CN110124541A - A kind of stable against biological contamination composite membrane and preparation method thereof that quinolone signal molecule inhibitor is modified - Google Patents
A kind of stable against biological contamination composite membrane and preparation method thereof that quinolone signal molecule inhibitor is modified Download PDFInfo
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- CN110124541A CN110124541A CN201910426944.8A CN201910426944A CN110124541A CN 110124541 A CN110124541 A CN 110124541A CN 201910426944 A CN201910426944 A CN 201910426944A CN 110124541 A CN110124541 A CN 110124541A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
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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
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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
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
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- 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
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
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- 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
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
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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
- B01D2325/30—Chemical resistance
Abstract
The invention discloses a kind of modified stable against biological contamination composite membranes and preparation method thereof of quinolone signal molecule inhibitor, belong to water treatment by membrane field.Include the following steps: that quinolone (PQS) signal sort and recognition methyl anthranilate (methyl anthranilate, MA) and nano material graphene oxide (GO) are prepared into stable nanocomposite GO/MA by dehydrating condensation effect first；Secondly, solvent, which is added, in GO/MA nanocomposite and Kynoar (PVDF) by blending method prepares casting solution；Recycle phase inversion, the modified composite membrane of preparation GO/MA-PVDF.It is tested by series of optimum, the compound membrane flux of GO/MA-PVDF prepared by the present invention significantly improves, and is 150L m‑2h‑ 1bar‑1；After the pollution experiment of 25h dynamic biological, the flux fall of modified GO/MA-PVDF composite membrane reduces 27% compared to the decline of pvdf membrane flux, and the biofilm components albumen and polyoses content of modified film surface reduce 67%, 39% respectively, cell quantity reduces 72%.Confirm that modified composite membrane has stable against biological contamination performance.
Description
Technical field
The present invention relates to a kind of modified stable against biological contamination composite membrane of quinolone (PQS) signal sort and recognition and its preparations
Method, more particularly, to a kind of preparation method of high-performance stable against biological contamination membrane for water treatment.The invention belongs to membrane technology water process
And the stable against biological contamination field of film.
Background technique
In recent years, membrane separation technique is widely used in drinking water and sewage treatment field.However cross-film caused by fouling membrane
Osmotic pressure increases, membrane flux and rejection decline, chemical cleaning frequency increase, and shortens the service life of film, increases operation
Cost, to limit the extensive use of membrane technology.Fouling membrane mainly includes inorganic pollution, organic contamination, colloid pollution and life
Object pollution.Wherein biological pollution is the most complicated, the most serious to the destructiveness of film, and pollution is also most difficult to control.Studies have shown that the greatest extent
Pipe can remove in water body 99% bacterium in pretreatment process, but later in the presence of nutriment, bacterium colony is remained to not
Disconnected to be proliferated and then form biomembrane, biological pollution is still inevitable.
With the progress of biotechnology, current research confirms quorum sensing (quorum sensing, QS) system of thallus
The group behavior of adjustable microorganism controls the formation and disintegration of biomembrane.Therefore, by adding signal sort and recognition,
Inhibit the quorum sensing of microorganism, it is possible to reduce or delay the formation of biomembrane, to maintain preferable film properties.Based on this kind
Biochemical method has the characteristics that efficient, low toxicity and can reduce thallus drug resistance.In intervention school-based, mostly
Number research controls the formation of biomembrane by control N- acyl homoserine lactones (AHL) signaling molecule.Recently, to environment
In generally existing microorganism pseudomonas aeruginosa research in find, quinolone (PQS) colony induction signaling molecule is in biology
It also plays a significant role in film forming process, and the research that membrane biological pollution is controlled using PQS system has also still been in step
Section.Therefore, by interfering PQS intervention school-based, composite membrane of the preparation with stable against biological contamination performance has important application
Prospect.
Methyl anthranilate (methyl anthranilate, MA) inhibits as a kind of effective PQS signaling molecule
Agent, structural property are stablized, and amino group is contained.The graphene oxide surface (GO) is rich in oxygen-containing functional group (hydroxyl, carboxyl, epoxy
Base), it can be covalently attached by condensation reaction with containing amino-compound.Therefore using GO as the carrier of immobilization MA, can prepare
Stable compound.In addition, the hydrophily of GO can increase film permeation flux, biggish specific surface area can increase the load of material
Amount, further increases the stable against biological contamination performance of film.Therefore, the present invention innovatively by PQS signal sort and recognition MA and receives
Rice material GO is in situ by way of blending to be implanted into PVDF, is prepared stable against biological contamination composite membrane, is promoted it in water treatment system
In application.
Summary of the invention
The purpose of the present invention is the biological pollution problems for film in existing membrane for water treatment system, are based on quorum sensing and life
The correlation that object film is formed innovatively will be in PQS inhibitor methyl anthranilate (MA) and nanometer by phase inversion
Between carrier GO be blended implantation pvdf membrane, prepare novel stable against biological contamination composite membrane.Specific steps are as follows:
The preparation of 1.GO/MA nanocomposite
GO ultrasonic disperse is obtained into uniform GO dispersion liquid in pure water.Then 1- (3- bis- is added in the dispersion liquid
Methylaminopropyl) -3- ethyl-carbodiimide hydrochloride (EDC) and MA, stir for 24 hours at room temperature, react GO and MA sufficiently.It will stir
Mixed liquor after mixing is centrifuged (8000-10000rad, 10min), discards supernatant, and repetitive operation 4 times.Finally by lower sediment thing
It is placed in 70 DEG C of baking ovens and is sufficiently dried for 24 hours, obtain nanocomposite GO/MA.
The preparation of 2 Modified Membranes
Pvdf membrane and Modified Membrane are prepared by phase inversion.PVDF casting solution group becomes PVDF powder, nano material and N,
N- dimethyl acetamide (DMAc) solvent.PVDF powder is dried in an oven, is continued PVDF powder and GO/ under stirring
MA is dissolved in DMAc solution.Casting solution stirring is for 24 hours until the powder of addition is completely dissolved.By its placement overnight to remove degassing
Bubble, after casting on non-woven fabrics and (being placed on glass plate) knifing for casting solution using automatic knifing machine, immediately by coating
Glass plate is immersed in coagulating bath, adjusts coagulation bath temperature.It falls off from glass plate to film, then blend film is immersed in pure water and is impregnated
More than for 24 hours, to remove remaining DMAc solvent.
The utility model has the advantages that
The advantages of quinolone signal molecule inhibitor and graphene oxide are modified composite membrane (GO/MA-PVDF) in the present invention
Be: graphene oxide is connected with methyl anthranilate by amido bond, active force compare common Van der Waals force or
Electrostatic adsorption force is stronger, in conjunction with stabilization, while can ensure that membrane flux；Colony induction signaling molecule inhibitor MA is added, it is suppressed that
The biofilm development of microorganism can reduce film surface EPS secretion, effectively improve the stable against biological contamination performance of membrane for water treatment system.
The film can be directly nested in existing film processing system equipment, not need to increase the structures such as dedicated dispensing pond, be saved
Investment.
Detailed description of the invention
Attached drawing 1 is the membrane flux variation diagram of pvdf membrane, GO-PVDF film, embodiment during biological pollution, and attached drawing 2 is
Pvdf membrane (A-1), GO-PVDF film (A-2), the laser confocal scanning of embodiment (A-3) film surface after biological pollution are aobvious
Micro mirror figure.
Specific embodiment
Below with reference to the embodiment of the present invention, clear, complete description, described reality are carried out to technical solution of the present invention
Applying example is only section Example of the invention.Based on the embodiments of the present invention, this field researcher do not make it is any
Other embodiments obtained, shall fall within the protection scope of the present invention under the premise of creative work.
Embodiment
(1) 50mg GO ultrasonic disperse is obtained into uniform GO dispersion liquid in 100mL pure water.
(2) 100 μ L EDC and 150 μ L MA are added in the dispersion liquid, stirs at room temperature for 24 hours, keeps GO and MA sufficiently anti-
It answers.
(3) mixed liquor after stirring is centrifuged (10000rad, 10min), discards supernatant.Repetitive operation 4 times.Finally will
Lower sediment thing is placed in 70 DEG C of baking ovens about for 24 hours to remove hydrone, and GO/MA nanocomposite is made.
(4) by (70 DEG C, for 24 hours) drying in an oven of PVDF powder, PVDF powder is dissolved under lasting stirring
Casting solution is prepared in dimethyl acetamide (DMAc) solution.Casting solution group becomes 20wt%PVDF and 80%DMAc.
By casting solution stirring for 24 hours until the powder of addition is completely dissolved under the conditions of (5) 20 DEG C.
(6) casting solution stirred evenly is stood overnight to remove bubble, uses automatic knifing machine (Elcometer
4340Motorized, Britain) it casting solution is cast in into supporting layer (is placed on glass plate) knifing (with a thickness of 200 μm).
(7) glass plate of coating is immersed in coagulating bath immediately, adjusts coagulation bath temperature.It is taken off from glass plate to film
It falls, then blend film is immersed in pure water at least for 24 hours, to remove remaining DMAc solvent, obtain PVDF original membrane.
(8) pvdf membrane prepared is carried out to biological pollution test in cross-flow filtration system, film is existed with ultrapure water
Operation is to flux stabilized under 0.1MPa pressure, and then progress biological pollution filtration experiment under the conditions of operating pressure 0.1MPa, right
Membrane flux is monitored on-line.After pollution, component analysis is carried out to film surface biomembrane.
Every test data such as table 1 of embodiment modified GO/MA-PVDF film and initial film PVDF, GO-PVDF.In table
As can be seen that GO/MA is added, the contact angle compared to pvdf membrane and the film that GO is added reduces, and Zeta negative potential increases, and illustrates to press down
The hydrophily and elecrtonegativity of the modified caudacoria of preparation MA increase, and membrane flux is improved compared to initial p VDF film.
Table 1
Fig. 1 be three kinds of PVDF, GO-PVDF, embodiment films during biological pollution film than permeation flux situation of change, by
It is found that after 25h biological pollution experiment, PVDF initial membrane flux has dropped 81%, GO-PVDF film (decline 73%) and compares figure
Pvdf membrane flux fall reduces 8%.GO slows down the biological pollution journey of film by effectively inactivating and removing microorganism
Degree.And embodiment influences formation and the matrix composition of biomembrane by inhibiting bacterial community induction system, mitigates film surface significantly
Biological pollution, flux depression 54% reduces 27% compared to PVDF initial film, inhibitory effect be much better than GO-PVDF film and
Pvdf membrane.The flux of embodiment and initial film reduces rapidly in initial 10h；Unlike variation during the late stages of developmet, embodiment
Flux decline tends to be steady, and two kinds of initial films are still in the trend drastically reduced, further illustrate MA action time in biology
The later stage of growth can significantly inhibit the amplification of biomembrane.
Table 2 discloses after biological pollution, and film surface biosphere extracellular polymeric (EPS, including albumen and polysaccharide) contains
Amount and cell quantity situation, compare initial film and embodiment significantly inhibits effect to the EPS content of biomembrane.Egg in embodiment
White concentration (150 μ g/mL) is lower by 67% than PVDF initial film (453 μ g/mL), and polysaccharide concentration (43 μ g/mL) is than PVDF initial film (70
μ g/mL) low 39%.And GO-PVDF initial film only reduces 18% protein content and 11% polyoses content compared to pvdf membrane.
Fig. 2 is the cell fluorescence situation of film surface, in conjunction with film surface cell quantity (table 2) it is found that GO-PVDF film surface cell number is reduced
45%, embodiment reduces 72% compared to pvdf membrane superficial cell quantity.Illustrate after inhibitor MA is added, compound GO/MA changes
Property film stable against biological contamination be much better than individual GO Modified Membrane and initial p VDF film, i.e., it is modified using signal sort and recognition MA
Pvdf membrane improves the stable against biological contamination performance of film.
Table 2
Claims (9)
1. a kind of preparation method of the modified stable against biological contamination composite membrane of quinolone signal molecule inhibitor, which is characterized in that packet
Include following steps:
(1) graphene oxide (GO) ultrasonic disperse is obtained into uniform GO dispersion liquid in pure water, then by 1- (3- diformazan ammonia
Base propyl) -3- ethyl-carbodiimide hydrochloride (EDC) and methyl anthranilate (MA) be added in dispersion liquid, and in room temperature
Under the conditions of be stirred until homogeneous, by after stirring mixed liquor be centrifugated, discard supernatant, lower sediment thing be finally placed in baking oven
In it is sufficiently dry, obtain nanocomposite GO/MA；
(2) PVDF powder is placed in baking oven and is dried, receive gained in the PVDF powder and step (1) of drying under stirring
Casting solution is prepared in the n,N-dimethylacetamide solvent (DMAc) that nano composite material GO/MA is successively dissolved in, it will be configured molten
Liquid is placed on magnetic stirring apparatus and is stirred until homogeneous；
(3) by uniform casting solution standing overnight, to remove bubble, casting solution cast in using automatic knifing machine be placed in it is smooth
Knifing is carried out on the non-woven fabrics of glass plate；
(4) glass plate of coating is soaked in deionized water immediately, carries out coagulating bath, it is to be filmed to fall off from glass plate,
Blend film is immersed in pure water, to remove remaining DMAc solvent, is transferred to after removal solvent spare in ultrapure water；
(5) using crossflow membrane filtration system for biological pollution experimental provision, pseudomonas aeruginosa is type strain, investigates preparation and changes
The stable against biological contamination performance of property composite membrane.
2. preparation method according to claim 1, it is characterised in that in step (1), inhibited using quinolone signal molecule
Agent MA and GO prepares nano antibacterial material by dehydrating condensation effect, and in 100mL pure water, GO dosage is 50mg, and MA is added
Amount is 150 μ L.
3. preparation method according to claim 1, it is characterised in that in step (1), lived using 25mg EDC to GO
Change, GO is promoted to react with MA, reaction temperature is 20 DEG C.
4. preparation method according to claim 1, it is characterised in that in step (1), centrifugal condition 10000rad,
10min。
5. preparation method according to claim 1, it is characterised in that in step (2), it is desirable that nanocomposite GO/MA and
PVDF powder is in anhydrous state, respectively dries the two in an oven, removes moisture removal, and oven temperature is 70 DEG C.
6. preparation method according to claim 1, it is characterised in that in step (2), using phase inversion, by antibacterial material
GO/MA and PVDF powder is mixed with composite membrane, and mixed process need to carry out under lasting stirring, and mixing temperature is 20 DEG C,
Solvent is DMAc, and being stirred the time is for 24 hours.
7. preparation method according to claim 1, it is characterised in that in step (2), the mass fraction of PVDF is respectively
20%.
8. preparation method according to claim 1, it is characterised in that in step (3), knifing is with a thickness of 200 μm.
9. preparation method according to claim 1, which is characterized in that it is modified super that a kind of signal sort and recognition MA has been made
Filter membrane, flux fall of the film in biological pollution experimentation reduce 27% more before modified.
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Cited By (4)
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| CN111298658A (en) * | 2020-03-03 | 2020-06-19 | 北华航天工业学院 | Method for controlling biological pollution of ultrafiltration membrane by using small molecular substances |
| CN112225361A (en) * | 2020-09-24 | 2021-01-15 | 北京金崇光药业有限公司 | Purified water for cleaning pseudo-ginseng powder and production process thereof |
| CN114191999A (en) * | 2021-11-08 | 2022-03-18 | 江苏大学 | Biological pollution resistance modification method for water treatment membrane material |
| CN114832642A (en) * | 2022-04-11 | 2022-08-02 | 贵州省材料产业技术研究院 | PVDF (polyvinylidene fluoride) antibacterial nanofiltration membrane for layer-by-layer self-assembly subject-object recognition and preparation method thereof |
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| CN114832642A (en) * | 2022-04-11 | 2022-08-02 | 贵州省材料产业技术研究院 | PVDF (polyvinylidene fluoride) antibacterial nanofiltration membrane for layer-by-layer self-assembly subject-object recognition and preparation method thereof |
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