CN106621844A - Anti-biological-pollution reverse osmosis membrane and preparation method thereof - Google Patents
Anti-biological-pollution reverse osmosis membrane and preparation method thereof Download PDFInfo
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- CN106621844A CN106621844A CN201611234599.0A CN201611234599A CN106621844A CN 106621844 A CN106621844 A CN 106621844A CN 201611234599 A CN201611234599 A CN 201611234599A CN 106621844 A CN106621844 A CN 106621844A
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- reverse osmosis
- osmosis membrane
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- biological contamination
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- 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
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/025—Reverse osmosis; Hyperfiltration
-
- 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
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
-
- 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
- B01D71/38—Polyalkenylalcohols; Polyalkenylesters; Polyalkenylethers; Polyalkenylaldehydes; Polyalkenylketones; Polyalkenylacetals; Polyalkenylketals
-
- 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
- B01D71/56—Polyamides, e.g. polyester-amides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/30—Cross-linking
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
- B01D2325/022—Asymmetric membranes
- B01D2325/023—Dense layer within the membrane
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/48—Antimicrobial properties
Abstract
The invention relates to the technical field of reverse osmosis membranes, in particular to an anti-biological-pollution reverse osmosis membrane and a preparation method thereof. The anti-biological-pollution reverse osmosis membrane comprises a dense membrane layer and a functional membrane layer crosslinked and cured on one surface of the dense membrane layer, wherein a plurality of nano-bulges are arranged on the surface of the surface, back to the dense membrane layer, of the functional membrane layer. The surface microstructure of the reverse osmosis membranes is changed, so that microbes such as bacteria and the like and tiny sundries cannot be attached to the membrane layer surface, and an anti-biological-pollution function is realized; the bulge structures are produced with physical means and cannot fail with use of the reverse osmosis membrane, and accordingly, the service life of the reverse osmosis membrane can be prolonged.
Description
Technical field
The present invention relates to reverse osmosis membrane technology field, more particularly to a kind of reverse osmosis membrane and its preparation side of stable against biological contamination
Method.
Background technology
Counter-infiltration is a kind of efficient liquid membrane separation technique, high with purifying rate, low power consumption and other advantages, at present by
It is widely used in the fields such as desalinization, wastewater treatment, drink water purifying.
But, as reverse osmosis membrane is in the use of clean water treatment, fouling membrane is increasingly severe, results even in reverse osmosis membrane
Directly fail.Therefore, the pollution problem of film has become one of subject matter that reverse osmosis membrane faces in application process.Problem
Concrete manifestation form be that during the use of reverse osmosis membrane, the microorganism such as bacterium causes anti-in film surface attachment and breeding
The permeance property of permeable membrane declines, and reduction of service life, causes economic loss, hinders the promotion and application of reverse osmosis membrane.
For the problems referred to above, the preparation method of some stable against biological contamination films is occurred in that in recent years, specifically include anti-to being combined
Antibacterials such as silver nanotube, titanium dioxide granule, doped quaternary ammonium salt class antibacterials etc. are added in permeable membrane, to reach reverse osmosis membrane
The effect of stable against biological contamination.But the antibacterials used in these patents are not green material, it is possible to which human body is caused
Adverse effect.
As can be seen here, or existing anti-pollution reverse osmosis membrane coats hydrophilic layer on reverse osmosis membrane surface, or adding anti-
Bacterium medicine, but hydrophilic coating and medicine can gradually be lost in, and so as to lose the function of the stable against biological contamination such as antibacterial, medicine can also
Human body or environment are impacted.
The content of the invention
Present invention aims to existing reverse osmosis membrane is susceptible to addition in pollution and reverse osmosis membrane resists micro- life
What thing medicament was present is susceptible to the problems such as failing with certain toxicity, or coating hydrophilic layer unfriendly to human body or environment,
A kind of reverse osmosis membrane of stable against biological contamination is provided.
Meanwhile, the present invention also correspondingly provides the preparation method of the reverse osmosis membrane of the stable against biological contamination.
To achieve the above object of the invention, the embodiment of the present invention employs following technical scheme：
A kind of reverse osmosis membrane of stable against biological contamination, the reverse osmosis membrane of the stable against biological contamination includes compact film, Yi Jijiao
Connection is solidified on the functional film layer on the surface of the compact film one；The functional film layer is received back on the surface of the compact film
Some projections of meter level.
And, the preparation method of the reverse osmosis membrane of above-mentioned stable against biological contamination is at least comprised the following steps：
Step S01. provide with the template of raised structures, the poly-vinyl alcohol solution that mass fraction is 0.2%～1.0%,
Mass fraction is 8%～15% curing agent solution and compact film；
The poly-vinyl alcohol solution is coated on the surface of the compact film one by step S02., controls thicknesses of layers for 2 μm
～5 μm；
Step S03. immerses the film layer that the coating of step S02 is obtained in the curing agent solution, right after standing 20s～40s
The film layer is dried process, obtains the membrane structure containing polyvinyl alcohol film layer；
Step S04. releasing agent is sprayed at after the template with raised structures, is imprinted in the polyvinyl alcohol film layer
Surface, heated cross-linking reaction simultaneously carries out separating treatment with the template with raised structures, obtains the stable against biological contamination
Reverse osmosis membrane.
The reverse osmosis membrane of the stable against biological contamination that the above embodiment of the present invention is provided, by physical means, by reverse osmosis membrane work(
Energy film layer is designed to nano level overshooting shape structure, due to changing reverse osmosis membrane surface microstructure so that micro- life such as bacterium
Thing and micro-impurities are difficult to be attached to film surface, play a part of stable against biological contamination, and due to being to adopt physical means
Manufacture raised structures, will not fail, so as to extend the service life of reverse osmosis membrane with use.
The preparation method of the reverse osmosis membrane of the stable against biological contamination that the above embodiment of the present invention is provided, using physical means, changes
Become the microstructure on reverse osmosis membrane surface, the method has process is simple, the raised structures that prepare are evenly distributed, antimicrobial attached
The features such as working well, the method is adapted to large-scale production surface and has bossed reverse osmosis membrane.
Description of the drawings
Technical scheme in order to be illustrated more clearly that the embodiment of the present invention, below by to be used needed for embodiment
Accompanying drawing is briefly described, it should be apparent that, drawings in the following description are only some embodiments of the present invention, for ability
For the those of ordinary skill of domain, on the premise of not paying creative work, can be attached to obtain others according to these accompanying drawings
Figure.
Fig. 1 is that the embodiment of the present invention is used to prepare the vertical view of the mould with raised structures of the reverse osmosis membrane of stable against biological contamination
Diagram is intended to；
Fig. 2 is the A- of the mould with raised structures that the embodiment of the present invention is used for the reverse osmosis membrane for preparing stable against biological contamination
A cross-sectional schematics；
Fig. 3 is the scanning electron microscope (SEM) photograph on the reverse osmosis membrane surface of stable against biological contamination provided in an embodiment of the present invention.
Specific embodiment
In order that the objects, technical solutions and advantages of the present invention become more apparent, it is right below in conjunction with drawings and Examples
The present invention is further elaborated.It should be appreciated that specific embodiment described herein is only to explain the present invention, and
It is not used in the restriction present invention.
The embodiment of the present invention provides a kind of reverse osmosis membrane of stable against biological contamination.The reverse osmosis membrane of the stable against biological contamination includes
Compact film, and crosslinking curing is in the functional film layer on the surface of the compact film one；The functional film layer is back to the densification
There are nano level some projections on the surface of film layer.
Wherein, back to the surface of the compact film, refer to functional film layer exposes table to functional film layer said herein
Face.
In any one embodiment, compact film is polyamide film layer, and polyamide film layer provides attachment for functional film layer
Substrate, functional film layer is played a supporting role as a part for reverse osmosis membrane.
In a preferred embodiment, functional film layer is polyvinyl alcohol film layer.
Preferably, the cross-sectional area of the projection of polyvinyl alcohol film layer is 7 × 103nm2～2 × 105nm2, the height of projection is
100nm～1 μm；Spacing between projection is 100nm～500nm.Nano level raised structures, reduce the microorganism such as bacterium and its
The possibility of his small objects attachment, in the water of flowing, the microorganism such as bacterium of close functional film layer, it will scratched by projection
Cell membrane, causes bacterial death.
It is further preferable that the structure of projection be cylindrical protrusion, conoid protuberance, denation or square protrusion in extremely
Few one kind, by the projection of cylindric either taper either triangle or square structure can effectively avoid microorganism or its
He is detained at object.
The reverse osmosis membrane of stable against biological contamination provided in an embodiment of the present invention, reverse osmosis membrane functional film layer is designed to nano level
Overshooting shape structure, due to changing reverse osmosis membrane surface microstructure so that the microorganism such as bacterium and micro-impurities are difficult to attached
In film surface, play a part of stable against biological contamination, and due to being the change of film layer physical form, will not because of using when
Between length and disappear such that it is able to effectively extend reverse osmosis membrane service life.
Correspondingly, the present invention is on the basis of the reverse osmosis membrane for providing stable against biological contamination, it is further provided the antibiont
A kind of preparation method of the reverse osmosis membrane of pollution.
In one embodiment, the preparation method of the reverse osmosis membrane of the stable against biological contamination, at least comprises the following steps：
Step S01. provide with the template of raised structures, the poly-vinyl alcohol solution that mass fraction is 0.2%～1.0%,
Mass fraction is 8%～15% curing agent solution and compact film；
The poly-vinyl alcohol solution is coated on the surface of the compact film one by step S02., controls thicknesses of layers for 2 μm
～5 μm；
Step S03. immerses the film layer that the coating of step S02 is obtained in the curing agent solution, right after standing 20～40s
The film layer is dried process, obtains the membrane structure containing polyvinyl alcohol film layer；
Step S04. releasing agent is sprayed at after the template with raised structures, is imprinted in the polyvinyl alcohol film layer
Surface, heated cross-linking reaction simultaneously carries out separating treatment with the template with raised structures, obtains the stable against biological contamination
Reverse osmosis membrane.
Wherein, the template with raised structures can adopt ready-made template, it is also possible to be made by following method.
In a preferred embodiment, the preparation method of the template with raised structures is as follows：
1) the high-purity aluminium flake of suitable size is taken, in the method, using 220mm (length) × 80mm (width) × 0.5mm
(thickness), purity is 99.999% aluminium flake, and as template raw material are processed；
2) above-mentioned aluminium flake is cleaned repeatedly using ethanol and acetone, surface liquid is dried up in nitrogen, then in argon
Under gas shielded, in 500 DEG C 2h is made annealing treatment so that aluminium flake is recrystallized, and eliminate the internal stress of aluminium flake, rise gentle rate of temperature fall control
System is in 5 DEG C/min；
3) 5～10min is soaked in the aluminium flake after annealing being placed in into ethanol and acetone, then deionized water cleaning,
And cleaned aluminium flake is placed in into ultrasonic cleaning in the sodium hydroxide solution that mass fraction is 0.5%～1.5%, to remove aluminium flake
The oxide skin(coating) on surface；
4) by ethanol that volumetric concentration is 95% and 70% perchloric acid according to 5:1 volume ratio carries out mixing as throwing
Light liquid, by step 3) aluminium flake that obtains is processed by shot blasting, the voltage of polishing is 18V～20V, polishing time be 5min～
10min；
5) using the aluminium flake after polishing as anode, graphite as negative electrode, in the phosphoric acid Anodic Oxidation 40min of 0.1M
～80min, the voltage of oxidation processes is 190V～200V, and temperature is 18 DEG C～25 DEG C.
Aluminium flake is processed through above-mentioned preparation method, obtains the porous oxidation aluminum dipping form as shown in Figure of description 1,2
Plate, porous alumina formwork is made up of aluminium substrate 1 and aluminum oxide 2.
Wherein, the concrete size of the template that said method makes is adopted for, aperture d=100nm～500nm, pitch of holes L=
100nm～500nm；Hole depth is 100nm～1 μm.
In a preferred embodiment, in the poly-vinyl alcohol solution of step S01, the alcoholysis degree of polyvinyl alcohol is more than or equal to
99%, molecular weight is 11400～15000, and high alcoholysis degree is conducive to improving cross-linking reaction degree so that polyethylene coating is preferable
Be solidificated in aramid layer surface.The aqueous solution manufacturability of the polyvinyl alcohol between molecular weight 11400-15000 is good, by applying
Film machine is coated, and can form the polyethylene coating of homogeneous thickness.
Preferably, the curing agent in curing agent solution be citric acid, other curing agent can adopt ethanedioic acid, glyoxal,
Maleic acid etc..Certainly first-selection citric acid, mainly due to citric acid natural organic acids is belonged to, harmless.
Preferably, described compact film is polyamide compact film.
Preferably, in step S02, poly-vinyl alcohol solution is coated on by compact film surface using desk-top film applicator, is controlled
Rotating speed is 90r/min.
In step S03, the preferred natural air drying of mode of dried process, it is to avoid film layer occurs fold affects performance.
Releasing agent in step S04 is preferably perfluoro decyl trichlorosilane.Because perfluoro decyl trichlorosilane can compare
The complete demoulding so that micro-protuberance structure is not destroyed, is at utmost preserved in aramid layer surface.
The above-mentioned template with raised structures is imprinted when the polyvinyl alcohol film surface, preferred pressure be 3MPa～
6MPa, the imprint time is 10min～20min, under the pressure and imprint time, template can be caused to be pressed into polyvinyl alcohol
Film surface, is avoided that pressure wears polyvinyl alcohol film again.
After impressing process, the template with raised structures is placed in into 80 together with the compact film for being coated with polyvinyl alcohol～
Toast in 90 DEG C of environment, make polyvinyl alcohol and compact film crosslink reaction, cross-linking reaction time is 10～20min, from
And obtain the reverse osmosis membrane of stable against biological contamination.
Cross-linking reaction terminates, and naturally cools to room temperature, you can the template with raised structures is anti-with stable against biological contamination
Permeable membrane is separated, and thus, the reverse osmosis membrane of the stable against biological contamination as shown in Figure of description 3 is obtained, it can be seen from figure 3 that instead
Permeable membrane surface has micro-protuberance structure.
The preparation method of the reverse osmosis membrane of stable against biological contamination provided in an embodiment of the present invention, using physical means, changes anti-
The microstructure on permeable membrane surface, there is the method process is simple, the raised structures of preparation to be evenly distributed, antimicrobial attachment effect
The features such as fruit is good, the method is adapted to large-scale production surface and has bossed reverse osmosis membrane.
The reverse osmosis membrane of stable against biological contamination prepared by the embodiment of the present invention can apply in water treatment field.Specifically include
In can apply to the fields such as desalinization, bitter desalination, pharmacy, biotechnology, sewage disposal.
In order to better illustrate the reverse osmosis membrane of stable against biological contamination provided in an embodiment of the present invention, do below by embodiment
It is further to illustrate.
Embodiment 1
(1) mould with raised structures is made：
Using the high-purity aluminium flake (purity 99.999%) of 220mm × 80mm × 0.5mm (length × width x thickness) as making
The parent material of template.
With the cleaning repeatedly of ethanol and acetone, dry up in nitrogen.Under argon gas protection, the aluminium flake after cleaning is placed in
Anneal 2h at 500 DEG C, rises gentle rate of temperature fall and controls in 5 DEG C/min；
Aluminium flake after annealing soaks respectively 5min in ethanol and acetone, and then deionized water is rinsed.Then in quality
Fraction be 0.5% sodium hydroxide solution in be cleaned by ultrasonic 10min, remove the oxide layer of aluminum flake surface；
By ethanol that volumetric concentration is 95% and 70% perchloric acid with 5:1 volume ratio mixes as polishing fluid, in room
With 18V voltage electropolishing aluminium flake 5min under temperature；
Using the aluminium flake after polishing as anode, graphite processes 60min, oxygen as negative electrode in 0.1M phosphoric acid Anodic Oxidation
Change voltage and be controlled to 60V, temperature control is at 20 DEG C.
(2) polyvinyl alcohol functional film layer is coated on fine and close layer surface：
It is that polyvinyl alcohol that 99%, molecular weight is 11400 is dissolved in the water and is heated to 95 DEG C by alcoholysis degree, makes quality point
Number is 0.5% polyvinyl alcohol water solution；
With desk-top film applicator by the aqueous solution of above-mentioned polyvinyl alcohol be coated in polyamide densification layer surface, rotating speed 90r/min,
Coating layer thickness is controlled for 5 microns；
Polyamide compacted zone after coating is contacted into 30s with the aqueous citric acid solution that mass fraction is 10%, and in air
In air-dry 1min, remove unnecessary liquid.
(3) polyvinyl alcohol film surface forms micro-protuberance structure：
Releasing agent perfluoro decyl trichlorosilane is sprayed into the porous alumina formwork surface of step (1) making；With impressing
Machine is impressed into alumina formwork on the polyethylene coating after air-drying, and the pressure for controlling to imprint is 4MPa, keeps 10min；
Then, the aramid layer that surface is coated with polyvinyl alcohol is together heated in an oven 80 together with alumina formwork
DEG C, cross-linking reaction 10min at being maintained at 80 DEG C；
Reaction to be crosslinked terminates, and the polyamide compacted zone comprising polyvinyl alcohol film layer is cooled to after room temperature, with oxidation aluminum dipping form
Plate is separated, and obtains the reverse osmosis membrane with anti-stable against biological contamination, the micro-protuberance size of the reverse osmosis membrane of the stable against biological contamination：Directly
Footpath d=500nm, spacing L=160nm, 1 μm of hole depth.
Embodiment 2
Except the oxidation voltage in (1) the step of embodiment 1 is changed into 130V, other are same as Example 1；Obtain micro-protuberance
Size：Diameter d=500nm, spacing L=330nm, 1 μm of hole depth.
Embodiment 3
Except the oxidation voltage in (1) the step of embodiment 1 is changed into 210V, other are same as Example 1；Obtain micro-protuberance
Size：Diameter d=500nm, spacing L=550nm, 1 μm of hole depth.
Embodiment 4
(1) mould with raised structures is made：
Using the high-purity aluminium flake (purity 99.999%) of 220mm × 80mm × 0.5mm (length × width x thickness) as making
The parent material of template.
With the cleaning repeatedly of ethanol and acetone, dry up in nitrogen.Under argon gas protection, the aluminium flake after cleaning is at 500 DEG C
Lower annealing 2h, rises gentle rate of temperature fall and controls in 5 DEG C/min；
Aluminium flake after annealing soaks respectively 5min in ethanol and acetone, and then deionized water is rinsed.Then in quality
Fraction be 0.5% sodium hydroxide solution in be cleaned by ultrasonic 10min, remove the oxide layer of aluminum flake surface；
By 95% ethanol and 70% perchloric acid with 5:1 volume ratio mixes as polishing fluid, electric with 18V at room temperature
Piezoelectricity polishes aluminium flake 5min；
Using the aluminium flake after polishing as anode, graphite processes 90min, oxygen as negative electrode in 0.12M sulfuric acid Anodic Oxidation
Change voltage and be controlled to 60V, temperature control is at 20 DEG C.
(2) polyvinyl alcohol functional film layer is coated on fine and close layer surface：
It is that polyvinyl alcohol that 99%, molecular weight is 11400 is dissolved in the water and is heated to 95 DEG C by alcoholysis degree, makes quality point
Number is 0.5% polyvinyl alcohol water solution；
With desk-top film applicator by the aqueous solution of above-mentioned polyvinyl alcohol be coated in polyamide densification layer surface, rotating speed 90r/min,
Coating layer thickness is controlled for 5 microns；
Polyamide compacted zone after coating is contacted into 30s with the aqueous citric acid solution that mass fraction is 10%, and in air
In air-dry 1min, remove unnecessary liquid.
(3) polyvinyl alcohol film surface forms micro-protuberance structure：
Releasing agent perfluoro decyl trichlorosilane is sprayed into the porous alumina formwork surface of step (1) making；With impressing
Machine is impressed into alumina formwork on the polyethylene coating after air-drying, and the pressure for controlling to imprint is 4MPa, keeps 10min；
Then, the aramid layer that surface is coated with polyvinyl alcohol is together heated in an oven 80 together with alumina formwork
DEG C, cross-linking reaction 10min at being maintained at 80 DEG C；
Reaction to be crosslinked terminates, and the polyamide compacted zone comprising polyvinyl alcohol film layer is cooled to after room temperature, with oxidation aluminum dipping form
Plate is separated, and obtains the reverse osmosis membrane with anti-stable against biological contamination, the micro-protuberance size of the reverse osmosis membrane of the stable against biological contamination：Directly
Footpath d=150nm, spacing L=160nm, 1 μm of hole depth.
Embodiment 5
Except the oxidation voltage in (1) the step of embodiment 4 is changed into 130V, other are same as Example 4；Obtain micro-protuberance
Size：Diameter d=150nm, spacing L=330nm, 1 μm of hole depth.
Embodiment 6
Except the oxidation voltage in (1) the step of embodiment 4 is changed into 210V, other are same as Example 4；Obtain micro-protuberance
Size：Diameter d=150nm, spacing L=550nm, 1 μm of hole depth.
Comparative example 1
It is 99% by alcoholysis degree, molecular weight is that 11400 polyvinyl alcohol is dissolved in the water and is heated to 95 DEG C, makes quality point
Number is 0.5% polyvinyl alcohol water solution；
The aqueous solution of the polyvinyl alcohol of above-mentioned preparation is coated in into polyamide densification layer surface, rotating speed with desk-top film applicator
90r/min, controls coating layer thickness for 5 microns；
Polyamide compacted zone after coating is contacted into 30s with the aqueous citric acid solution that mass fraction is 10%, then in sky
1min is air-dried in gas, unnecessary liquid is removed；
The polyamide compacted zone that surface is coated with polyvinyl alcohol is heated into an oven 80 DEG C, cross-linking reaction 10 minutes.
The polyamide composite reverse osmosis membrane of polyvinyl alcohol must be coated with to surface.
In order to detect the performance of the diaphragm that embodiment 1～6 and comparative example 1 are obtained, every kind of diaphragm takes 5 and carries out antibiont
Pollution capacity is tested.
Stable against biological contamination aptitude tests
Diaphragm (embodiment 1～6 and comparative example 1) is immersed in into respectively E. coli broth (CFU=106/ ml) in,
37 DEG C are cultivated after 24) hour, the number of bacteria on observation analysis reverse osmosis membrane surface, and (each example takes 5 pieces of diaphragms and surveys acquired results
The mean value of examination) it is shown in Table 1.
The stable against biological contamination aptitude tests data of table 1
| Example is not | Micro-protuberance diameter/nm | Micro-protuberance spacing/nm | Number of bacteria/mm2 |
| Embodiment 1 | 500 | 160 | 37 |
| Embodiment 2 | 500 | 330 | 83 |
| Embodiment 3 | 500 | 550 | 431 |
| Embodiment 4 | 150 | 160 | 343 |
| Embodiment 5 | 150 | 330 | 816 |
| Embodiment 6 | 150 | 550 | 1729 |
| Comparative example 1 | N/A | N/A | 2161 |
The durability test of stable against biological contamination ability
Diaphragm (embodiment 1-6 and comparative example 1) is continuously run 48 hours on cross-current type diaphragm check-out console.Test condition
For the 2000ppmNaCl aqueous solution, 225psi operating pressures, 25 DEG C of temperature, pH=7.Then diaphragm is immersed in into Escherichia coli training
Nutrient solution (CFU=106/ ml) in, after cultivating 24 hours at 37 DEG C, the number of bacteria on observation analysis reverse osmosis membrane surface, gained knot
Really (each example takes the mean value of 5 pieces of Membrane probings) is shown in Table 2.
Table 2 uses stable against biological contamination aptitude tests data after 48 hours
As known from Table 1, after is made with raised structures on reverse osmosis membrane surface, bacterium can effectively be reduced in reverse osmosis membrane
The adhesion amount on surface.And work as the diameter (radial dimension) of projection in Nano grade, and when being smaller than 300nm, the attachment of bacterium
Measurer is greatly reduced.
As known from Table 2, after using 48 hours, the number of bacteria on the reverse osmosis membrane surface with surface micro-protuberance structure does not have
There is significant change, and the number of bacteria of conventional polyvinyl alcohol coating surface increased.The result shows that micro-protuberance structure has
There is durability, long-term anti-microbial property is better than conventional polyvinyl alcohol coating.
Presently preferred embodiments of the present invention is the foregoing is only, not to limit the present invention, all essences in the present invention
Any modification, equivalent or improvement made within god and principle etc., should be included within the scope of the present invention.
Claims (10)
1. a kind of reverse osmosis membrane of stable against biological contamination, it is characterised in that：The reverse osmosis membrane of the stable against biological contamination includes dense film
Layer, and crosslinking curing is in the functional film layer on the surface of the compact film one；The functional film layer is back to the compact film
There are nano level some projections on surface.
2. the reverse osmosis membrane of stable against biological contamination as claimed in claim 1, it is characterised in that：The cross-sectional area of the projection is 7
×103nm2～2 × 105nm2, the height of the projection is 100nm～1 μm；Spacing between the projection is 100nm～500nm.
3. the reverse osmosis membrane of stable against biological contamination as claimed in claim 1, it is characterised in that：The functional film layer is polyvinyl alcohol
Film layer, the thickness of the polyvinyl alcohol film layer is 2 μm～5 μm.
4. the reverse osmosis membrane of stable against biological contamination as claimed in claim 1, it is characterised in that：The compact film is polyamide
Layer.
5. the reverse osmosis membrane of the stable against biological contamination as described in any one of claim 1-2, it is characterised in that：The projection is cylinder
At least one in projection, conoid protuberance, denation or square protrusion.
6. a kind of preparation method of the reverse osmosis membrane of stable against biological contamination, at least comprises the following steps：
Step S01. provides template, the poly-vinyl alcohol solution that mass fraction is 0.2%～1.0%, quality with raised structures
Fraction is 8%～15% curing agent solution and compact film；
The poly-vinyl alcohol solution is coated on the surface of the compact film one by step S02., controls thicknesses of layers for 2 μm～5 μ
m；
Step S03. immerses the film layer that the coating of step S02 is obtained in the curing agent solution, after standing 20～40s, to described
Film layer is dried process, obtains the membrane structure containing polyvinyl alcohol film layer；
Step S04. is sprayed at after the template with raised structures using releasing agent, is imprinted in the polyvinyl alcohol film layer
Surface, heated cross-linking reaction simultaneously carries out separating treatment with the template with raised structures, obtains the stable against biological contamination
Reverse osmosis membrane.
7. the preparation method of the reverse osmosis membrane of stable against biological contamination as claimed in claim 6, it is characterised in that：The polyvinyl alcohol
Alcoholysis degree be more than or equal to 99%, molecular weight be 11400～15000；And/or the curing agent is citric acid, ethanedioic acid, horse
Any one in sour；And/or the compact film is polyamide film layer.
8. the preparation method of the reverse osmosis membrane of stable against biological contamination as claimed in claim 6, it is characterised in that：Step S03
Dried process mode be natural air drying.
9. the preparation method of the reverse osmosis membrane of stable against biological contamination as claimed in claim 6, it is characterised in that：The pressure of the impressing
Power is 3MPa～6MPa, and the imprint time is 10min～20min；And/or the releasing agent is perfluoro decyl trichlorosilane.
10. the preparation method of the reverse osmosis membrane of stable against biological contamination as claimed in claim 6, it is characterised in that：It is described with prominent
The mold tabs spacing for playing structure is 100nm～500nm；The hole depth that projection is formed is 100nm～1 μm；Projection it is a diameter of
100nm～500nm.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110449033A (en) * | 2019-08-27 | 2019-11-15 | 湖北中泉环保技术有限公司 | The cleaning method of ultrafiltration membrane surface organic sediment |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06218211A (en) * | 1992-12-03 | 1994-08-09 | Shinsei Denshi Kogyo:Kk | Electret filter |
| JPH09141071A (en) * | 1995-11-22 | 1997-06-03 | Toray Ind Inc | Laminated membrane, its production and method for using the same |
| CN101462024A (en) * | 2008-12-24 | 2009-06-24 | 北京时代沃顿科技有限公司 | Composite reverse osmosis membrane with high-intensity anti-pollution layer and preparation method thereof |
| JP2010000719A (en) * | 2008-06-20 | 2010-01-07 | Mitsubishi Rayon Co Ltd | Film-like replica mold, its manufacturing method, and manufacturing method of film product having fine uneven structure |
| CN102762287A (en) * | 2010-02-16 | 2012-10-31 | 日东电工株式会社 | Composite separation membrane and separation membrane element using same |
| CN102985600A (en) * | 2010-07-12 | 2013-03-20 | 麦克德米德影印有限公司 | Method of molding polymeric materials to impart a desired texture thereto |
| WO2015166725A1 (en) * | 2014-04-28 | 2015-11-05 | シャープ株式会社 | Filter having sterilizing activity, and container |
| JP2016034613A (en) * | 2014-08-01 | 2016-03-17 | 株式会社東芝 | Filter for filtration and treatment method |
| CN105633420A (en) * | 2014-11-03 | 2016-06-01 | 中国科学院大连化学物理研究所 | Method for preparing fuel cell thin film electrode by using nanoporous gold |
-
2016
- 2016-12-28 CN CN201611234599.0A patent/CN106621844A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06218211A (en) * | 1992-12-03 | 1994-08-09 | Shinsei Denshi Kogyo:Kk | Electret filter |
| JPH09141071A (en) * | 1995-11-22 | 1997-06-03 | Toray Ind Inc | Laminated membrane, its production and method for using the same |
| JP2010000719A (en) * | 2008-06-20 | 2010-01-07 | Mitsubishi Rayon Co Ltd | Film-like replica mold, its manufacturing method, and manufacturing method of film product having fine uneven structure |
| CN101462024A (en) * | 2008-12-24 | 2009-06-24 | 北京时代沃顿科技有限公司 | Composite reverse osmosis membrane with high-intensity anti-pollution layer and preparation method thereof |
| CN102762287A (en) * | 2010-02-16 | 2012-10-31 | 日东电工株式会社 | Composite separation membrane and separation membrane element using same |
| CN102985600A (en) * | 2010-07-12 | 2013-03-20 | 麦克德米德影印有限公司 | Method of molding polymeric materials to impart a desired texture thereto |
| WO2015166725A1 (en) * | 2014-04-28 | 2015-11-05 | シャープ株式会社 | Filter having sterilizing activity, and container |
| JP2016034613A (en) * | 2014-08-01 | 2016-03-17 | 株式会社東芝 | Filter for filtration and treatment method |
| CN105633420A (en) * | 2014-11-03 | 2016-06-01 | 中国科学院大连化学物理研究所 | Method for preparing fuel cell thin film electrode by using nanoporous gold |
Non-Patent Citations (1)
| Title |
|---|
| 朱健: "《微米纳米技术丛书·MEMS与微***系列 RF MEMS器件设计、加工和应用》", 31 December 2012 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110449033A (en) * | 2019-08-27 | 2019-11-15 | 湖北中泉环保技术有限公司 | The cleaning method of ultrafiltration membrane surface organic sediment |
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