcohol and 5mL butyl titanate that beaker is added, the another 0.5mL glacial acetic acid that is added is used as inhibitor
It is 2 that concentrated nitric acid, which adjusts solution ph, obtains A liquid with magnetic stirrer 0.5h.10mL dehydrated alcohol and 5mL are taken with pipette
Deionized water is put into beaker, adjusts solution ph with concentrated nitric acid as 2, obtains B liquid.B liquid is instilled into A with the speed of 0.05mL/s
Liquid continues to be vigorously stirred 0.5h obtaining faint yellow colloidal sol.It is to be vigorously stirred 2h in 1mol/L ammonium chloride addition colloidal sol by 2mL concentration
Still aging 6h forms N-TiO afterwards2Gel.PVDF (Kynoar) is dissolved in NMP (- 2 pyrrolidones of 1- methyl) solution
It prepares PVDF concentration and is the adhesive coating of 20wt%, and be applied to the dry Al of cleaning2O3Ceramic super-filtering film (average pore size
About 15nm) surface, 10 μm of adhesive layer thickness.The N-TiO that will be aged2Gel coating is in Al2O3Ultrafiltration ceramic super-filtering film table
Face, to film surface after natural drying in 70 DEG C of drying 6h, is then transferred in Muffle furnace under the conditions of 350 DEG C by 20 μm of coating layer thickness
2h is calcined to get finished product.
N-TiO obtained2Nanofiltration membrane average pore size is about 1.8nm, pure water flux 31Lm-2·h-1·bar-1。
Nature visible light is simulated using xenon lamp, under the xenon lamp irradiation of 200W, N-TiO2Nanofiltration membrane energy catalytic degradation methylene blue
Solution, removal rate reaches 92% after reacting 5h.
Embodiment 2
15mL dehydrated alcohol is taken, beaker is added in 8mL butyl titanate, and it is 2 that solution ph is adjusted by inhibitor of concentrated nitric acid,
A liquid is obtained with magnetic stirrer 0.5h.It takes 15mL dehydrated alcohol and 8mL deionized water to be put into beaker, is adjusted with concentrated nitric acid
Solution ph is 2, obtains B liquid.B liquid is instilled into A liquid with the speed of 0.1mL/s, continue to be vigorously stirred 0.5h obtain it is faint yellow molten
Glue.It is that still aging 6h forms N-TiO after being vigorously stirred 2h in 1mol/L urea liquid addition colloidal sol by 1.4mL concentration2Gel.
PVDF (Kynoar) is dissolved in that the coating that PVDF concentration is 18wt% is prepared in DMF (N,N-dimethylformamide) solution is viscous
Agent is tied, and is applied to the dry Al of cleaning2O3Ceramic super-filtering film (average pore size is about 10nm) surface, 10 μ of adhesive layer thickness
m.The N-TiO that will be aged2Gel coating is in Al2O3Ceramic excessive filtration film surface, 18 μm of coating layer thickness, to film surface naturally dry
Afterwards in 80 DEG C of drying 8h, then it is transferred in Muffle furnace under the conditions of 400 DEG C and calcines 2h to get finished product.
N-TiO obtained2Nanofiltration membrane average pore size is about 1.5nm, pure water flux 26Lm-2·h-1·bar-1。
Under the xenon lamp irradiation of 200W, N-TiO2Nanofiltration membrane energy catalytic degradation methylene blue solution, removal rate reaches after reacting 5h
83%.
Embodiment 3
Using titanium tetrachloride as presoma, ammonium hydroxide is nitrogen source, prepares N-TiO using sol-gel method2.Take the anhydrous second of 10mL
Beaker is added in pure and mild 8mL titanium tetrachloride, and for the another 1mL glacial acetic acid that is added as inhibitor, adjusting solution ph with concentrated nitric acid is 3, is used
Magnetic stirrer 1h obtains A liquid.It takes 10mL dehydrated alcohol and 10mL deionized water to be put into beaker, solution is adjusted with concentrated nitric acid
PH value is 3, obtains B liquid.B liquid is instilled into A liquid with the speed of 0.2mL/s, continues to be vigorously stirred 1h obtaining TiO2Colloidal sol.It will
Still aging 8h forms N-TiO after being vigorously stirred 2h in the ammonium hydroxide addition colloidal sol of 2mL2mol/L2Gel.By PVC (polyvinyl chloride)
It is dissolved in the adhesive coating for preparing PVC concentration in NMP (- 2 pyrrolidones of 1- methyl) solution as 20wt%, and is applied to cleaning
Dry Al2O3Ceramic super-filtering film (average pore size is about 10nm) surface, 8 μm of adhesive layer thickness.The N-TiO that will be aged2It is solidifying
Glue is coated in Al2O3Ceramic excessive filtration film surface, 10 μm of coating layer thickness, to film surface after natural drying in 80 DEG C of drying 10h, then
It is transferred in Muffle furnace under the conditions of 300 DEG C and calcines 1h to get finished product.
N-TiO obtained2Nanofiltration membrane average pore size is about 1.7nm, pure water flux 29Lm-2·h-1·bar-1。
Under the xenon lamp irradiation of 200W, N-TiO2Nanofiltration membrane energy catalytic degradation methylene blue solution, removal rate reaches after reacting 5h
78%.
As seen from the above embodiment, the present invention provides a kind of visible light catalytic type composite ceramics nanofiltration membrane and its preparation sides
The average pore size of method, composite ceramics nanofiltration membrane produced by the present invention is about 1.5~1.8nm, illustrates that composite ceramics of the invention are received
Filter membrane separation accuracy with higher, can reach nanofiltration effect；Composite ceramics nanofiltration membrane prepared by the present invention under visible light,
92% is reached to the removal rate of methylene blue solution in 5h, illustrates to utilize N-TiO in the case where sunlight irradiates2Coating can be film
The contaminant degradation on surface falls, thus alleviate the pollution condition of film surface, it is whole without using specific ultraviolet light condition
Energy consumption is lower.
In addition, the present invention is by nanometer N-TiO2Coating is attached to the surface of ceramic super-filtering film, due to N-TiO2Nanoparticle
Coating, can make Ceramic excessive filtration film surface more fine and close, and membrane aperture reduces, and improve the separation accuracy of ceramic super-filtering film, reach and receive
Filter effect.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of visible light catalytic type composite ceramics nanofiltration membrane, including ceramic super-filtering film and it is attached to the Ceramic excessive filtration film surface
Nanometer N-TiO2Coating.
2. visible light catalytic type composite ceramics nanofiltration membrane according to claim 1, which is characterized in that the ceramic super-filtering film
With nanometer N-TiO2It further include binder between coating.
3. visible light catalytic type composite ceramics nanofiltration membrane according to claim 1 or 2, which is characterized in that the nanometer N-
TiO2Coating with a thickness of 2~50 μm.
4. visible light catalytic type composite ceramics nanofiltration membrane according to claim 1 or 2, which is characterized in that the nanometer N-
TiO2The molar ratio of N and Ti is 0.05~0.2:1 in coating.
5. the preparation method of the described in any item visible light catalytic type composite ceramics nanofiltration membranes of Claims 1 to 4, including following step
It is rapid:
(1) by titanium source, dehydrated alcohol and inhibitor mixed, the pH value of mixed liquor is adjusted, solution A is obtained；Adjust dehydrated alcohol water
The pH value of solution, obtains solution B；The pH value of the solution A and solution B is 2~4；
(2) solution B is slowly added dropwise into solution A, obtains TiO2Colloidal sol；
(3) Xiang Suoshu TiO2Nitrogen source is added in colloidal sol, forms N-TiO after ageing2Gel；
(4) by the N-TiO2Gel coating successively passes through naturally dry, drying and calcining, obtaining can to Ceramic excessive filtration film surface
Light-exposed catalytic type composite ceramics nanofiltration membrane.
6. preparation method according to claim 5, which is characterized in that titanium source, dehydrated alcohol, inhibition in the step (2)
The volume ratio of agent and water is preferably (5~10): (20~40): (0.5~2): (5~10).
7. preparation method according to claim 5, which is characterized in that further include super in ceramics before carrying out step (4)
Filter membrane surface coated with adhesive.
8. preparation method according to claim 5, which is characterized in that the temperature dried in the step (4) is 60~80
DEG C, the time of drying is 2~12h.
9. preparation method according to claim 5, which is characterized in that the temperature calcined in the step (4) is 250~
400 DEG C, heating rate is 0.5~3 DEG C/min, and the time of calcining is 0.5~2h.
10. any one of the described in any item visible light catalytic type composite ceramics nanofiltration membranes of Claims 1 to 4 or claim 5~9
The visible light catalytic type composite ceramics nanofiltration membrane that the preparation method is prepared is under visible light action in separation field
Using.
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